WO2011102425A1 - Oxide sintered body, oxide mixture, manufacturing methods for same, and targets using same - Google Patents

Oxide sintered body, oxide mixture, manufacturing methods for same, and targets using same Download PDF

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Publication number
WO2011102425A1
WO2011102425A1 PCT/JP2011/053405 JP2011053405W WO2011102425A1 WO 2011102425 A1 WO2011102425 A1 WO 2011102425A1 JP 2011053405 W JP2011053405 W JP 2011053405W WO 2011102425 A1 WO2011102425 A1 WO 2011102425A1
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Prior art keywords
transparent conductive
oxide
resistance
titanium
zinc
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PCT/JP2011/053405
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French (fr)
Japanese (ja)
Inventor
邦彦 中田
岳 吉川
吉伸 中村
晶雄 鈴木
翔平 堀田
Original Assignee
住友化学株式会社
学校法人大阪産業大学
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Priority claimed from JP2010268610A external-priority patent/JP2011190528A/en
Application filed by 住友化学株式会社, 学校法人大阪産業大学 filed Critical 住友化学株式会社
Priority to CN2011800102349A priority Critical patent/CN102762518A/en
Priority to KR1020127024066A priority patent/KR20120129972A/en
Publication of WO2011102425A1 publication Critical patent/WO2011102425A1/en

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Definitions

  • the present invention relates to an oxide sintered body, an oxide mixture, a production method thereof, and a target using them.
  • Transparent conductive films that combine electrical conductivity and light transmission have been used as electrodes in solar cells, liquid crystal display elements, and other various light receiving elements, as well as automotive windows, heat ray reflective films for buildings, and antistatic properties. It is used in a wide range of applications, such as transparent anti-fogging elements for anti-fogging in membranes and frozen showcases.
  • a transparent conductive film having a low resistance and excellent conductivity is suitable for a solar cell, a liquid crystal display element such as a liquid crystal, organic electroluminescence, and inorganic electroluminescence, a touch panel, and the like.
  • the transparent conductive film for example, a tin oxide (SnO 2 ) -based thin film, a zinc oxide (ZnO) -based thin film, and an indium oxide (In 2 O 3 ) -based thin film are known.
  • tin oxide-based transparent conductive film those containing antimony as a dopant (ATO) and those containing fluorine as a dopant (FTO) are known, and as a zinc oxide-based transparent conductive film, Those containing aluminum as a dopant (AZO) and those containing gallium as a dopant (GZO) are known, and indium oxide-based transparent conductive films include those containing tin as a dopant (ITO; Indium Tin Oxide). It has been. Among them, the most industrially used is an indium oxide-based transparent conductive film, and in particular, an ITO film is widely used because of its low resistance and excellent conductivity.
  • the target used as a film raw material in these film formation methods is made of a solid containing a metal element constituting the film to be formed, and is a sintered body or a mixture of metal, metal oxide, metal nitride, metal carbide, etc. Body, and in some cases, a single crystal.
  • the target when an oxide film such as ITO is formed by sputtering, the target is generally an alloy target made of a metal element constituting the film (In—Sn alloy in the case of an ITO film), Alternatively, an oxide target (a sintered body or a mixture made of In—Sn—O in the case of an ITO film) obtained by sintering or mixing an oxide containing a metal element constituting the film is used.
  • an alloy target when an alloy target is used, all the oxygen in the formed film is supplied from the oxygen gas in the atmosphere, so the amount of oxygen gas in the atmosphere tends to fluctuate, and as a result, the oxygen in the atmosphere It may be difficult to keep the film formation rate depending on the amount of gas and the characteristics (specific resistance, transmittance) of the film obtained constant.
  • oxide targets that is, oxide sintered bodies or oxide mixtures
  • an indium oxide-based transparent conductive film such as an ITO film is expensive and may be depleted of resources because In (indium), which is an essential raw material, is a rare metal, and has toxicity and is harmful to the environment and the human body.
  • In (indium) which is an essential raw material
  • ITO film has toxicity and is harmful to the environment and the human body.
  • an industrially versatile transparent conductive film that can be substituted for an ITO film because it may adversely affect the film.
  • a zinc oxide-based transparent conductive film that can be industrially manufactured by a sputtering method has attracted attention, and research is being conducted to improve its conductive performance.
  • Non-patent Document 1 attempts have been made to dope ZnO with various dopants in order to increase conductivity, and the optimum doping amount and the lowest resistivity have been reported for each of the various dopants.
  • the optimum doping amount is 2 wt%, and the minimum resistivity at that time is 5.6 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the zinc oxide-based transparent conductive film has been improved to obtain a low resistance comparable to that of the ITO film at the laboratory level.
  • conventional zinc oxide-based transparent conductive films are excellent in terms of conductivity, but have the disadvantage of being inferior in chemical durability such as heat resistance, moisture resistance, and chemical resistance (alkali resistance, acid resistance).
  • the zinc oxide-based transparent conductive film has poor chemical resistance (acid resistance and alkali resistance) as described above, it is necessary to pattern the zinc oxide-based transparent conductive film in a desired shape (for example, an element) In the case of use for such applications, there is a problem that an appropriate wet etching solution does not exist and patterning cannot be performed satisfactorily.
  • zinc oxide has a very high dissolution rate in acids and alkalis, etching with an acid or alkali on a zinc oxide-based transparent conductive film results in a very high etching rate. (Specifically, it is 100 times or more compared with the ITO film) and it immediately dissolved, and a good pattern shape could not be obtained.
  • the tin oxide-based transparent conductive film has excellent chemical resistance (acid resistance and alkali resistance) and is stable against acids and alkalis.
  • patterning by etching cannot be performed. Therefore, the zinc oxide-based transparent conductive film and the tin oxide-based transparent conductive film have a drawback that they can only be used for applications that do not require patterning. Therefore, as a means for enabling patterning of a zinc oxide-based thin film, it has been proposed that a specific acid can be used as an etchant and a specific element can be doped to reduce the etching rate (Patent Document 1). .
  • etching a zinc oxide-based thin film doped with 6 at% of Ti in ZnO (where “at%” is the number of atoms of the additive element with respect to the total number of atoms of zinc and the additive element of 100)
  • An example of etching a zinc oxide thin film doped with 3 at% Ti is disclosed.
  • Patent Document 2 describes that the durability of a zinc oxide-based transparent conductive film is improved by adding titanium oxide (TiO 2 ) having extremely strong durability to zinc oxide.
  • Patent Document 2 since the Ti element as the tetravalent element is substituted and dissolved in the site in the crystal of the zinc element, which is the divalent element, the charge balance is greatly lost, and the crystal structure is distorted. Since it is large and causes ionic impurity scattering, it is difficult to develop sufficient conductivity.
  • JP 2008-159814 A Japanese Patent No. 4295811
  • a first object of the present invention is to provide an oxide sintered body and an oxide mixture suitable for obtaining a zinc oxide-based transparent conductive film having both excellent conductivity and chemical durability, and methods for producing the same. And a target using them.
  • the second object of the present invention is to provide a method for forming a zinc oxide-based transparent conductive film having both excellent conductivity and chemical durability, a zinc oxide-based transparent conductive film formed by this method, and this film. It is to provide a transparent conductive substrate provided.
  • a third problem of the present invention is a zinc oxide thin film that has a sufficiently low etching rate at the time of patterning, can control the etching rate easily and reliably, has a good pattern shape, and has high conductivity. It is to provide a patterning method capable of obtaining the above.
  • the oxide sintered body of the present invention is substantially composed of zinc, titanium, and oxygen, and the atomic ratio Ti / (Zn + Ti) of titanium to the total of zinc and titanium exceeds 0.02 and is 0.1 or less. It is.
  • the method for producing an oxide sintered body according to the present invention after molding a raw material powder containing the following (A) and / or (B), the obtained molded body is subjected to inert atmosphere, vacuum or reduction. This is a method of sintering at 600 ° C. to 1500 ° C. in an atmosphere.
  • the method for producing an oxide sintered body according to the present invention is as follows. After the raw material powder containing (A) and / or (B) is molded, the obtained molded body is sintered at 600 ° C. to 1500 ° C. in an air atmosphere or an oxidizing atmosphere, and then further vacuumed in an inert atmosphere. In this method, annealing is performed in a reducing atmosphere.
  • the oxide mixture of the present invention comprises zinc oxide and titanium oxide.
  • titanium with respect to the sum of zinc and titanium has an atomic ratio Ti / (Zn + Ti) of more than 0.02 and 0.1 or less.
  • the method for producing an oxide mixture according to the present invention is obtained by molding a raw material powder containing a mixed powder of titanium oxide powder and zinc oxide powder or a mixed powder of titanium oxide powder and zinc hydroxide powder. In this method, the body is annealed at 50 ° C. or higher and lower than 600 ° C. in an air atmosphere, an inert atmosphere, a vacuum or a reducing atmosphere.
  • the target of the present invention is a target obtained by processing the oxide sintered body or the oxide mixture.
  • the method for forming a zinc oxide-based transparent conductive film according to the present invention comprises zinc oxide selected from the group consisting of a pulse laser deposition method (PLD method), a sputtering method, an ion plating method, and an electron beam (EB) vapor deposition method.
  • a method of forming a transparent organic conductive film, which is substantially composed of zinc, titanium and oxygen, and the atomic ratio Ti / (Zn + Ti) of titanium to the total of zinc and titanium is more than 0.02 and not more than 0.1.
  • a target obtained by processing a certain oxide sintered body or oxide mixture is used.
  • the zinc oxide-based transparent conductive film of the present invention is a film formed by the method for forming the zinc oxide-based transparent conductive film.
  • the transparent conductive substrate of this invention is a board
  • the atomic ratio Ti / (Zn + Ti) of titanium with respect to the total of zinc and titanium is more than 0.02 and not more than 0.1
  • the second target of the present invention is a target obtained by processing a zinc oxide-based transparent conductive film forming material.
  • the second method for forming a zinc oxide-based transparent conductive film according to the present invention is the sputtering method, ion plating method, pulse laser deposition method (PLD method) or electron beam (EB) vapor deposition using the second target.
  • PLD method pulse laser deposition method
  • EB electron beam
  • a zinc oxide-based transparent conductive film is formed by a method.
  • the transparent conductive substrate of this invention is a board
  • the patterning method according to the present invention is a method of patterning by etching a zinc oxide thin film with an acid, wherein the zinc oxide thin film contains zinc oxide as a main component, and the number of titanium atoms relative to the total of zinc and titanium.
  • the ratio Ti / (Zn + Ti) is a thin film having a ratio exceeding 0.02 and not more than 0.1.
  • a zinc oxide-based transparent conductive film having excellent conductivity and chemical durability can be formed by sputtering, ion plating, PLD, or EB vapor deposition.
  • the transparent conductive film formed in this manner is extremely useful industrially because it has the advantage that it does not require toxic indium, which is a rare metal.
  • a zinc oxide-based transparent conductive film having a good pattern shape and high conductivity can be obtained.
  • the oxide sintered body of the present invention is a titanium-doped zinc oxide sintered body substantially composed of zinc, titanium, and oxygen.
  • substantially means that 99% or more of all atoms constituting the oxide sintered body are composed of zinc, titanium, or oxygen.
  • the atomic ratio Ti / (Zn + Ti) of titanium to the total of zinc and titanium is more than 0.02 and 0.1 or less.
  • the value of Ti / (Zn + Ti) is 0.02 or less, chemical durability such as chemical resistance of a film formed using an oxide sintered body as a target is insufficient, and oxide sintering is performed. Since it becomes difficult for the zinc titanate compound to be formed in the body, the strength of the sintered body is reduced, making it difficult to process the target.
  • the value of Ti / (Zn + Ti) exceeds 0.1, there is a high possibility that a titanium oxide crystal phase that is desired not to be included in the oxide sintered body is formed as described later.
  • the oxide sintered body of the present invention is preferably composed of a zinc oxide phase and a zinc titanate compound phase, or composed of a zinc titanate compound phase.
  • the oxide titanate contains a zinc titanate compound phase in this way, the strength of the sintered body itself increases, so cracks occur. It is hard to produce.
  • the zinc titanate compound include ZnTiO 3 and Zn 2 TiO 4 , those in which a titanium element is dissolved in these zinc sites, those in which oxygen deficiency is introduced, and those having a Zn / Ti ratio. Non-stoichiometric compositions slightly deviating from the compound are also included.
  • examples of zinc oxide include ZnO, a solution in which a titanium element is dissolved, a material in which oxygen deficiency is introduced, and a material having a non-stoichiometric composition due to zinc deficiency.
  • the zinc oxide phase usually has a wurtzite structure.
  • the oxide sintered body of the present invention does not substantially contain a titanium oxide crystal phase.
  • the oxide sintered body contains a crystal phase of titanium oxide, the resulting film may lack uniformity in physical properties such as specific resistance.
  • titanium oxide since the value of Ti / (Zn + Ti) described above is 0.1 or less, titanium oxide usually reacts completely with zinc oxide, and titanium oxide is contained in the oxide sintered body. A crystalline phase is unlikely to occur. Examples of the crystalline phase of titanium oxide include TiO 2 , Ti 2 O 3 , and TiO, as well as substances in which other elements such as Zn are dissolved in these crystals.
  • the oxide sintered body of the present invention contains at least one element selected from the group consisting of gallium, aluminum, tin, silicon, germanium, zirconium and hafnium (hereinafter sometimes referred to as “additive element”), Furthermore, it is preferable to contain.
  • additive element the specific resistance of the oxide sintered body itself can be reduced in addition to the specific resistance of the film formed using the oxide sintered body as a target.
  • the film formation rate during DC sputtering depends on the specific resistance of the oxide sintered body as a sputtering target, and the productivity during film formation is improved by lowering the specific resistance of the oxide sintered body itself. Can do.
  • the total content is 0.05% or less with respect to the total amount of all the metal elements which comprise oxide sinter by atomic ratio. If the content of the additive element exceeds 0.05%, the specific resistance of the film formed using the oxide sintered body as a target may increase.
  • the additive element may be present in the oxide sintered body in the form of an oxide, or may be present in a form substituted (solid solution) in the zinc site of the zinc oxide phase, or titanic acid.
  • the zinc compound phase may exist in a form substituted (solid solution) with titanium sites and / or zinc sites.
  • the oxide sintered body of the present invention may contain other elements such as indium, iridium, ruthenium, rhenium as impurities in addition to the essential elements and additive elements of zinc and titanium.
  • the total content of elements contained as impurities is preferably 0.5% or less in terms of atomic ratio with respect to the total amount of all metal elements constituting the oxide sintered body.
  • the specific resistance of the oxide sintered body of the present invention is preferably 5 k ⁇ ⁇ cm or less.
  • the deposition rate during direct current sputtering depends on the specific resistance of the oxide sintered body as a sputtering target. Therefore, if the specific resistance of the oxide sintered body exceeds 5 k ⁇ ⁇ cm, the direct current sputtering is stable. There is a risk that film formation cannot be performed.
  • the specific resistance of the oxide sintered body of the present invention is preferably as low as possible. Specifically, it should be 100 ⁇ ⁇ cm or less.
  • the oxide sintered body of the present invention is preferably obtained by a method for producing an oxide sintered body according to the present invention described later, but is not limited to those obtained by these production methods.
  • a combination of titanium metal and zinc oxide powder or zinc hydroxide powder, or a combination of titanium oxide and zinc metal may be obtained as a raw material powder.
  • the method for producing an oxide sintered body according to the present invention includes forming the raw material powder containing the following (A) and / or (B), and then sintering the obtained molded body, This is a method for obtaining an oxide sintered body.
  • the raw material powder may be a mixed powder of titanium oxide powder and zinc oxide powder, a mixed powder of titanium oxide powder and zinc hydroxide powder, or a powder containing zinc titanate compound powder. It may be a mixed powder of zinc powder and zinc titanate compound powder or a mixed powder of titanium oxide powder, zinc hydroxide powder and zinc titanate compound powder. It is preferable to include a mixed powder of titanium oxide powder and zinc oxide powder or a mixed powder of titanium oxide powder and zinc hydroxide powder.
  • the oxide sintered body of the present invention is In that case, titanium or zinc metal particles are likely to be present in the oxide sintered body, and when this is used as a target, the metal particles on the surface of the target melt during the film formation. There is a tendency that the composition of the obtained film and the composition of the target are largely different without being released.
  • titanium oxide powder titanium oxide (TiO 2 ) made of tetravalent titanium, titanium oxide (Ti 2 O 3 ) made of trivalent titanium, titanium oxide (TiO) made of divalent titanium, or the like is used.
  • Ti 2 O 3 powder it is preferable to use Ti 2 O 3 powder. Because the crystal structure of Ti 2 O 3 is trigonal and the zinc oxide mixed with it has a hexagonal wurtzite structure, the symmetry of the crystal structure is the same, and it is replaced when solid-phase sintering is performed. It is because it can be considered that it dissolves easily.
  • the purity of the titanium oxide powder is preferably 99% by weight or more.
  • the ratio of the low-valent titanium oxide mixture can be controlled.
  • the structure of this low-valence titanium oxide can be confirmed by the results of instrumental analysis such as an X-ray diffraction apparatus (X-ray diffraction, XRD), an X-ray photoelectron spectrometer (X-ray Photoelectron Spectroscopy, XPS).
  • the zinc oxide powder a powder of ZnO or the like having a wurtzite structure is usually used, and a powder obtained by firing this ZnO in advance in a reducing atmosphere and containing oxygen deficiency may be used.
  • the purity of the zinc oxide powder is preferably 99% by weight or more.
  • the zinc hydroxide powder may be either amorphous or crystalline.
  • the zinc titanate compound powders of ZnTiO 3 , Zn 2 TiO 4 and the like can be used, and it is particularly preferable to use Zn 2 TiO 4 powder.
  • the average particle size of each compound (powder) used as the raw material powder is preferably 5 ⁇ m or less, and more preferably 1 ⁇ m or less.
  • the BET specific surface area of raw material powder is not specifically limited.
  • the mixing ratio of each powder is Ti / (Zn + Ti) in atomic ratio in the finally obtained oxide sintered body, depending on the type of compound (powder) used. What is necessary is just to set suitably so that a value may become said range. At that time, considering that zinc has a higher vapor pressure than titanium and is likely to be volatilized when sintered, the desired composition of the desired oxide sintered body (atomic ratio of Zn and Ti), It is preferable to set the mixing ratio in advance so that the amount of zinc increases.
  • the easiness of volatilization of zinc varies depending on the atmosphere during sintering.
  • the atmosphere during sintering For example, when zinc oxide powder is used, only the volatilization of zinc oxide powder itself occurs in an air atmosphere or an oxidizing atmosphere.
  • zinc oxide When sintered in a reducing atmosphere, zinc oxide is reduced, and it becomes easier to volatilize metal zinc than zinc oxide, so the amount of zinc lost increases (however, as described later, it is once sintered)
  • the amount of zinc to be increased with respect to the target composition may be set in consideration of the sintering atmosphere or the like.
  • each of the compounds (powder) used as the raw material powder may be only one kind, or two or more kinds may be used in combination.
  • the method for molding the raw material powder is not particularly limited, and for example, the raw material powder may be mixed and the obtained mixture may be molded.
  • the mixing can be performed using a known mixing method such as a ball mill, a vibration mill, an attritor, a dyno mill, or a dynamic mill.
  • the raw material powder and the aqueous solvent are mixed, and the obtained slurry is sufficiently mixed, then solid-liquid separated, dried and granulated, and the obtained granulated product may be formed.
  • the wet mixing may be performed by, for example, a wet ball mill using a hard ZrO 2 ball or a vibration mill, and the mixing time in the case of using a wet ball mill or a vibration mill is preferably about 12 to 78 hours.
  • raw material powder may be dry-mixed as it is, wet mixing is more preferable.
  • Known methods may be employed for solid-liquid separation, drying, and granulation.
  • the obtained granulated product is molded, for example, the granulated product is put into a mold and 1 ton using a cold forming machine such as a cold press or a cold isostatic press (CIP), a uniaxial press or the like. It can be formed by applying a pressure of / cm 2 or more.
  • a cold forming machine such as a cold press or a cold isostatic press (CIP), a uniaxial press or the like. It can be formed by applying a pressure of / cm 2 or more.
  • Sintering of the obtained compact is performed in an inert atmosphere (nitrogen, argon, helium, neon, etc.), vacuum, reducing atmosphere (carbon dioxide, hydrogen, ammonia, etc.), air atmosphere and oxidizing atmosphere (oxygen concentration is higher than air). High atmosphere) at 600 ° C. to 1500 ° C.
  • an annealing treatment in an inert atmosphere, a vacuum, or a reducing atmosphere applied after sintering in an air atmosphere or an oxidizing atmosphere causes oxygen deficiency in the oxide sintered body and lowers the specific resistance. To do. Therefore, even if sintering is performed in an inert atmosphere, a vacuum, or a reducing atmosphere, if it is desired to further reduce the specific resistance, it is preferable to perform annealing after the sintering.
  • the sintering temperature is preferably 600 ° C. to 1700 ° C., more preferably 600 ° C. to 1500 ° C., further preferably 1000 ° C. to 1500 ° C., and most preferably 1000 ° C. to 1300 ° C. And If the sintering temperature is lower than 600 ° C., the sintering does not proceed sufficiently, so that the target density is lowered. On the other hand, if it exceeds 1500 ° C., zinc oxide itself decomposes and disappears.
  • the rate of temperature increase is 5 ° C./min to 10 ° C./min up to 1000 ° C., and 1 ° C./min to 4 ° C. over 1000 ° C. to 1500 ° C. / Min is preferable in terms of making the sintered density uniform.
  • Sintering is performed, for example, by preventing the decomposition in a state where the molded body is buried in the ZnO powder, whereby the density of the obtained sintered body is preferably 80% or more, more preferably 90%. It is preferable to do.
  • a target composed of a high-density sintered body is preferable for reducing fine particles in the ablation plume, which may cause deterioration in film quality, that is, crystallinity and surface morphology, particularly in the case of the fs-PLD method. .
  • the sintering time (that is, the holding time at the sintering temperature) is preferably 0.5 to 48 hours, more preferably 3 to 15 hours.
  • Sintering is not particularly limited, and may be performed using an electric furnace, a gas furnace, a reduction furnace, or the like. Atmospheric pressure firing method, hot press method, hot isobaric press (HIP) method, discharge plasma Known methods such as a sintering (SPS) method and a cold isostatic pressing (CIP) method can be employed.
  • SPS sintering
  • CIP cold isostatic pressing
  • Examples of the atmosphere in performing the annealing treatment include an atmosphere made of at least one selected from the group consisting of nitrogen, argon, helium, carbon dioxide and hydrogen, and a vacuum.
  • a method of annealing treatment for example, a method of heating at normal pressure while introducing a non-oxidizing gas such as nitrogen, argon, helium, carbon dioxide, hydrogen, or a method of heating under vacuum (preferably 2 Pa or less)
  • the former method is advantageous from the viewpoint of production cost.
  • the annealing temperature is preferably 1000 ° C. to 1400 ° C., more preferably 1100 ° C. to 1300 ° C.
  • the annealing time is preferably 7 hours to 15 hours, more preferably 8 hours to 12 hours. If the annealing temperature is less than 1000 ° C., introduction of oxygen vacancies by annealing may be insufficient. On the other hand, when it exceeds 1400 ° C., zinc is likely to be volatilized, and the composition of the obtained oxide sintered body (atom ratio of Zn and Ti) may be different from a desired ratio.
  • the oxide mixture of the present invention comprises zinc oxide and titanium oxide. That is, the oxide mixture of the present invention is a mixture substantially consisting of zinc, titanium and oxygen. Here, “substantially” means that 99% or more of all atoms constituting the oxide mixture are composed of zinc, titanium, or oxygen.
  • the atomic ratio Ti / (Zn + Ti) of titanium to the total of zinc and titanium is more than 0.02 and 0.1 or less.
  • the above-described titanium oxide powder can be used.
  • Zinc oxide usually has a wurtzite structure.
  • the oxide mixture of the present invention is obtained by mixing zinc oxide powder and titanium oxide powder and molding the mixture, for example, uniaxial press molding. In order to increase the mechanical strength of the oxide mixture, the shaped oxide mixture may be heated below 600 ° C. If zinc oxide and titanium oxide are less than 600 ° C., they are not sintered to produce a composite oxide or the like.
  • Titanium (III) oxide is oxidized in an atmosphere containing oxygen (air atmosphere and oxidizing atmosphere) and heated to 400 ° C. or higher to change to titanium (IV) oxide.
  • the heating temperature is less than 600 ° C. in a reducing atmosphere and an inert atmosphere in which oxygen is not present, it can exist as a mixture without sintering.
  • the atmosphere contains oxygen (oxidizing atmosphere and air atmosphere), it is preferable to heat at less than 400 ° C. By heating in this way, the mechanical strength of the oxide mixture can be increased. Since the strength of the mixture itself increases, for example, even if a film is formed under severe conditions (high power, etc.) as a target, cracks are hardly generated.
  • the oxide mixture of the present invention may contain the above-described additive elements and impurities.
  • the contents of additive elements and impurities are as described above.
  • the method for producing the oxide mixture of the present invention comprises forming the mixed powder of titanium oxide powder and zinc oxide powder or the mixed powder of titanium oxide powder and zinc hydroxide powder, thereby forming the oxide mixture of the present invention. Is the way to get.
  • the raw material powder may be a mixed powder of titanium oxide powder and zinc oxide powder or a mixed powder of titanium oxide powder and zinc hydroxide powder. It is preferable to include a mixed powder of titanium oxide powder and zinc oxide powder or a mixed powder of titanium oxide powder and zinc hydroxide powder.
  • these titanium oxide powder, zinc oxide powder and zinc hydroxide powder those similar to the above-mentioned oxide sintered body can be used.
  • the mixing ratio of each powder depends on the type of compound (powder) used, What is necessary is just to set suitably so that the value of Ti / (Zn + Ti) may become the above-mentioned range by atomic ratio in the oxide mixture finally obtained.
  • the method for forming the raw material powder is not particularly limited, and is performed, for example, by the same method as that for the oxide sintered body.
  • the obtained molded body is heated and annealed to increase the mechanical strength.
  • Annealing is performed by a known method such as an atmospheric annealing method, a hot press method, an HIP method, an SPS method, or a CIP method.
  • an atmosphere for example, nitrogen, argon, helium, carbon dioxide, vacuum (preferably 2 Pa or less), hydrogen, etc.
  • an air atmosphere such as an air atmosphere, an inert atmosphere, a vacuum, a reducing atmosphere, or an oxidizing atmosphere (oxygen concentration higher than air) (Atmosphere) is performed at 50 ° C or higher and lower than 600 ° C.
  • an oxidizing atmosphere oxygen concentration higher than air
  • annealing is advantageously performed at normal pressure.
  • the annealing time (that is, the holding time at the annealing temperature) is preferably 1 hour to 15 hours. If the annealing time is less than 1 hour, the mechanical strength is not sufficiently improved.
  • the target of the present invention is a target used for film formation by, for example, a pulse laser deposition method (PLD method), a sputtering method, an ion plating method, or an electron beam (EB) evaporation method.
  • PLD method pulse laser deposition method
  • sputtering method a sputtering method
  • ion plating method a ion plating method
  • EB electron beam
  • the solid material used at the time of such film-forming may be called a "tablet”, in this invention, these are described as a "target.”
  • a general film forming method such as another vacuum film forming method such as a vacuum vapor deposition method, a chemical vapor deposition method, a mist CVD method, or a sol-gel method.
  • the target of the present invention is obtained by processing the above-described oxide sintered body or oxide mixture of the present invention into a predetermined shape and predetermined dimensions.
  • a processing method in particular is not restrict
  • the surface of the oxide sintered body or the oxide mixture is subjected to surface grinding and the like, then cut to a predetermined size, and then attached to a support base, whereby the target of the present invention can be obtained.
  • a plurality of oxide sintered bodies or oxide mixtures may be divided into divided shapes to form a large area target (composite target).
  • PLD method Pulse laser deposition method
  • the PLD method can be adopted as the method for forming the zinc oxide-based transparent conductive film of the present invention.
  • the specific method and conditions are not particularly limited except that the above-described target (film forming material) is used, and known methods and conditions may be appropriately employed.
  • PLD method is demonstrated, it is not limited to these.
  • a pulse laser beam is focused on a film forming material such as a target, and the film forming material (a mixture of titanium oxide and zinc oxide) on the surface of the target is obtained by the high power density of the focused laser pulse.
  • the film forming material a mixture of titanium oxide and zinc oxide
  • both the target and the substrate are installed in a high vacuum chamber, and their operations are controlled by a feedthrough mechanism.
  • the most widely used pulse laser source in the PLD method is an excimer laser.
  • the excimer laser has a pulse width of several nanoseconds (ns) and a wavelength in the UV region. Its typical fluence (energy range density) is a few J / cm 2 for a typical 10 mm 2 focused spot.
  • the nanosecond laser PLD method generates large droplets having a size of several microns, and is not suitable for a wide range of industrial nanosecond PLDs. Therefore, it is preferable to use a femtosecond laser or a similar ultrashort pulse laser as an ablation energy source (pulse laser source) used in the PLD method.
  • femtosecond to picosecond laser pulses have a much higher peak power due to their ultrashort pulse width, and the ablation mechanism is essentially that of nanosecond laser ablation.
  • the basic difference is that during the femtosecond pulse width, only negligible heat conduction occurs inside the target, so ablation basically occurs in an unmelted situation. Therefore, it is preferable to use the femtosecond PLD method (fs-PLD method) because a thin film in which no droplet is generated can be obtained.
  • the pulse width of the laser beam of the femtosecond pulse laser to be used is usually 10 fs to 1 ps, and the pulse energy is usually 2 ⁇ J to 100 mJ.
  • the beam is magnified 10 times with a microscope, and then condensed on the target surface with a condenser lens. By condensing this small, the fluence (energy density) at the focused spot can be changed to a maximum of 250 J / cm 2 with a spot size of 400 ⁇ m 2 .
  • the ablation threshold of the film-forming material (Ti-containing ZnO) when using a femtosecond laser is the case for a nanosecond pulse laser Is relatively low.
  • a fluence higher than 1 J / cm 2 is sufficient to ablate the Ti-containing ZnO target and generate ablation plasma.
  • a high fluence of up to 5 J / cm 2 is preferred to reduce the number of particles in the plasma plume.
  • a transparent thin film can be deposited by pulse laser on a simple substrate, or a multilayer periodic structure can be deposited directly.
  • a pulse laser is incident from the back surface of the substrate and is focused on the target through the substrate, the film forming material ablated from the target adheres to the surface of the substrate facing the target.
  • the distance from the substrate to the target can be changed by translating the substrate relative to the target. If the substrate is away from the target, a large area thin film can be formed.
  • a fine pattern with the same size as the laser focused spot is formed on the substrate due to the short distance between the substrate and the target and the narrow angular distribution of the ablation plume at the base. can do.
  • a pattern structure for example, periodic lines, lattices, dots
  • a multilayer periodic dielectric structure can be deposited by alternately performing two deposition processes using different materials at each of a long distance and a short distance between the substrate and the target.
  • the substrate is mounted on a substrate heater that can be heated up to 900 ° C.
  • the substrate manipulator then applies lateral and rotational motion to the surface of the substrate, and the substrate manipulator can be used to adjust the distance between the substrate and the target.
  • the vacuum system is operated at a base pressure of 1.5 ⁇ 10 ⁇ 8 Torr by being evacuated by a turbo molecular pump.
  • different gases can be filled into the chamber from the inlet and outlet, for example, the chamber can be filled with 0.1-20 milliTorr of oxygen.
  • Laser ablation occurs when a laser beam is focused on the target surface.
  • the laser focused spot is fixed, while the disk-type target is rotated around its surface vertical axis to perform lateral translation back and forth along its surface. Do. This corresponds to scanning the laser beam across the target surface.
  • the angular velocity of rotation is usually about 1 rev / sec.
  • the translational velocity in the lateral direction is usually about 0.3 mm / second, and the fluence is usually about 20 J / cm ⁇ 2 .
  • the pulse repetition frequency is kept at 1 kHz.
  • the substrate Before condensing the laser beam on the target surface, the substrate is heated to a maximum of 600 ° C. to release the gas, and then the substrate is treated with oxygen plasma for about 5 minutes to carbonize the substrate. It is preferable to remove the contamination due to hydrogen.
  • pre-ablation pre-ablation
  • the purpose of pre-ablation is to clean the target surface that is dirty during the manufacturing process. During pre-ablation, a shutter is inserted between the target and the substrate to protect the substrate surface.
  • a sputtering method may be employed as the method for forming the zinc oxide-based transparent conductive film of the present invention.
  • the specific method and conditions are not particularly limited except that the above-described film forming materials are used, and a known sputtering method and conditions may be appropriately employed.
  • Film formation by sputtering is performed, for example, by placing a target in a sputtering apparatus, introducing a sputtering gas into the apparatus, and applying a direct current (dc) or a high frequency (rf) electric field or performing sputtering.
  • dc direct current
  • rf high frequency
  • an inert gas for example, Ar
  • an oxidizing gas or a reducing gas can be used in combination.
  • oxygen it is preferable not to contain oxygen qualitatively, and the oxygen concentration is preferably less than 0.05%, for example.
  • the film formation conditions by the sputtering method are not particularly limited.
  • the pressure is usually 0.1 to 10 Pa
  • the substrate temperature is usually 25 to 300 ° C.
  • the method of sputtering is not particularly limited.
  • the sputtering method direct current sputtering method
  • the RF sputtering method high frequency sputtering method
  • the AC sputtering method alternating current sputtering method
  • the DC sputtering method has an advantage that the film forming speed is higher than other methods, the sputtering efficiency is excellent, and the DC sputtering apparatus is inexpensive, easy to control, and consumes less power.
  • these methods cannot be employed when the target is an insulator.
  • the RF sputtering method can be used even if the target is an insulator.
  • an ion plating method can be adopted as the method for forming the zinc oxide-based transparent conductive film of the present invention.
  • a film forming material evaporation material
  • the evaporation material is heated by irradiating, for example, argon plasma to the evaporation material.
  • argon plasma argon plasma
  • each particle of the vapor deposition material that has passed through the plasma is formed on a substrate placed at a position facing the hearth or the like.
  • the specific method and conditions of the ion plating method are not particularly limited except that the film forming material described above is used, and a known method and conditions of the ion plating method may be appropriately employed.
  • FIG. 1 shows an example of an ion plating apparatus suitable for performing the ion plating method.
  • the ion plating apparatus 10 includes a vacuum vessel 12 that is a film forming chamber, a plasma gun (plasma beam generator) 14 that is a plasma source that supplies a plasma beam PB into the vacuum vessel 12, and a bottom portion in the vacuum vessel 12.
  • An anode member 16 that is disposed and on which the plasma beam PB is incident is provided, and a transport mechanism 18 that appropriately moves a substrate holding member WH that holds a substrate W to be deposited above the anode member 16.
  • the plasma gun 14 is a pressure gradient type, and its main body is provided on the side wall of the vacuum vessel 12.
  • Reference numeral 20a indicates a carrier gas introduction path made of an inert gas such as Ar, which is the source of the plasma beam PB.
  • the anode member 16 includes a hearth 16a as a main anode for guiding the plasma beam PB downward, and an annular auxiliary anode 16b disposed around the hearth 16a.
  • the hearth 16a is controlled to an appropriate positive potential and sucks the plasma beam PB emitted from the plasma gun 14 downward.
  • a through hole TH is formed at a central portion where the plasma beam PB is incident, and a vapor deposition material 22 is loaded in the through hole TH.
  • the vapor deposition material 22 is a tablet formed into a columnar shape or a rod shape, and is heated and sublimated by an electric current from the plasma beam PB to generate a vapor deposition material.
  • the hearth 16a has a structure for gradually raising the vapor deposition material 22, and the upper end of the vapor deposition material 22 always protrudes from the through hole TH of the hearth 16a by a certain amount.
  • the auxiliary anode 16b is composed of an annular container arranged concentrically around the hearth 16a, and a permanent magnet 24a and a coil 24b are accommodated in the container.
  • the permanent magnet 24a and the coil 24b are magnetic field control members, and form a cusp-like magnetic field directly above the hearth 16a, whereby the direction of the plasma beam PB incident on the hearth 16a is controlled and corrected.
  • the transport mechanism 18 has a large number of rollers 18b arranged in the transport path 18a at equal intervals in the horizontal direction to support the substrate holding member WH, and rotates the rollers 18b to move the substrate holding member WH horizontally at a predetermined speed. And a drive device (not shown) to be moved.
  • the substrate W is held by the substrate holding member WH.
  • the substrate W may be fixedly disposed above the inside of the vacuum vessel 12 without providing the transport mechanism 18 for transporting the substrate W.
  • Reference numeral 20b indicates a supply path for supplying an atmospheric gas other than oxygen
  • reference numeral 20c indicates a supply path for supplying an inert gas such as Ar to the hearth 16a.
  • Reference numeral 20d denotes an exhaust system.
  • the vapor deposition material 22 is attached to the through hole TH of the hearth 16a disposed at the lower part of the vacuum vessel 12.
  • the substrate W is disposed at an opposing position above the hearth 16a.
  • a process gas corresponding to the film forming conditions is introduced into the vacuum vessel 12.
  • a DC voltage is applied between the cathode 14a of the plasma gun 14 and the hearth 16a.
  • a discharge is generated between the cathode 14a of the plasma gun 14 and the hearth 16a, thereby generating a plasma beam PB.
  • the plasma beam PB reaches the hearth 16a by being guided by a magnetic field determined by the steering coil 14 and the permanent magnet 24a in the auxiliary anode 16b. At this time, since argon gas is supplied around the steamed material 22, the plasma beam PB is easily attracted to the hearth 16a.
  • the vapor deposition material 22 exposed to the plasma is gradually heated.
  • the vapor deposition material 22 sublimates and the vapor deposition material evaporates (emits).
  • the vapor deposition material is ionized by the plasma beam PB, adheres (incides) to the substrate W, and is formed into a film.
  • the flight direction of the vapor deposition material can be controlled by controlling the magnetic field above the hearth 16a by the permanent magnet 24a and the coil 24b, the plasma activity distribution and the reactivity of the substrate W above the hearth 16a.
  • the film formation speed distribution on the substrate W can be adjusted in accordance with the distribution, and a thin film having a uniform film quality can be obtained over a wide area.
  • An electron beam (EB) vapor deposition method can be adopted as the method for forming the zinc oxide-based transparent conductive film of the present invention.
  • the specific method and conditions are not particularly limited except that the above-described film forming material is used, and a known electron beam (EB) vapor deposition method and conditions may be appropriately employed.
  • EB electron beam
  • a raw material target (tablet) is heated and evaporated by irradiating an electron beam in a vacuum, and this is deposited on an opposing transparent substrate for vapor deposition. Can be made on top.
  • the zinc oxide-based transparent conductive film of the present invention is a transparent conductive film made of titanium-doped zinc oxide formed by the above-described method for forming a zinc oxide-based transparent conductive film.
  • the atomic ratio (Ti / (Zn + Ti)) of titanium and zinc contained in the zinc oxide-based transparent conductive film of the present invention is as described above. As a result, the film can exhibit excellent conductivity due to the doping effect of titanium, and has excellent chemical durability.
  • titanium is substituted and dissolved in zinc sites of a zinc oxide wurtzite crystal structure.
  • the film thickness of the zinc oxide-based transparent conductive film of the present invention may be appropriately set according to the application, and is not particularly limited, but is preferably 50 nm to 600 nm, more preferably 100 nm to 500 nm. If the thickness is less than 50 nm, sufficient specific resistance may not be ensured. On the other hand, if the thickness exceeds 600 nm, the film may be colored.
  • the transparent conductive substrate of the present invention comprises the above-described zinc oxide-based transparent conductive film on a transparent base material.
  • the transparent substrate is not particularly limited as long as it can maintain the shape in various film forming methods.
  • inorganic materials such as various glasses, thermoplastic resins and thermosetting resins (for example, epoxy resin, polymethyl methacrylate, polycarbonate, polystyrene, polyethylene sulfide, polyethersulfone, polyolefin, polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose)
  • a plate-like material, a sheet-like material, a film-like material or the like formed of a resin such as a plastic such as polyimide can be used, and a glass plate, a resin film, or a resin sheet is particularly preferable.
  • the visible light transmittance of the transparent substrate is usually 90% or more, preferably 95% or more.
  • the roll-to-roll film formation method used in the industry is used. It is preferable to form a film in a state where a tensile stress is applied while being controlled. Further, the resin film or the resin sheet may be formed in a heated state in advance, or the resin film or the resin sheet may be cooled during the film formation. It is also effective to increase the speed of transporting the resin film or resin sheet (for example, at 1.0 m / min or more) in order to reduce the time for damage during film formation. Film formation is possible even if the distance between the target resin film or resin sheet and the target is short, which is advantageous as an industrial process.
  • the transparent base material may be formed with any of a single layer or multiple layers of an insulating layer, a semiconductor layer, a gas barrier layer, or a protective layer as required.
  • the insulating layer include a silicon oxide film and a silicon nitride oxide film.
  • the semiconductor layer include a thin film transistor (TFT), and the semiconductor layer is mainly formed on a glass substrate.
  • the gas barrier layer include a silicon oxide film, a silicon nitride oxide film, and a magnesium aluminate film, and the gas barrier layer is formed on a resin plate or a resin film as a water vapor barrier film.
  • a protective layer is for protecting the surface of a base material from a damage
  • one layer or two or more layers of inorganic compounds can be stacked.
  • the atomic ratio Ti / (Zn + Ti) of titanium with respect to the total of zinc and titanium is more than 0.02 and not more than 0.1, and the main component is zinc oxide. It consists of an oxide mixture or oxide sintered body containing at least one oxide of gallium and aluminum and titanium oxide.
  • the ratio of the number of atoms of gallium or aluminum is 0.5% or more and 6% or less with respect to the total number of metal atoms.
  • the ratio of the number of atoms of gallium or aluminum is less than 0.5%, the effect of improving conductivity is insufficient.
  • gallium or aluminum cannot be completely substituted and dissolved in the zinc site and is precipitated at the crystal grain boundary, resulting in a decrease in conductivity and a decrease in transmittance.
  • Both Al and Ga may be used. In that case, what is necessary is just to satisfy the above-mentioned conditions of 0.5% or more and 6% or less in the total amount thereof.
  • the oxide mixture or oxide sintered body As the manufacturing method of the oxide mixture or oxide sintered body here, the oxide mixture or oxidation described above is used except that a mixed powder further added with aluminum oxide powder or gallium oxide powder is used as the raw material powder. This is the same as the manufacturing method of the sintered product.
  • the ratio of the number of atoms of gallium or aluminum is 0.5% or more and 6% or less with respect to the total number of metal atoms.
  • the ratio of the number of atoms of gallium or aluminum is less than 0.5%, the effect of improving conductivity is insufficient.
  • gallium or aluminum cannot be completely substituted and dissolved in the zinc site and is precipitated at the crystal grain boundary, leading to a decrease in conductivity and a decrease in transmittance.
  • Both Al and Ga may be used. In that case, what is necessary is just to satisfy the above-mentioned conditions of 1% or more and 6% or less in the total amount thereof.
  • the oxide mixture and oxide sintered body are prepared by mixing zinc oxide powder, titanium oxide powder and aluminum oxide powder, or mixing zinc oxide powder, titanium oxide powder and gallium oxide powder, and press-molding. Is.
  • the titanium oxide powder is as described above, and trivalent titanium oxide (III) or divalent titanium oxide (II) is preferable.
  • the crystal phase of titanium oxide is specifically Ti 2 O 3 (III) and TiO (II).
  • the zinc oxide-based transparent conductive film-forming material of the present invention may contain the above-described additive elements (however, excluding gallium and aluminum) and impurities.
  • the contents of additive elements and impurities are as described above.
  • the specific resistance of the formed transparent conductive film is reduced, and the conductivity can be improved.
  • the content of the additive element exceeds 0.05%, the specific resistance of a film formed from the obtained zinc oxide-based transparent conductive film forming material may increase.
  • the additive element may be present in the oxide mixture or oxide sintered body in the form of an oxide, or is present in the form substituted (solid solution) in the zinc site of the zinc oxide phase. Alternatively, it may be present in a form substituted (solid solution) in the titanium site of the titanium oxide phase.
  • the oxide sintered body constituting the zinc oxide-based transparent conductive film forming material of the present invention preferably has a relative density of 93% or more, more preferably 95% to 100%.
  • the relative density is defined as the density of the oxide sintered body divided by the theoretical density and multiplied by 100. If the relative density is less than 93%, the characteristic of the sintered body, that is, the high film formation rate may be impaired.
  • the oxide mixture and the oxide sintered body are not particularly limited, and are manufactured by the above-described method, for example.
  • the zinc oxide-based transparent conductive film forming material of the present invention is processed into a target used for film formation by, for example, sputtering, ion plating, pulse laser deposition (PLD), or electron beam (EB) evaporation.
  • a zinc oxide-based transparent conductive film is formed using the processed target, and a transparent conductive substrate is obtained by forming the conductive film on the transparent substrate.
  • the zinc oxide thin film as described above is etched with an acid.
  • the etching solution that can be used in the present invention is not particularly limited as long as it contains an acid.
  • an etching solution used for patterning a conventional transparent conductive film such as an ITO film can be used.
  • the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrohalic acid (such as hydroiodic acid and hydrobromic acid), and mixtures thereof (such as aqua regia), Examples include organic acids such as oxalic acid, acetic acid, formic acid, propionic acid, succinic acid, malonic acid, butyric acid, citric acid.
  • Etching solutions containing these are usually used as (water) solutions dissolved in a suitable solvent.
  • the acid itself may be used.
  • various salts such as ammonium sulfate and ferric chloride can be dissolved in the etching solution. Only 1 type may be used for etching liquid and it may use 2 or more types together.
  • the concentration of the etching solution is not particularly limited, and may be set as appropriate according to the liquid temperature of the etching solution, the curing level of the film, and the like so as to obtain a desired etching rate.
  • the temperature of the etching solution is preferably 10 ° C. to 150 ° C., more preferably 20 ° C. to 100 ° C. If the temperature of the etching solution is less than 10 ° C., etching may not be possible. On the other hand, if the temperature exceeds 150 ° C., a solvent such as water tends to volatilize and it may be difficult to control the concentration of the etching solution. .
  • etching solution there is no particular limitation on the processing method when performing etching using the etching solution.
  • an appropriate solvent for example, methyl cellosolve acetate
  • the specific method and conditions for forming and removing the resist film and removing the exposed portion with the etching solution For example, in a wet etching process applied to a conventional transparent conductive film such as an ITO film. What is necessary is just to carry out suitably according to a method and conditions.
  • the thin film patterned according to the present invention has high conductivity.
  • the transparent conductive substrate obtained by forming and patterning the zinc oxide thin film on the transparent substrate has a specific resistance. Usually, it is 2 ⁇ 10 ⁇ 3 ⁇ ⁇ cm or less, preferably 1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm or less, more preferably 8 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less.
  • the surface resistance (sheet resistance) varies depending on the application, but is usually 5 to 10,000 ⁇ / ⁇ , preferably 10 to 300 ⁇ / ⁇ .
  • the thin film patterned by the present invention is usually excellent in transparency.
  • a transparent conductive substrate obtained by forming and patterning the zinc oxide thin film on the transparent base material is transparent.
  • the rate is usually 85% or more, preferably 90% or more in the visible light region.
  • the total light transmittance is preferably 80% or more, more preferably 85% or more, and the haze value is preferably 10% or less, more preferably 5% or less.
  • the transparent conductive film formed using the oxide sintered body or oxide mixture of the present invention or the target of the present invention has excellent conductivity and chemical durability (heat resistance, moisture resistance, chemical resistance (resistance to resistance).
  • the transparent conductive film formed using the oxide sintered body or oxide mixture of the present invention or the target of the present invention is used as a transparent radio wave absorber, an ultraviolet absorber, and a transparent semiconductor device as another metal. It can also be used in combination with a film or a metal oxide film.
  • the thin film patterned by the present invention is obtained by sufficiently controlling the etching rate, the formed pattern shape is accurate.
  • the heat resistance after the heat test is 1.5 times or less than the surface resistance before the heat test, it can be said that the heat resistance is excellent.
  • ⁇ Alkali resistance> The transparent conductive substrate was immersed in a 3% NaOH aqueous solution (40 ° C.) for 10 minutes, and the presence or absence of a change in film quality on the substrate before and after immersion was confirmed visually.
  • ⁇ Acid resistance> The transparent conductive substrate was immersed in a 3% HCl aqueous solution (40 ° C.) for 10 minutes, and the presence or absence of a change in film quality on the substrate before and after immersion was confirmed visually.
  • Example 1 ⁇ Production of oxide mixture> Zinc oxide powder (ZnO powder; purity 99.9%, average particle size 1 ⁇ m or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (Ti 2 O 3 powder; purity 99.9%, average particle size 1 ⁇ m or less) , Manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, these were put in a resin pot at a ratio of the atomic ratio of Zn: Ti of 94: 6 and wet mixed by a wet ball mill mixing method. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
  • the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
  • the obtained molded body was annealed by holding it in an air atmosphere at 300 ° C. for 1 hour to obtain an oxide mixture (1).
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • the crystal structure of the oxide mixture (1) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), the crystal phase of zinc oxide (ZnO) and titanium oxide (Ti 2 O 3 ) It was a mixture.
  • the obtained oxide mixture (1) is processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and a transparent conductive film is formed by sputtering using the sputtering target to produce a transparent conductive substrate.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 94: 6.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-).
  • EDX was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 5.8 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 11.6 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent conductive substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Example 2 ⁇ Production of oxide mixture> Zinc oxide powder (ZnO powder; purity 99.9%, average particle size 1 ⁇ m or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (Ti 2 O 3 powder; purity 99.9%, average particle size 1 ⁇ m or less) , Manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, these were put in a resin pot at a ratio of the atomic ratio of Zn: Ti of 95: 5 and wet mixed by a wet ball mill mixing method. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
  • the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
  • the obtained compact was annealed by holding it at 500 ° C. for 1 hour in an inert atmosphere (100% Ar atmosphere) to obtain an oxide mixture (2).
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • the obtained oxide mixture (2) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target.
  • a transparent film having a film thickness of 500 nm was formed by a sputtering method in the same manner as in Example 1.
  • a conductive film was formed to produce a transparent conductive substrate.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.9 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 9.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent conductive substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder ZnO powder; purity 99.9%, average particle size 1 ⁇ m or less, manufactured by Wako Pure Chemical Industries, Ltd.
  • titanium oxide powder Ti 2 O 3 powder; purity 99.9%, average particle size 1 ⁇ m or less (manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, these were put in a resin pot at a ratio of the Zn: Ti atomic number ratio of 99: 1, and wet mixed by a wet ball mill mixing method. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
  • the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
  • the obtained compact was annealed by holding it at 500 ° C. for 1 hour in an inert atmosphere (100% Ar atmosphere) to obtain an oxide mixture (C1).
  • an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation)
  • the obtained oxide mixture (C1) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a transparent conductive film was formed by sputtering in the same manner as in Example 1.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 1.2 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and the surface resistance was 24 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent conductive substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 70% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film which is transparent and has low resistance but inferior in chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). Is clear.
  • Example 3 Manufacture of oxide sinter>
  • the disk-shaped molded body obtained in the same manner as in Example 1 was heated up to 1000 ° C. at 5 ° C./min, over 1000 ° C. up to 1500 ° C. at 1 ° C./min, and sintered at the sintering temperature. Sintering was performed by holding at 1500 ° C. for 5 hours, and then annealing treatment was performed at 1300 ° C. for 5 hours in an inert atmosphere (100% Ar atmosphere) to obtain an oxide sintered body (3).
  • the obtained oxide sintered body (3) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a film thickness was formed on the substrate by sputtering as in Example 1.
  • a 500 nm transparent conductive film was formed.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 6.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 12.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Example 4 Manufacture of oxide sinter>
  • the disc-shaped molded body obtained in the same manner as in Example 2 was heated up to 1000 ° C. at 5 ° C./min, in excess of 1000 ° C. to 1300 ° C. at 1 ° C./min in an inert atmosphere (100% Ar atmosphere).
  • the oxide was sintered by being heated and held at a sintering temperature of 1300 ° C. for 5 hours to obtain an oxide sintered body (4).
  • the crystal structure of the oxide sintered body (4) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
  • the obtained oxide sintered body (4) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by a sputtering method in the same manner as in Example 1.
  • a transparent conductive film was formed to produce a transparent conductive substrate.
  • the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 5.8 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 11.6 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Comparative Example 2 Manufacture of oxide sinter>
  • the disc-shaped molded body obtained in the same manner as in Comparative Example 1 was heated in an inert atmosphere (100% Ar atmosphere) up to 1000 ° C. at 5 ° C./min, over 1000 ° C. to 1300 ° C. at 1 ° C./min.
  • the oxide was sintered by being heated and held at a sintering temperature of 1300 ° C. for 5 hours to obtain an oxide sintered body (C2).
  • the obtained oxide sintered body (C2) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by a sputtering method in the same manner as in Example 1.
  • a transparent conductive film was formed to produce a transparent conductive substrate.
  • the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 8.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 16 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 70% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film which is transparent and has low resistance but inferior in chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). Is clear.
  • Example 5 ⁇ Manufacture of oxide sinter (hot press method)> Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.), the element number ratio of zinc element to titanium element is 97.0: 3.0 Were weighed so as to be, put in a polypropylene container, and further 2 mm ⁇ zirconia balls and ethanol as a mixed solvent were added. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (5).
  • the crystal structure of the oxide sintered body (5) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
  • the obtained oxide sintered body (5) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by sputtering in the same manner as in Example 1.
  • a transparent conductive film was formed to produce a transparent conductive substrate.
  • the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Example 6 ⁇ Manufacture of oxide sinter (hot press method)> Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), titanium oxide (Ti 2 O 3 (III), manufactured by Kojundo Chemical Laboratory Co., Ltd.), the ratio of the number of elements of zinc element and titanium element is 97.0: It weighed so that it might be set to 3.0, it put into the container made from a polypropylene, and also ethanol was added as a 2 mm diameter zirconia ball
  • the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (6).
  • the obtained oxide sintered body (6) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by sputtering in the same manner as in Example 1.
  • a transparent conductive film was formed to produce a transparent conductive substrate.
  • the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • Example 7 ⁇ Manufacture of oxide sintered body (pressureless sintering method of TiO (II))> Zinc oxide powder (ZnO powder; purity 99.9%, average particle size 1 ⁇ m or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (TiO (II) powder; purity 99.9%, average particle size) 1 ⁇ m or less, manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, put them in a resin pot at a Zn: Ti atomic ratio of 97: 3, and wet-mixed by a wet ball mill mixing method did. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
  • the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
  • the obtained disk-shaped molded body was heated in an inert atmosphere (100% Ar atmosphere) up to 1000 ° C. at 5 ° C./min, over 1000 ° C. to 1300 ° C. at 1 ° C./min, and baked.
  • the oxide sintered body (7) was obtained by sintering by holding at 1300 ° C., which is a sintering temperature, for 5 hours.
  • the obtained oxide sintered body (7) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by sputtering in the same manner as in Example 1.
  • a transparent conductive film was formed to produce a transparent conductive substrate.
  • the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • the obtained disk-shaped molded body was heated in an inert atmosphere (100% Ar atmosphere) up to 1000 ° C. at 5 ° C./min, over 1000 ° C. to 1300 ° C. at 1 ° C./min, and baked.
  • the oxide sintered body (C3) was obtained by sintering at 1300 ° C. which is a sintering temperature for 5 hours.
  • the obtained oxide sintered body (C3) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by a sputtering method in the same manner as in Example 1.
  • a transparent conductive film was formed to produce a transparent conductive substrate.
  • the composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed using a calibration curve by the fluorescent X-ray method in the same manner as in Example 1.
  • Zn: Ti (atomic ratio) 88 : 12.
  • the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, and the surface resistance was 420.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 66% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film having both transparency and chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance), but high resistance. It is clear.
  • Example 8 ⁇ Manufacture of oxide sintered body (pressureless sintering method of TiO (II))> Zinc oxide powder (ZnO powder; purity 99.9%, average particle size 1 ⁇ m or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (TiO (II) powder; purity 99.9%, average particle size 1 ⁇ m or less) , Manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, these were put into a resin pot at a ratio of the Zn: Ti atomic ratio of 93: 7, and wet mixed by a wet ball mill mixing method. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
  • the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
  • the obtained disk-shaped molded body was heated in an inert atmosphere (100% Ar atmosphere) up to 1000 ° C. at 5 ° C./min, over 1000 ° C. to 1300 ° C. at 1 ° C./min, and baked.
  • the oxide sintered body (8) was obtained by sintering by holding at 1300 ° C., which is a sintering temperature, for 5 hours.
  • the obtained oxide sintered body (8) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by sputtering in the same manner as in Example 1.
  • a transparent conductive film was formed to produce a transparent conductive substrate.
  • the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 5.9 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 11.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Example 9 Manufacture of oxide sintered body (pressureless sintering method of TiO (II))> Zinc oxide powder (ZnO powder; purity 99.9%, average particle size 1 ⁇ m or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (TiO (II) powder; purity 99.9%, average particle size 1 ⁇ m or less) , Manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, these were put into a resin pot at a ratio of the atomic ratio of Zn: Ti of 91: 9, and wet mixed by a wet ball mill mixing method. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
  • the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
  • the obtained disk-shaped molded body was heated in an inert atmosphere (100% Ar atmosphere) up to 1000 ° C. at 5 ° C./min, over 1000 ° C. to 1300 ° C. at 1 ° C./min, and baked. Sintering was carried out by holding at 1300 ° C., which is a sintering temperature, for 5 hours to obtain an oxide sintered body (9).
  • the obtained oxide sintered body (9) was processed into a disk shape of 50 mm ⁇ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by sputtering in the same manner as in Example 1.
  • a transparent conductive film was formed to produce a transparent conductive substrate.
  • the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.2 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and the surface resistance was 44.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 65% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Example 10 Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was annealed at 400 ° C.
  • the obtained oxide mixture (10) was processed into a disk shape of 50 mm ⁇ to prepare a target, and a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive substrate.
  • a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive substrate.
  • the above-mentioned target and a transparent substrate quartz glass substrate
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • FE-SEM field structure electron microscope
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 5.1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 10.2 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.)
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • FE-SEM field structure electron microscope
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 14.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 88% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the acrylic transparent resin sheet before film formation averaged 93%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 93%.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm.
  • This molded body was first annealed at 500 ° C. for 3 hours in an atmospheric atmosphere of normal pressure (101.325 kPa) to obtain an oxide mixture (11).
  • the crystal structure of the oxide mixture (11) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), it was a mixture of crystal phases of zinc oxide (ZnO) and titanium oxide.
  • the obtained oxide mixture (11) was processed into a disk shape of 50 mm ⁇ to prepare a target, and a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive substrate. .
  • a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.)
  • Ar gas purity 99.9995% or more, Ar pure
  • 5N Ar gas
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • FE-SEM field structure electron microscope
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 8.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 16 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 62% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 800 ° C.
  • EDX-700L energy dispersive fluorescent X-ray apparatus
  • ZnO zinc oxide
  • Zn 2 TiO 4 zinc titanate
  • a target is prepared, and a transparent conductive film is formed by sputtering using this to obtain a transparent conductive substrate.
  • a transparent conductive film is formed by sputtering using this to obtain a transparent conductive substrate.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • FE-SEM field structure electron microscope
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing at a ratio of the Zn: Ti atomic ratio of 99: 1. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was annealed at 400 ° C.
  • oxide mixture (C4) was obtained by 3 hours in an argon atmosphere at normal pressure (101.325 kPa) to obtain an oxide mixture (C4).
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • the target was prepared by processing the obtained oxide mixture (C4) into a disk shape of 50 mm ⁇ , and a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive substrate.
  • a transparent conductive film quartz glass substrate
  • sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 100 W, and a substrate temperature of 130 ° C. to form a transparent conductive film having a thickness of 200 nm on the substrate.
  • the composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation).
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-).
  • EDX was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and the surface resistance was 125 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 70% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 2.6 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was inferior.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 2.0 times the surface resistance before the heat test, and the heat resistance was poor.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared after immersion.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared. From the above, the obtained film on the transparent conductive substrate is transparent, but has high resistance and poor chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that
  • the obtained oxide sintered body (C5) was processed into a shape of 4 inches ⁇ and 6 mmt, and bonded to an oxygen-free copper backing plate using indium solder to prepare a target. And using this target, the film-forming by sputtering method was performed on condition of the following, the transparent conductive film with a film thickness of 300 nm was formed on the transparent base material (quartz glass substrate), and the transparent conductive substrate was obtained.
  • the Al content in the formed film was 2.3% by weight.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.6 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 25.3 ⁇ / ⁇ .
  • the transmittance of the obtained transparent conductive substrate was an average of 88% in the visible region (380 nm to 780 nm) and an average of 55% in the infrared region (780 nm to 2700 nm).
  • the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 3.2 times the surface resistance before the moisture resistance test, and the moisture resistance was poor.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 7.0 times the surface resistance before the heat test, and it was found that the heat resistance was poor.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared after immersion.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared. From the above, the obtained film on the transparent conductive substrate is transparent and low resistance, but is a transparent conductive film inferior in chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 1000 ° C.
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • crystal structure of the oxide mixture (13) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), the crystal phase of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) And no titanium oxide was present.
  • the obtained oxide sintered body (13) is processed into a disk shape of 50 mm ⁇ to prepare a target, and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • the above-mentioned target and a transparent substrate quartz glass substrate
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • FE-SEM field structure electron microscope
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • a target is prepared, and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • FE-SEM field structure electron microscope
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • the obtained oxide sintered body (15) is processed into a disk shape of 50 mm ⁇ to prepare a target, and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • the above-mentioned target and a transparent substrate quartz glass substrate
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • FE-SEM field structure electron microscope
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 (III); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. These were mixed at a ratio of the Zn: Ti atomic ratio of 88:12 to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (C6).
  • ZnO manufactured by Wako Pure Chemical Industries, Ltd., special grade
  • titanium oxide powder Ti 2 O 3 (III); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. These were mixed at a ratio of the Zn: Ti atomic ratio of 88
  • the target oxide is produced by processing the obtained oxide sintered body (C6) into a disk shape of 50 mm ⁇ , and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation).
  • Zn: Ti atomic ratio
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-).
  • EDX was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc, but the crystallinity was lowered.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.2 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, and the surface resistance was 440 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 66% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the obtained film on the transparent conductive substrate is a transparent conductive film that is transparent and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that it is a resistance.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing the Zn: Ti at an atomic ratio of 88:12. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (C7).
  • EDX-700L energy dispersive fluorescent X-ray apparatus
  • the crystal structure of the oxide sintered body (C7) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
  • the target oxide is produced by processing the obtained oxide sintered body (C7) into a disk shape of 50 mm ⁇ , and a transparent conductive film is formed by sputtering using this to obtain a transparent conductive substrate.
  • a transparent conductive film quartz glass substrate
  • sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of 500 nm on the substrate.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation).
  • Zn: Ti atomic ratio
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-).
  • EDX was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc, but the crystallinity was lowered.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, and the surface resistance was 420 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 66% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the obtained film on the transparent conductive substrate is a transparent conductive film that is transparent and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that it is a resistance.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 (III); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. These were mixed at a ratio of the Zn: Ti atomic ratio of 93: 7 to obtain a raw material powder mixture. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (16) (hot pressing method).
  • the obtained oxide sintered body (16) is processed into a disk shape of 50 mm ⁇ to prepare a target, and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • the above-mentioned target and a transparent substrate quartz glass substrate
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-).
  • EDX was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 6.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 12.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing the Zn: Ti at an atomic ratio of 93: 7. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (17) (hot press method).
  • the crystal structure of the oxide sintered body (17) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
  • the target oxide is produced by processing the obtained oxide sintered body (17) into a disk shape of 50 mm ⁇ , and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was heated at 500 ° C.
  • the target was produced by processing the obtained oxide mixture (18) into a disk shape of 20 mm ⁇ , and a transparent conductive film was formed by using the PLD method to obtain a transparent conductive substrate.
  • a transparent conductive film was formed by using the PLD method to obtain a transparent conductive substrate.
  • the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 14.7 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Example 20 A target was produced by processing the oxide mixture (18) obtained in Example 19 into a disk shape of 20 mm ⁇ . Using this target, the transparent substrate (quartz glass substrate) in Example 19 was replaced with an acrylic transparent resin sheet (80 mm ⁇ 80 mm ⁇ 2 mmt flat plate), and the film formation conditions (Substrate Temperature) were changed as follows. In the same manner as in Example 19, a 300 nm-thick transparent conductive film was formed by the PLD method with a film formation time of 120 minutes.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4. Further, this transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 19, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis-oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 6.3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 21 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 65% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the resin sheet before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Example 21 Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was sintered at 800 ° C.
  • the obtained oxide sintered body (19) is processed into a disk shape of 20 mm ⁇ to produce a target, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate.
  • a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate.
  • PS-2000 pulse laser deposition apparatus
  • the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 14.7 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing at a ratio of the Zn: Ti atomic ratio of 99: 1. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was heated at 400 ° C.
  • oxide mixture (C8) was obtained by 3 hours under an argon atmosphere at normal pressure (1.01325 ⁇ 10 2 kPa) to obtain an oxide mixture (C8).
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • the obtained oxide mixture (C8) was processed into a disk shape of 20 mm ⁇ to prepare a target, and using this, the PLD method was performed in a film formation time of 120 minutes in the same manner as in Example 19.
  • a transparent conductive film having a thickness of 320 nm was formed.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 99: 1.
  • this transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 19, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis-oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.34 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and the surface resistance was 73.2 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was 90% on average in the visible region (380 nm to 780 nm).
  • the transmittance in the visible region of the quartz glass substrate before film formation is the same as in Example 19.
  • the surface resistance after the moisture resistance test was 2.4 times the surface resistance before the moisture resistance test, and the moisture resistance was poor.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 2.2 times the surface resistance before the heat test, which is inferior in heat resistance.
  • the film on the transparent conductive substrate obtained is transparent, but has high resistance and poor conductivity, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that the transparent conductive film is inferior.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 800 ° C.
  • EDX-700L energy dispersive fluorescent X-ray apparatus
  • ZnO zinc oxide
  • Zn 2 TiO 4 zinc titanate
  • a target is prepared, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate. It was. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
  • PS-2000 pulse laser deposition apparatus
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 97: 3.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 14.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders, and these are Zn: Ti Were mixed at a ratio of 97: 3 to obtain a mixture of raw material powders. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 800 ° C.
  • EDX-700L energy dispersive fluorescent X-ray apparatus
  • ZnO zinc oxide
  • Zn 2 TiO 4 zinc titanate
  • a target is prepared, and a transparent conductive film is formed by using the PLD method to form a transparent conductive substrate. Obtained. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
  • PS-2000 pulse laser deposition apparatus
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 97: 3.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 13.3 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 (III); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. These were mixed in such a ratio that the Zn: Ti atomic ratio was 97: 3 to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (22) (hot press sintering).
  • a target is prepared, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate.
  • a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.)
  • the above target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( Using a “Comex 205 type” manufactured by Co., Ltd., a transparent conductive film having a film thickness of 300 nm was formed under the following film forming conditions with a film forming time of 120 minutes.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 97: 3.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 14.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture.
  • the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, and heat treatment at 1000 ° C. for 4 hours.
  • a disk-shaped oxide sintered body (23) (hot press sintering).
  • a target is prepared, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate. It was. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
  • PS-2000 pulse laser deposition apparatus
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 97: 3.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 13.3 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.7 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.3 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing the Zn: Ti at an atomic ratio of 93: 7. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (24) (hot press sintering).
  • a target is prepared, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate. It was. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
  • PS-2000 pulse laser deposition apparatus
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 93: 7.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 9.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 30.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 67% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.4 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing at a ratio of the Zn: Ti atomic ratio of 88:12. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (C9) (hot press sintering).
  • C9 hot press sintering
  • a target is prepared, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate. It was. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
  • PS-2000 pulse laser deposition apparatus
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 88:12.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 1.1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, and the surface resistance was 367.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was 90% on average in the visible region (380 nm to 780 nm) and 75% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the obtained film on the transparent conductive substrate is a transparent conductive film that is transparent and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that it is a resistance.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 (III); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. These were mixed at a ratio of the Zn: Ti atomic ratio of 88:12 to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (C10) (hot press sintering).
  • C10 hot press sintering
  • a target is prepared, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate. It was. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
  • PS-2000 pulse laser deposition apparatus
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 88:12.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.4 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, and the surface resistance was 800.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was 90% on average in the visible region (380 nm to 780 nm) and 75% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the obtained film on the transparent conductive substrate is a transparent conductive film that is transparent and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that it is a resistance.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was annealed at 500 ° C.
  • an oxide mixture 25.
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • a tablet is produced by processing the obtained oxide mixture (25) into a disk shape of 20 mm ⁇ , and a transparent conductive film is formed by ion plating using this to form a transparent conductive substrate. Obtained.
  • ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm).
  • a transparent substrate a non-alkali glass substrate having a thickness of 0.7 mm.
  • a 200 nm transparent conductive film was formed.
  • Preheating temperature of substrate before film formation 250 ° C.
  • Pressure during film formation 0.3 Pa
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-).
  • EDX was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 36.5 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing at a ratio of the Zn: Ti atomic ratio of 99: 1. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was annealed at 400 ° C.
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • ion plating is performed under the following conditions, and the film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm).
  • a transparent substrate a non-alkali glass substrate having a thickness of 0.7 mm.
  • a 150 nm transparent conductive film was formed.
  • Preheating temperature of substrate before film formation 250 ° C.
  • Pressure during film formation 0.3 Pa
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 99: 1.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-).
  • EDX was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.0 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and the surface resistance was 467 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 91% in the visible region (380 to 780 nm) and an average of 70% in the infrared region (780 to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the film on the transparent conductive substrate obtained is a transparent conductive film that is transparent but has high resistance and inferior chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-).
  • EDX was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 8.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 160 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 91% in the visible region (380 to 780 nm) and an average of 70% in the infrared region (780 to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the surface resistance after the moisture resistance test was 1.8 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.5 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is transparent and low resistance even when the film thickness is 100 nm or less, and has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that this is a transparent conductive film having both properties.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-).
  • EDX was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 8.5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 42.5 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 85% in the visible region (380 nm to 780 nm) and an average of 65% in the infrared region (780 nm to 2700 nm).
  • the transmittance of the heat-resistant transparent resin film before film formation in the visible region (380 nm to 780 nm) was 90% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 90% on average.
  • the surface resistance after the moisture resistance test was 1.8 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.5 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is transparent and low resistance even when the substrate is a heat resistant film, and has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that this is a transparent conductive film having both properties.
  • Example 30 Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm.
  • This compact was sintered at 800 ° C.
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • ZnO zinc oxide
  • Zn 2 TiO 4 zinc titanate
  • the obtained oxide sintered body (26) is processed into a disk shape of 20 mm ⁇ to produce a tablet, and a transparent conductive film is formed by ion plating using the tablet, thereby forming a transparent conductive substrate.
  • a transparent conductive film is formed by ion plating using the tablet, thereby forming a transparent conductive substrate.
  • ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.)
  • ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm).
  • a 200 nm transparent conductive film was formed.
  • Preheating temperature of substrate before film formation 250 ° C.
  • Pressure during film formation 0.3 Pa
  • Atmospheric gas conditions during film formation: Argon 160 sccm
  • Oxygen 2 sccm
  • Discharge current during film formation 100 A Deposition time: 200 seconds
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.8 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 39.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders.
  • the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (27).
  • the crystal structure of the oxide sintered body (27) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
  • a tablet is produced, and a transparent conductive film is formed by ion plating using the tablet, thereby forming a transparent conductive substrate.
  • ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm).
  • a 200 nm transparent conductive film was formed.
  • Preheating temperature of substrate before film formation 250 ° C.
  • Pressure during film formation 0.3 Pa
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 36.5 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders, and these are Zn: Ti Were mixed at a ratio of 97: 3 to obtain a mixture of raw material powders.
  • the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped sintered body. Further, the sintered body was sintered at 800 ° C.
  • oxide sintered body 28
  • EDX-700L energy dispersive fluorescent X-ray apparatus
  • RINT2000 X-ray diffractometer
  • crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
  • the obtained oxide sintered body (28) is processed into a disk shape of 20 mm ⁇ to produce a tablet, and a transparent conductive film is formed by ion plating using the tablet, thereby forming a transparent conductive substrate.
  • a transparent conductive film is formed by ion plating using the tablet, thereby forming a transparent conductive substrate.
  • ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.)
  • ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm).
  • a 200 nm transparent conductive film was formed.
  • Preheating temperature of substrate before film formation 250 ° C.
  • Pressure during film formation 0.3 Pa
  • Atmospheric gas conditions during film formation: Argon 160 sccm
  • Oxygen 2 sccm
  • Discharge current during film formation 100 A Deposition time: 200 seconds
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 97: 3.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 6.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 30.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders, and these are Zn: Ti Were mixed at a ratio of 97: 3 to obtain a mixture of raw material powders. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 1000 ° C.
  • EDX-700L energy dispersive fluorescent X-ray apparatus
  • ZnO zinc oxide
  • Zn 2 TiO 4 zinc titanate
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 95: 5.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 6.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 30.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders, and these are Zn: Ti Were mixed at a ratio of 98.5: 1.5 to obtain a raw material powder mixture. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 1000 ° C.
  • oxide sintered body (C12) was obtained by 4 hours in an argon atmosphere at normal pressure (1.01325 ⁇ 10 2 kPa) to obtain an oxide sintered body (C12).
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • the crystal structure of the oxide sintered body (C12) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 98.5: 1.5.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 1.2 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and the surface resistance was 60.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 70% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the surface resistance after the moisture resistance test was 2.6 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was inferior.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 2.0 times the surface resistance before the heat test, and the heat resistance was poor.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared after immersion.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared. From the above, the film on the obtained transparent conductive substrate is transparent and low resistance, but is a transparent conductive film inferior in chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance) Is clear.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders, and these are Zn: Ti Were mixed at a ratio of 88:12 to obtain a mixture of raw material powders. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 1000 ° C.
  • oxide sintered body (C13) was obtained by 4 hours in an argon atmosphere at normal pressure (1.01325 ⁇ 10 2 kPa) to obtain an oxide sintered body (C13).
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • the crystal structure of this oxide sintered body (C13) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
  • the obtained oxide sintered body (C13) is processed into a disk shape of 20 mm ⁇ to produce a tablet, and a transparent conductive film is formed by ion plating using the tablet.
  • a transparent conductive film is formed by ion plating using the tablet.
  • ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.), ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm).
  • a 200 nm transparent conductive film was formed.
  • Preheating temperature of substrate before film formation 250 ° C.
  • Pressure during film formation 0.3 Pa
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 88:12.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.4 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, and the surface resistance was 1200.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was 90% on average in the visible region (380 nm to 780 nm) and 73% on average in the infrared region (780 nm to 2700 nm).
  • the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.1 times that before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
  • the obtained film on the transparent conductive substrate is a transparent conductive film that is transparent and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that it is a resistance.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 (III); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. These were mixed at a ratio of the Zn: Ti atomic ratio of 93: 7 to obtain a raw material powder mixture. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (30).
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 93: 7.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 1.1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and the surface resistance was 55.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 67% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing the Zn: Ti at an atomic ratio of 93: 7. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (31).
  • the obtained oxide sintered body (31) is processed into a disk shape of 20 mm ⁇ to produce a tablet, and a transparent conductive film is formed by ion plating using the tablet, thereby forming a transparent conductive substrate.
  • a transparent conductive film is formed by ion plating using the tablet, thereby forming a transparent conductive substrate.
  • ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.)
  • ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm).
  • a 200 nm transparent conductive film was formed.
  • Preheating temperature of substrate before film formation 250 ° C.
  • Pressure during film formation 0.3 Pa
  • the composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 93: 7.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM).
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 9.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 47.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 67% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
  • Example 36 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the element number ratio of zinc element, gallium element, and titanium element is 93.0: 2.0: 5.0, put it in a polypropylene container, and then add ethanol as a 2mm ⁇ zirconia ball and mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • Relative density 100 ⁇ [(density of sintered body) / (theoretical density)]
  • theoretical density (Zinc oxide simple substance density ⁇ mixing weight ratio + gallium oxide simple substance density ⁇ mixing weight ratio + titanium oxide simple substance density ⁇ mixing weight ratio)
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. 0.7 ⁇ 10 ⁇ 4 ⁇ cm.
  • the surface resistance was 9.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put in an electric furnace and heat-treated at 300 ° C. in an air atmosphere to obtain an oxide mixture. The obtained oxide mixture was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Sputtering device "E-200S” manufactured by Canon Anelva Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 ⁇ 10 ⁇ 4 Pa Ar pressure: 0.5 Pa
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. 0.6 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. The surface resistance was 9.2 ⁇ / ⁇ . The specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 57% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • the obtained sintered body was processed into a shape of 4 inches ⁇ and 6 mm thick, and bonded to an oxygen-free copper backing plate using indium solder to prepare a target. And using this target, the film-forming by sputtering method was performed on the following conditions, the transparent conductive film with a film thickness of 500 nm was formed on the transparent base material (quartz glass substrate), and the transparent conductive substrate was obtained.
  • the Al content in the formed film was 2.3% by weight.
  • Sputtering equipment Canon Anelva “E-200S” Sputtering method: DC magnetron sputtering Magnetic field strength: 1000 Gauss (directly above the target, horizontal component)
  • the specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.4 ⁇ / ⁇ .
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 50% in the infrared region (780 nm to 2700 nm).
  • the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 2.1 times the surface resistance before the moisture resistance test, and the moisture resistance was poor.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 2.0 times the surface resistance before the heat test, and the heat resistance was poor.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared after immersion.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared.
  • Example 38 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, gallium element, and titanium element is 96.5: 0.5: 3.0, put in a polypropylene container, and then add 2mm ⁇ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put in an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 96.8% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 36. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. The surface resistance was 8.2 ⁇ / ⁇ . The specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 39 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, gallium element and titanium element is 94.5: 0.5: 5.0, put in a polypropylene container, and then add 2mm ⁇ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body.
  • the relative density of the sintered body was calculated from the size of the sintered body, it was 94.6%.
  • the relative density is obtained in the same manner as in Example 36.
  • the obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. 0.6 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 9.2 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 40 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, gallium element and titanium element is 92.5: 0.5: 7.0, put in a polypropylene container, and then add 2mm ⁇ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 93.9% when the relative density of this sintered compact was computed from the size of a sintered compact. The relative density is obtained in the same manner as in Example 36. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. The surface resistance was 11.0 ⁇ / ⁇ . The specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 41 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, gallium element and titanium element is 96.5: 0.5: 3.0, put in a polypropylene container, and then add 2mm ⁇ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 96.7% when the relative density of this sintered compact was computed from the size of a sintered compact. The relative density is obtained in the same manner as in Example 36. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 9 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 7.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 42 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, gallium element and titanium element is 94.5: 0.5: 5.0, put in a polypropylene container, and then add 2mm ⁇ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 94.5% when the relative density of this sintered compact was computed from the size of a sintered compact. The relative density is obtained in the same manner as in Example 36. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor. 4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 8.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 43 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, gallium element and titanium element is 92.5: 0.5: 7.0, put in a polypropylene container, and then add 2mm ⁇ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body.
  • the relative density of the sintered body was calculated from the size of the sintered body, it was 94.0%.
  • the relative density is obtained in the same manner as in Example 36.
  • the obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. The surface resistance was 10.6 ⁇ / ⁇ . The specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 44 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.)
  • a mixture of raw material powders was obtained by weighing so that the element number ratio of zinc element, gallium element and titanium element was 96.5: 0.5: 3.0.
  • the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 9 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 7.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 45 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.)
  • a mixture of raw material powders was obtained by weighing so that the element number ratio of zinc element, gallium element and titanium element was 94.5: 0.5: 5.0.
  • the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours.
  • the relative density of the sintered body was calculated from the size of the sintered body and found to be 95.6%. The relative density is obtained in the same manner as in Example 36. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor. 4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 8.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 46 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the element number ratio of zinc element, aluminum element and titanium element is 96.5: 0.5: 3.0, put it in a polypropylene container, and then add ethanol as a 2mm ⁇ zirconia ball and mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 96.9% when the relative density of this sintered compact was computed from the size of the sintered compact.
  • the relative density is obtained from the following formula.
  • the obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • Relative density 100 ⁇ [(density of sintered body) / (theoretical density)]
  • theoretical density (Zinc oxide simple substance density ⁇ mixing weight ratio + Aluminum oxide simple substance density ⁇ mixing weight ratio + titanium oxide simple substance density ⁇ mixing weight ratio)
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. The surface resistance was 8.2 ⁇ / ⁇ . The specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 47 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, aluminum element and titanium element is 94.5: 0.5: 5.0, put it in a polypropylene container, and then add ethanol as a 2mm ⁇ zirconia ball and mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 94.8% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. 0.6 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 9.2 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 48 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, aluminum element and titanium element is 92.5: 0.5: 7.0, put in a polypropylene container, and then add 2mm ⁇ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 94.2% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. The surface resistance was 11.0 ⁇ / ⁇ . The specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 49 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the element number ratio of zinc element, aluminum element and titanium element is 96.5: 0.5: 3.0, put it in a polypropylene container, and then add ethanol as a 2mm ⁇ zirconia ball and mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 96.8% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 9 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 7.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 50 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, aluminum element and titanium element is 94.5: 0.5: 5.0, put it in a polypropylene container, and then add ethanol as a 2mm ⁇ zirconia ball and mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 94.7% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor. 4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 8.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 51 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, aluminum element and titanium element is 92.5: 0.5: 7.0, put in a polypropylene container, and then add 2mm ⁇ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 94.2% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. The surface resistance was 11.0 ⁇ / ⁇ . The specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 52 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.)
  • a mixture of raw material powders was obtained by weighing so that the element number ratio of zinc element, aluminum element and titanium element was 96.5: 0.5: 3.0.
  • the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped sintered body.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 9 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 7.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • Example 53 Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.)
  • a mixture of raw material powders was obtained by weighing so that the element number ratio of zinc element, aluminum element and titanium element was 94.5: 0.5: 5.0.
  • the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped sintered body.
  • the relative density of the sintered body was calculated from the size of the sintered body and found to be 95.8%. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Target size 50.8mm ⁇ 3mm thickness
  • Substrate temperature 250 ° C
  • Sputtering power 30W
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor. 4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the surface resistance was 8.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
  • the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body.
  • the relative density of the sintered body was calculated from the size of the sintered body, it was 93.0%.
  • the relative density is obtained in the same manner as in Example 46.
  • the obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
  • the obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
  • a film was formed by sputtering.
  • the sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
  • Substrate used Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
  • the obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
  • the transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
  • FE-SEM field emission electron microscope
  • the sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 2 ⁇ 10 ⁇ 3 ⁇ ⁇ cm. The surface resistance was 164 ⁇ / ⁇ . The specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 50% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the surface resistance after the moisture resistance test was 1.3 times the surface resistance before the moisture resistance test and was excellent in moisture resistance.
  • the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.3 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
  • the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent.
  • the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
  • the obtained film on the transparent conductive substrate is a transparent conductive film that has both chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance), alkali resistance, and acid resistance. Although it is a film, it has low near-infrared transmittance and high resistance.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by High Purity Chemicals Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • ZnO manufactured by Wako Pure Chemical Industries, Ltd., special grade
  • Ti 2 O 3 titanium oxide powder
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was annealed at 400 ° C.
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • RINT2000 X-ray diffractometer
  • a target is prepared by processing the obtained oxide mixture (32) into a disk shape of 50 mm ⁇ , and a zinc oxide-based thin film is formed by sputtering using the target to obtain a transparent conductive substrate.
  • the above-mentioned target and a transparent substrate quartz glass substrate
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 8.3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 16.6 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1% by mass citric acid aqueous solution at 30 ° C. for 60 seconds.
  • the film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.27 nm / second.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 800 ° C.
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • ZnO zinc oxide
  • Zn 2 TiO 4 zinc titanate
  • a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.)
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the zinc oxide thin film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM).
  • the specific resistance of the zinc oxide thin film on the obtained transparent conductive substrate was 4.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.8 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1% by mass citric acid aqueous solution at 30 ° C. for 60 seconds.
  • the film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.40 nm / second.
  • the etching rate is 0.5 nm / second or less, the level is sufficiently controllable.
  • this thin film is patterned using the citric acid aqueous solution as an etchant using a predetermined pattern mask, good etching is achieved. A pattern could be formed.
  • the etching rate can be easily controlled, and a conductive zinc oxide thin film pattern was obtained.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing at a ratio of the Zn: Ti atomic ratio of 99: 1. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was annealed at 400 ° C.
  • oxide mixture (C14) was obtained by 3 hours under an atmospheric pressure (0.1013 MPa) argon atmosphere to obtain an oxide mixture (C14).
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • the obtained oxide mixture (C14) is processed into a disk shape of 50 mm ⁇ to prepare a target, and a zinc oxide-based thin film is formed by sputtering using this to obtain a transparent conductive substrate.
  • the zinc oxide thin film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM).
  • the specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 2.25 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and the surface resistance was 112.5 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 70% on average in the infrared region (780 nm to 2700 nm).
  • this film it is difficult to control because the etching rate is 1.0 nm / second or more, and when this thin film is patterned using a citric acid aqueous solution similar to Example 1 as an etching solution using a mask of a predetermined pattern, It was difficult to form a good etching pattern.
  • a zinc oxide thin film doped with aluminum atoms was formed on soda lime glass (thickness 0.7 mm) by a direct current magnetron sputtering method using a zinc oxide sputtering target containing 2% by mass of aluminum oxide. Sputtering was performed at a power of 75 W during film formation, a film formation pressure of 0.5 Pa, an oxygen partial pressure of 0 Pa, a substrate temperature of room temperature, and a film formation time of 30 minutes.
  • Example 54 the etching rate of the formed thin film was examined and found to be 1.5 nm / second.
  • this film it is difficult to control because the etching rate is 1.0 nm / second or more, and when this thin film is patterned using a citric acid aqueous solution similar to Example 1 as an etching solution using a mask of a predetermined pattern, It was difficult to form a good etching pattern.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing at a ratio where the atomic ratio of Zn: Ti was 92: 8. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was annealed at 400 ° C.
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • the crystal structure of this oxide mixture (34) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), the crystal phase of zinc oxide (ZnO) and titanium oxide (Ti 2 O 3 ) It was a mixture.
  • a target is prepared by processing the obtained oxide mixture (34) into a disk shape of 50 mm ⁇ , and a zinc oxide-based thin film is formed by sputtering using this to obtain a transparent conductive substrate.
  • the above-mentioned target and a transparent substrate quartz glass substrate
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 7.6 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 15.2 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1% by mass citric acid aqueous solution at 30 ° C. for 60 seconds.
  • the film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.27 nm / second.
  • the etching rate is 0.5 nm / second or less, the level is sufficiently controllable.
  • this thin film is patterned using the citric acid aqueous solution as an etchant using a predetermined pattern mask, good etching is achieved. A pattern could be formed.
  • the etching rate can be easily controlled, and a conductive zinc oxide thin film pattern was obtained.
  • Example 57 Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 800 ° C.
  • a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.)
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the etching rate is 0.5 nm / second or less, the level is sufficiently controllable.
  • this thin film is patterned using the citric acid aqueous solution as an etchant using a predetermined pattern mask, good etching is achieved. A pattern could be formed.
  • the etching rate can be easily controlled, and a conductive zinc oxide thin film pattern was obtained.
  • Example 58 Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (36).
  • a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.)
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the zinc oxide thin film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM).
  • the specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1% by mass citric acid aqueous solution at 30 ° C. for 60 seconds.
  • the film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.40 nm / second.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • a mixture of raw material powders was obtained by mixing the Zn: Ti at an atomic ratio of 88:12. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (C15).
  • a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.)
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the zinc oxide thin film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM).
  • the specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 2.1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, and the surface resistance was 420.0 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1% by mass citric acid aqueous solution at 30 ° C. for 60 seconds.
  • the film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.16 nm / second.
  • the etching rate is 0.5 nm / second or less, the level is sufficiently controllable.
  • this thin film is patterned using the citric acid aqueous solution as an etchant using a predetermined pattern mask, good etching is achieved. A pattern could be formed.
  • the etching rate can be easily controlled, and a conductive zinc oxide thin film pattern was obtained. Although the etching rate was sufficiently controllable, the resistance was high.
  • Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders.
  • Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture.
  • the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (37).
  • a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.)
  • Ar gas purity 99.9995% or more, Ar pure
  • Gas 5N
  • the zinc oxide thin film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM).
  • the specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the surface resistance was 8.4 ⁇ / ⁇ .
  • the specific resistance distribution on the transparent substrate was uniform in the plane.
  • the transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm).
  • the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
  • the etching rate of the film was examined by measuring the rate of decrease in film thickness (nm / second) when the formed thin film was immersed in a 1 mol / l acetic acid aqueous solution at 20 ° C. for 120 seconds.
  • the film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.33 nm / second.
  • the etching rate is 0.5 nm / second or less, the level is sufficiently controllable.
  • this thin film is patterned using the citric acid aqueous solution as an etchant using a predetermined pattern mask, good etching is achieved. A pattern could be formed.
  • the etching rate can be easily controlled, and a conductive zinc oxide thin film pattern was obtained.
  • a zinc oxide thin film doped with aluminum atoms was formed on soda lime glass (thickness 0.7 mm) by a direct current magnetron sputtering method using a zinc oxide sputtering target containing 2% by mass of aluminum oxide. Sputtering was performed at a power of 75 W during film formation, a film formation pressure of 0.5 Pa, an oxygen partial pressure of 0 Pa, a substrate temperature of room temperature, and a film formation time of 30 minutes.
  • the etching rate of the formed thin film was examined in the same manner as in Example 1, it was 1.5 nm / second.
  • the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1 mol / l acetic acid aqueous solution at 20 ° C. for 120 seconds. The film thickness was measured using a stylus type film thickness meter (“Alpha-Step IQ” manufactured by Tencor). As a result, the etching rate of the formed thin film was 2.42 nm / second.
  • this film it is difficult to control because the etching rate is 1.0 nm / second or more.
  • this thin film is patterned using an acetic acid aqueous solution similar to that in Example 59 as an etchant using a mask having a predetermined pattern, it is good. It was difficult to form an etching pattern.

Abstract

The disclosed oxide sintered body is substantially formed from zinc, titanium, and oxygen, and the atomic ratio (Ti/(Zn+Ti) of the titanium to the sum of the zinc and the titanium is greater than 0.02 but does not exceed 0.1. The disclosed oxide mixture is formed from zinc oxide and titanium oxide, and the atomic ratio (Ti/(Zn+Ti) of the titanium to the sum of the zinc and the titanium is greater than 0.02 but does not exceed 0.1. An electrically conductive transparent zinc oxide film exhibiting excellent conductivity and chemical durability can be formed through using the disclosed oxide sintered body or oxide mixture.

Description

酸化物焼結体、酸化物混合体、それらの製造方法およびそれらを用いたターゲットOxide sintered body, oxide mixture, production method thereof, and target using them
　本発明は、酸化物焼結体、酸化物混合体、それらの製造方法およびそれらを用いたターゲットに関する。 The present invention relates to an oxide sintered body, an oxide mixture, a production method thereof, and a target using them.
　導電性と光透過性とを兼ね備えた透明導電膜は、従来、太陽電池、液晶表示素子、その他各種受光素子における電極などとして利用されているほか、自動車窓や建築用の熱線反射膜、帯電防止膜、冷凍ショーケース等における防曇用透明発熱体など、幅広い用途に利用されている。特に、低抵抗で導電性に優れた透明導電膜は、太陽電池や、液晶、有機エレクトロルミネッセンス、無機エレクトロルミネッセンスなどの液晶表示素子や、タッチパネルなどに好適であることが知られている。 Transparent conductive films that combine electrical conductivity and light transmission have been used as electrodes in solar cells, liquid crystal display elements, and other various light receiving elements, as well as automotive windows, heat ray reflective films for buildings, and antistatic properties. It is used in a wide range of applications, such as transparent anti-fogging elements for anti-fogging in membranes and frozen showcases. In particular, it is known that a transparent conductive film having a low resistance and excellent conductivity is suitable for a solar cell, a liquid crystal display element such as a liquid crystal, organic electroluminescence, and inorganic electroluminescence, a touch panel, and the like.
　従来、透明導電膜としては、例えば、酸化スズ（ＳｎＯ2）系の薄膜、酸化亜鉛（ＺｎＯ）系の薄膜、そして酸化インジウム（Ｉｎ2Ｏ3）系の薄膜が知られている。具体的には、酸化スズ系の透明導電膜としては、アンチモンをドーパントとして含むもの（ＡＴＯ）やフッ素をドーパントとして含むもの（ＦＴＯ）が知られており、酸化亜鉛系の透明導電膜としては、アルミニウムをドーパントとして含むもの（ＡＺＯ）やガリウムをドーパントとして含むもの（ＧＺＯ）が知られており、酸化インジウム系の透明導電膜としては、スズをドーパントとして含むもの（ＩＴＯ；Ｉｎｄｉｕｍ　Ｔｉｎ　Ｏｘｉｄｅ）が知られている。中でも、最も工業的に利用されているのは酸化インジウム系の透明導電膜であり、とりわけＩＴＯ膜は、低抵抗で導電性に優れることから、幅広く実用化されている。 Conventionally, as the transparent conductive film, for example, a tin oxide (SnO 2 ) -based thin film, a zinc oxide (ZnO) -based thin film, and an indium oxide (In 2 O 3 ) -based thin film are known. Specifically, as the tin oxide-based transparent conductive film, those containing antimony as a dopant (ATO) and those containing fluorine as a dopant (FTO) are known, and as a zinc oxide-based transparent conductive film, Those containing aluminum as a dopant (AZO) and those containing gallium as a dopant (GZO) are known, and indium oxide-based transparent conductive films include those containing tin as a dopant (ITO; Indium Tin Oxide). It has been. Among them, the most industrially used is an indium oxide-based transparent conductive film, and in particular, an ITO film is widely used because of its low resistance and excellent conductivity.
　このような透明導電膜を形成する際には、従来、スパッタリング法、イオンプレーティング法、パルスレーザ堆積法（ＰＬＤ法）、エレクトロンビーム（ＥＢ）蒸着法、スプレー法、ゾルゲル法などが工業的に汎用されている。これらの成膜方法において膜原料として用いられるターゲットは、成膜しようとする膜を構成する金属元素を含む固体からなり、金属、金属酸化物、金属窒化物、金属炭化物などの焼結体や混合体、場合によっては単結晶で形成される。 Conventionally, when forming such a transparent conductive film, sputtering, ion plating, pulse laser deposition (PLD), electron beam (EB) vapor deposition, spray, sol-gel, etc. are industrially used. It is widely used. The target used as a film raw material in these film formation methods is made of a solid containing a metal element constituting the film to be formed, and is a sintered body or a mixture of metal, metal oxide, metal nitride, metal carbide, etc. Body, and in some cases, a single crystal.
　例えば、ＩＴＯのような酸化物の膜をスパッタリング法で形成する際には、ターゲットとしては、一般に、膜を構成する金属元素からなる合金ターゲット（ＩＴＯ膜の場合にはＩｎ－Ｓｎ合金）か、もしくは膜を構成する金属元素を含む酸化物を焼結もしくは混合して得られた酸化物ターゲット（ＩＴＯ膜の場合にはＩｎ－Ｓｎ－Ｏからなる焼結体や混合体）が用いられる。ただし、合金ターゲットを用いると、形成される膜中の酸素は全て雰囲気中の酸素ガスから供給されることになるので、雰囲気中の酸素ガス量が変動しやすくなり、その結果、雰囲気中の酸素ガス量に依存する成膜速度や得られる膜の特性（比抵抗、透過率）を一定に保つことが困難になる場合がある。他方、酸化物ターゲットを用いた場合には、膜に供給される酸素の一部はターゲット自体から供給され、不足分のみが雰囲気中の酸素ガスから供給されることになるので、雰囲気中の酸素ガス量の変動は、合金ターゲットを用いる場合に比べ抑えることができ、その結果、一定の膜厚を有し一定の膜特性を有する透明導電膜を容易に製造することが可能となる。したがって、これまで、工業的に用いるターゲットとしては、酸化物ターゲット（すなわち酸化物焼結体または酸化物混合体）が用いられてきた。 For example, when an oxide film such as ITO is formed by sputtering, the target is generally an alloy target made of a metal element constituting the film (In—Sn alloy in the case of an ITO film), Alternatively, an oxide target (a sintered body or a mixture made of In—Sn—O in the case of an ITO film) obtained by sintering or mixing an oxide containing a metal element constituting the film is used. However, when an alloy target is used, all the oxygen in the formed film is supplied from the oxygen gas in the atmosphere, so the amount of oxygen gas in the atmosphere tends to fluctuate, and as a result, the oxygen in the atmosphere It may be difficult to keep the film formation rate depending on the amount of gas and the characteristics (specific resistance, transmittance) of the film obtained constant. On the other hand, when an oxide target is used, part of the oxygen supplied to the film is supplied from the target itself, and only the deficiency is supplied from the oxygen gas in the atmosphere. Variations in the gas amount can be suppressed as compared with the case where an alloy target is used, and as a result, a transparent conductive film having a certain film thickness and certain film characteristics can be easily manufactured. Therefore, until now, oxide targets (that is, oxide sintered bodies or oxide mixtures) have been used as targets for industrial use.
　ところで、ＩＴＯ膜の如き酸化インジウム系の透明導電膜は、その必須原料であるＩｎ（インジウム）が、希少金属であるため高価で且つ資源枯渇のおそれがあり、しかも毒性を有し環境や人体に対して悪影響を及ぼす可能性があるため、近年、ＩＴＯ膜に代替し得る工業的に汎用可能な透明導電膜が要望されている。そのような中、スパッタリング法による工業的製造も可能である酸化亜鉛系透明導電膜が注目されており、その導電性能を高めるべく研究が進められている。具体的には、導電性を高めるべくＺｎＯに種々のドーパントをドープさせる試みがなされており、種々のドーパントごとに最適ドープ量と最低抵抗率が報告されている（非特許文献１）。この報告によれば、例えば、ＴｉＯ2をドープさせる場合には、ドープ量は２ｗｔ％が最適であり、その時の最低抵抗率は５．６×１０-4Ω・ｃｍであることが示されている。このように、酸化亜鉛系透明導電膜は、実験室レベルではＩＴＯ膜に遜色のない程度の低抵抗が得られるよう改善されてきている。しかし、これまでの酸化亜鉛系透明導電膜は、導電性の点では優れるが、耐熱性、耐湿性、耐薬品性（耐アルカリ性、耐酸性）などの化学的耐久性に劣るという欠点を有する。 By the way, an indium oxide-based transparent conductive film such as an ITO film is expensive and may be depleted of resources because In (indium), which is an essential raw material, is a rare metal, and has toxicity and is harmful to the environment and the human body. In recent years, there is a demand for an industrially versatile transparent conductive film that can be substituted for an ITO film because it may adversely affect the film. Under such circumstances, a zinc oxide-based transparent conductive film that can be industrially manufactured by a sputtering method has attracted attention, and research is being conducted to improve its conductive performance. Specifically, attempts have been made to dope ZnO with various dopants in order to increase conductivity, and the optimum doping amount and the lowest resistivity have been reported for each of the various dopants (Non-patent Document 1). According to this report, for example, when TiO 2 is doped, the optimum doping amount is 2 wt%, and the minimum resistivity at that time is 5.6 × 10 −4 Ω · cm. Yes. As described above, the zinc oxide-based transparent conductive film has been improved to obtain a low resistance comparable to that of the ITO film at the laboratory level. However, conventional zinc oxide-based transparent conductive films are excellent in terms of conductivity, but have the disadvantage of being inferior in chemical durability such as heat resistance, moisture resistance, and chemical resistance (alkali resistance, acid resistance).
　また、酸化亜鉛系透明導電膜は、上記のように耐薬品性（耐酸性、耐アルカリ性）に乏しいため、酸化亜鉛系透明導電膜に所望の形状のパターニングを施すことが必要な場合（例えば素子などの用途に用いる場合）、適当なウェットエッチング液が存在せず、良好にパターニングできないという問題がある。詳しくは、酸化亜鉛には酸やアルカリへの溶解速度が非常に高いという性質があるため、酸化亜鉛系透明導電膜に対して酸やアルカリを用いてエッチングを行なうと、エッチングレートが非常に大きく（具体的には、ＩＴＯ膜に比べ１００倍以上）、即座に溶解してしまい、良好なパターン形状を得ることができなかったのである。一方、酸化スズ系透明導電膜は、耐薬品性（耐酸性、耐アルカリ性）に優れており、酸やアルカリに対して安定であるため、通常のエッチング液では溶解させにくく、逆の意味でウェットエッチングによるパターンニングできないという問題を有する。したがって、酸化亜鉛系透明導電膜や酸化スズ系透明導電膜は、これまで、パターニングする必要がない用途にしか利用できないという欠点を有する。そこで、酸化亜鉛系薄膜のパターニングを可能にする手段として、特定の酸をエッチング液とし、特定の元素をドープすることにより、エッチングレートを低く抑えることができることが提案されている（特許文献１）。具体的には、ＺｎＯにＴｉを６ａｔ％（ここで、「ａｔ％」は、亜鉛および添加元素の総原子個数１００に対する添加元素の原子個数）ドープした酸化亜鉛系薄膜のエッチング例と、ＺｎＯにＴｉを３ａｔ％ドープした酸化亜鉛系薄膜のエッチング例が開示されている。 In addition, since the zinc oxide-based transparent conductive film has poor chemical resistance (acid resistance and alkali resistance) as described above, it is necessary to pattern the zinc oxide-based transparent conductive film in a desired shape (for example, an element) In the case of use for such applications, there is a problem that an appropriate wet etching solution does not exist and patterning cannot be performed satisfactorily. Specifically, because zinc oxide has a very high dissolution rate in acids and alkalis, etching with an acid or alkali on a zinc oxide-based transparent conductive film results in a very high etching rate. (Specifically, it is 100 times or more compared with the ITO film) and it immediately dissolved, and a good pattern shape could not be obtained. On the other hand, the tin oxide-based transparent conductive film has excellent chemical resistance (acid resistance and alkali resistance) and is stable against acids and alkalis. There is a problem that patterning by etching cannot be performed. Therefore, the zinc oxide-based transparent conductive film and the tin oxide-based transparent conductive film have a drawback that they can only be used for applications that do not require patterning. Therefore, as a means for enabling patterning of a zinc oxide-based thin film, it has been proposed that a specific acid can be used as an etchant and a specific element can be doped to reduce the etching rate (Patent Document 1). . Specifically, an example of etching a zinc oxide-based thin film doped with 6 at% of Ti in ZnO (where “at%” is the number of atoms of the additive element with respect to the total number of atoms of zinc and the additive element of 100) An example of etching a zinc oxide thin film doped with 3 at% Ti is disclosed.
　しかし、特許文献１で開示されている酸化亜鉛系薄膜では、エッチングレートの抑制効果が不十分で、エッチングレートを確実に制御することが困難になる場合がある。さらに、この薄膜をＩＴＯ膜に代替する導電性膜として利用しようとする場合、その導電性は必ずしも満足し得るレベルではない。 However, the zinc oxide-based thin film disclosed in Patent Document 1 has an insufficient etching rate suppression effect, and it may be difficult to reliably control the etching rate. Furthermore, when this thin film is to be used as a conductive film that substitutes for an ITO film, its conductivity is not always satisfactory.
　また、酸化亜鉛系透明導電膜の環境や化学的な脆弱性は、異種の金属元素を添加することにより制御できることも知られている。特に、非常に強い耐久性を有する酸化チタン（ＴｉＯ2）を酸化亜鉛中に添加することにより、酸化亜鉛系透明導電膜の耐久性が向上することが、特許文献２に記載されている。 It is also known that the environment and chemical vulnerability of a zinc oxide-based transparent conductive film can be controlled by adding different kinds of metal elements. In particular, Patent Document 2 describes that the durability of a zinc oxide-based transparent conductive film is improved by adding titanium oxide (TiO 2 ) having extremely strong durability to zinc oxide.
　しかし、特許文献２では、２価の元素である亜鉛元素の結晶中サイトに４価の元素であるＴｉ元素が置換固溶しているため、電荷のバランスの崩れが大きく、結晶構造のひずみが大きいことや、イオン性不純物散乱の要因となることから、十分な導電性を発現することが困難である。 However, in Patent Document 2, since the Ti element as the tetravalent element is substituted and dissolved in the site in the crystal of the zinc element, which is the divalent element, the charge balance is greatly lost, and the crystal structure is distorted. Since it is large and causes ionic impurity scattering, it is difficult to develop sufficient conductivity.
特開２００８－１５９８１４号公報JP 2008-159814 A 特許第４２９５８１１号Japanese Patent No. 4295811
　本発明の第１の課題は、優れた導電性と化学的耐久性とを兼ね備えた酸化亜鉛系透明導電膜を得るのに好適な酸化物焼結体および酸化物混合体と、それらの製造方法およびそれらを用いたターゲットとを提供することにある。本発明の第２の課題は、優れた導電性と化学的耐久性とを兼ね備えた酸化亜鉛系透明導電膜の形成方法と、この方法により形成される酸化亜鉛系透明導電膜と、この膜を備えた透明導電性基板とを提供することにある。本発明の第３の課題は、パターニングする際のエッチングレートが十分に低く、エッチングレートを容易かつ確実に制御することが可能であり、良好なパターン形状を有するとともに導電性も高い酸化亜鉛系薄膜を得ることができるパターニング方法を提供することにある。 A first object of the present invention is to provide an oxide sintered body and an oxide mixture suitable for obtaining a zinc oxide-based transparent conductive film having both excellent conductivity and chemical durability, and methods for producing the same. And a target using them. The second object of the present invention is to provide a method for forming a zinc oxide-based transparent conductive film having both excellent conductivity and chemical durability, a zinc oxide-based transparent conductive film formed by this method, and this film. It is to provide a transparent conductive substrate provided. A third problem of the present invention is a zinc oxide thin film that has a sufficiently low etching rate at the time of patterning, can control the etching rate easily and reliably, has a good pattern shape, and has high conductivity. It is to provide a patterning method capable of obtaining the above.
　本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、以下の構成からなる解決手段を見出し、本発明を完成するに至った。
　すなわち、本発明の酸化物焼結体は、実質的に亜鉛、チタンおよび酸素からなり、亜鉛とチタンとの合計に対するチタンの原子数比Ｔｉ／（Ｚｎ＋Ｔｉ）が０．０２を超え０．１以下である。
　本発明に係る酸化物焼結体の製造方法は、以下の（Ａ）および／または（Ｂ）を含む原料粉末を成形した後、得られた成形体を、不活性雰囲気中、真空中または還元雰囲気中６００℃～１５００℃で焼結する方法である。
（Ａ）酸化チタン粉と酸化亜鉛粉との混合粉もしくは酸化チタン粉と水酸化亜鉛粉との混合粉
（Ｂ）チタン酸亜鉛化合物粉
　本発明に係る酸化物焼結体の製造方法は、以下の（Ａ）および／または（Ｂ）を含む原料粉末を成形した後、得られた成形体を大気雰囲気中または酸化雰囲気中６００℃～１５００℃で焼結し、その後さらに不活性雰囲気中、真空中または還元雰囲気中でアニール処理を施す方法である。
（Ａ）酸化チタン粉と酸化亜鉛粉との混合粉もしくは酸化チタン粉と水酸化亜鉛粉との混合粉
（Ｂ）チタン酸亜鉛化合物粉
　本発明の酸化物混合体は、酸化亜鉛および酸化チタンからなり、亜鉛とチタンとの合計に対するチタンが原子数比Ｔｉ／（Ｚｎ＋Ｔｉ）が０．０２を超え０．１以下である。
　本発明に係る酸化物混合体の製造方法は、酸化チタン粉と酸化亜鉛粉との混合粉もしくは酸化チタン粉と水酸化亜鉛粉との混合粉を含む原料粉末を成形した後、得られた成形体に大気雰囲気中、不活性雰囲気中、真空中または還元雰囲気中５０℃以上６００℃未満でアニール処理を施す方法である。
　本発明のターゲットは、上記酸化物焼結体または上記酸化物混合体を加工して得られるターゲットである。
　本発明に係る酸化亜鉛系透明導電膜の形成方法は、パルスレーザ堆積法（ＰＬＤ法）、スパッタリング法、イオンプレーティング法およびエレクトロンビーム（ＥＢ）蒸着法からなる群より選ばれる１種により酸化亜鉛系透明導電膜を形成する方法であって、実質的に亜鉛、チタンおよび酸素からなり亜鉛とチタンとの合計に対するチタンの原子数比Ｔｉ／（Ｚｎ＋Ｔｉ）が０．０２を超え０．１以下である酸化物焼結体または酸化物混合体を加工して得られるターゲットを用いる方法である。
　本発明の酸化亜鉛系透明導電膜は、上記酸化亜鉛系透明導電膜の形成方法により形成された膜である。
　本発明の透明導電性基板は、透明基材上に、上記酸化亜鉛系透明導電膜を備える基板である。
　本発明の酸化亜鉛系透明導電膜形成材料は、亜鉛とチタンとの合計に対するチタンの原子数比Ｔｉ／（Ｚｎ＋Ｔｉ）が０．０２を超え０．１以下であり、酸化亜鉛を主成分とし、ガリウムおよびアルミニウムのうち少なくとも一方の酸化物と、酸化チタンとを含み、ガリウムまたはアルミニウムの原子数の割合が全金属原子数に対して０．５％以上６％以下であり、かつ前記酸化チタンが、式ＴｉＯ2-X（Ｘ＝０．１～１）で表される低原子価酸化チタンである酸化物混合体または酸化物焼結体からなる。
　本発明の第二のターゲットは、酸化亜鉛系透明導電膜形成材料を加工して得られるターゲットである。
　本発明に係る第二の酸化亜鉛系透明導電膜の形成方法は、上記第二のターゲットを用いて、スパッタリング法、イオンプレーティング法、パルスレーザ堆積法（ＰＬＤ法）またはエレクトロンビーム（ＥＢ）蒸着法により酸化亜鉛系透明導電膜を形成する方法である。
　本発明の透明導電性基板は、透明基材上に、上記透明導電膜の形成方法により形成された酸化亜鉛系透明導電膜を備える基板である。
　本発明に係るパターニング方法は、酸化亜鉛系薄膜を酸によりエッチングしてパターニングする方法であって、前記酸化亜鉛系薄膜が、酸化亜鉛を主成分とし、亜鉛とチタンとの合計に対するチタンの原子数比Ｔｉ／（Ｚｎ＋Ｔｉ）が０．０２を超え０．１以下の薄膜である方法である。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a solution means having the following configuration and have completed the present invention.
That is, the oxide sintered body of the present invention is substantially composed of zinc, titanium, and oxygen, and the atomic ratio Ti / (Zn + Ti) of titanium to the total of zinc and titanium exceeds 0.02 and is 0.1 or less. It is.
In the method for producing an oxide sintered body according to the present invention, after molding a raw material powder containing the following (A) and / or (B), the obtained molded body is subjected to inert atmosphere, vacuum or reduction. This is a method of sintering at 600 ° C. to 1500 ° C. in an atmosphere.
(A) Mixed powder of titanium oxide powder and zinc oxide powder or mixed powder of titanium oxide powder and zinc hydroxide powder (B) Zinc titanate compound powder The method for producing an oxide sintered body according to the present invention is as follows. After the raw material powder containing (A) and / or (B) is molded, the obtained molded body is sintered at 600 ° C. to 1500 ° C. in an air atmosphere or an oxidizing atmosphere, and then further vacuumed in an inert atmosphere. In this method, annealing is performed in a reducing atmosphere.
(A) Mixed powder of titanium oxide powder and zinc oxide powder or mixed powder of titanium oxide powder and zinc hydroxide powder (B) Zinc titanate compound powder The oxide mixture of the present invention comprises zinc oxide and titanium oxide. Therefore, titanium with respect to the sum of zinc and titanium has an atomic ratio Ti / (Zn + Ti) of more than 0.02 and 0.1 or less.
The method for producing an oxide mixture according to the present invention is obtained by molding a raw material powder containing a mixed powder of titanium oxide powder and zinc oxide powder or a mixed powder of titanium oxide powder and zinc hydroxide powder. In this method, the body is annealed at 50 ° C. or higher and lower than 600 ° C. in an air atmosphere, an inert atmosphere, a vacuum or a reducing atmosphere.
The target of the present invention is a target obtained by processing the oxide sintered body or the oxide mixture.
The method for forming a zinc oxide-based transparent conductive film according to the present invention comprises zinc oxide selected from the group consisting of a pulse laser deposition method (PLD method), a sputtering method, an ion plating method, and an electron beam (EB) vapor deposition method. A method of forming a transparent organic conductive film, which is substantially composed of zinc, titanium and oxygen, and the atomic ratio Ti / (Zn + Ti) of titanium to the total of zinc and titanium is more than 0.02 and not more than 0.1. In this method, a target obtained by processing a certain oxide sintered body or oxide mixture is used.
The zinc oxide-based transparent conductive film of the present invention is a film formed by the method for forming the zinc oxide-based transparent conductive film.
The transparent conductive substrate of this invention is a board | substrate provided with the said zinc oxide type transparent conductive film on a transparent base material.
In the zinc oxide-based transparent conductive film-forming material of the present invention, the atomic ratio Ti / (Zn + Ti) of titanium with respect to the total of zinc and titanium is more than 0.02 and not more than 0.1, and the main component is zinc oxide. It contains at least one oxide of gallium and aluminum and titanium oxide, the ratio of the number of atoms of gallium or aluminum is 0.5% or more and 6% or less with respect to the total number of metal atoms, and the titanium oxide And an oxide mixture or an oxide sintered body, which is a low-valent titanium oxide represented by the formula TiO 2-X (X = 0.1 to 1).
The second target of the present invention is a target obtained by processing a zinc oxide-based transparent conductive film forming material.
The second method for forming a zinc oxide-based transparent conductive film according to the present invention is the sputtering method, ion plating method, pulse laser deposition method (PLD method) or electron beam (EB) vapor deposition using the second target. In this method, a zinc oxide-based transparent conductive film is formed by a method.
The transparent conductive substrate of this invention is a board | substrate provided with the zinc oxide type transparent conductive film formed by the formation method of the said transparent conductive film on a transparent base material.
The patterning method according to the present invention is a method of patterning by etching a zinc oxide thin film with an acid, wherein the zinc oxide thin film contains zinc oxide as a main component, and the number of titanium atoms relative to the total of zinc and titanium. In this method, the ratio Ti / (Zn + Ti) is a thin film having a ratio exceeding 0.02 and not more than 0.1.
　本発明によれば、スパッタリング法、イオンプレーティング法、ＰＬＤ法またはＥＢ蒸着法によって、優れた導電性と化学的耐久性とを有する酸化亜鉛系透明導電膜を形成することができる。このようにして形成された透明導電膜は、希少金属であり毒性を有するインジウムを必須としないという利点も有するので、工業的に極めて有用である。さらに本発明によれば、良好なパターン形状を有するとともに導電性も高い酸化亜鉛系透明導電膜を得ることができる。 According to the present invention, a zinc oxide-based transparent conductive film having excellent conductivity and chemical durability can be formed by sputtering, ion plating, PLD, or EB vapor deposition. The transparent conductive film formed in this manner is extremely useful industrially because it has the advantage that it does not require toxic indium, which is a rare metal. Furthermore, according to the present invention, a zinc oxide-based transparent conductive film having a good pattern shape and high conductivity can be obtained.
本発明において好適に用いることができるイオンプレーティング装置の一例を示す概略図である。It is the schematic which shows an example of the ion plating apparatus which can be used suitably in this invention.
　（酸化物焼結体）
　本発明の酸化物焼結体は、実質的に亜鉛、チタンおよび酸素からなるチタンドープ酸化亜鉛の焼結体である。ここで、「実質的」とは、酸化物焼結体を構成する全原子の９９％以上が亜鉛、チタンまたは酸素からなることを意味する。 (Oxide sintered body)
The oxide sintered body of the present invention is a titanium-doped zinc oxide sintered body substantially composed of zinc, titanium, and oxygen. Here, “substantially” means that 99% or more of all atoms constituting the oxide sintered body are composed of zinc, titanium, or oxygen.
　本発明の酸化物焼結体は、亜鉛とチタンの合計に対するチタンの原子数比Ｔｉ／（Ｚｎ＋Ｔｉ）が０．０２を超え０．１以下である。このＴｉ／（Ｚｎ＋Ｔｉ）の値が０．０２以下の場合、酸化物焼結体をターゲットとして用いて形成された膜の耐薬品性など化学的耐久性が不十分となり、しかも、酸化物焼結体中にチタン酸亜鉛化合物が形成されにくくなるため焼結体の強度が低下し、ターゲットへの加工が困難になる。一方、Ｔｉ／（Ｚｎ＋Ｔｉ）の値が０．１を超える場合、後述するように酸化物焼結体中に含まれないことが望まれる酸化チタン結晶相が形成される可能性が高く、この酸化物焼結体をターゲットとして形成された膜の導電性や透明性が低下する傾向にある。前記原子数比は、好ましくはＴｉ／（Ｚｎ＋Ｔｉ）＝０．０２５～０．０９、より好ましくはＴｉ／（Ｚｎ＋Ｔｉ）＝０．０３～０．０９、さらに好ましくはＴｉ／（Ｚｎ＋Ｔｉ）＝０．０３～０．０８、最も好ましくはＴｉ／（Ｚｎ＋Ｔｉ）＝０．０４～０．０８である。 In the oxide sintered body of the present invention, the atomic ratio Ti / (Zn + Ti) of titanium to the total of zinc and titanium is more than 0.02 and 0.1 or less. When the value of Ti / (Zn + Ti) is 0.02 or less, chemical durability such as chemical resistance of a film formed using an oxide sintered body as a target is insufficient, and oxide sintering is performed. Since it becomes difficult for the zinc titanate compound to be formed in the body, the strength of the sintered body is reduced, making it difficult to process the target. On the other hand, when the value of Ti / (Zn + Ti) exceeds 0.1, there is a high possibility that a titanium oxide crystal phase that is desired not to be included in the oxide sintered body is formed as described later. There exists a tendency for the electroconductivity and transparency of the film | membrane formed by using a sintered compact as a target to fall. The atomic ratio is preferably Ti / (Zn + Ti) = 0.025 to 0.09, more preferably Ti / (Zn + Ti) = 0.03 to 0.09, and further preferably Ti / (Zn + Ti) = 0. 03 to 0.08, most preferably Ti / (Zn + Ti) = 0.04 to 0.08.
　本発明の酸化物焼結体は、酸化亜鉛相とチタン酸亜鉛化合物相とから構成されるか、または、チタン酸亜鉛化合物相から構成されることが好ましい。例えば、過酷な条件（高電力など）で成膜しても、このように酸化物焼結体中にチタン酸亜鉛化合物相が含まれていると、焼結体自体の強度が増すので、クラックを生じにくい。チタン酸亜鉛化合物としては、例えば、ＺｎＴｉＯ3やＺｎ2ＴｉＯ4のほか、これらの亜鉛サイトにチタン元素が固溶したものや、酸素欠損が導入されているものや、Ｚｎ／Ｔｉ比がこれらの化合物から僅かにずれた非化学量論組成のものも挙げられる。また、酸化亜鉛としては、例えば、ＺｎＯのほか、これにチタン元素が固溶したものや、酸素欠損が導入されているものや、亜鉛欠損により非化学量論組成となったものも挙げられる。酸化亜鉛相は、通常、ウルツ鉱型構造を有する。 The oxide sintered body of the present invention is preferably composed of a zinc oxide phase and a zinc titanate compound phase, or composed of a zinc titanate compound phase. For example, even if the film is formed under harsh conditions (high power, etc.), if the oxide titanate contains a zinc titanate compound phase in this way, the strength of the sintered body itself increases, so cracks occur. It is hard to produce. Examples of the zinc titanate compound include ZnTiO 3 and Zn 2 TiO 4 , those in which a titanium element is dissolved in these zinc sites, those in which oxygen deficiency is introduced, and those having a Zn / Ti ratio. Non-stoichiometric compositions slightly deviating from the compound are also included. Further, examples of zinc oxide include ZnO, a solution in which a titanium element is dissolved, a material in which oxygen deficiency is introduced, and a material having a non-stoichiometric composition due to zinc deficiency. The zinc oxide phase usually has a wurtzite structure.
　本発明の酸化物焼結体は、実質的に酸化チタンの結晶相を含有しないことが好ましい。酸化物焼結体に酸化チタンの結晶相が含有されると、得られる膜が、比抵抗のなどの物性における均一性に欠けるものとなるおそれがある。本発明の酸化物焼結体は、上述したＴｉ／（Ｚｎ＋Ｔｉ）の値が０．１以下であるので、通常、酸化チタンが酸化亜鉛に完全に反応し、酸化物焼結体中に酸化チタン結晶相は生じにくい。なお、酸化チタンの結晶相としては、例えば、ＴｉＯ2、Ｔｉ2Ｏ3、ＴｉＯのほか、これらの結晶にＺｎなど他の元素が固溶された物質も挙げられる。 It is preferable that the oxide sintered body of the present invention does not substantially contain a titanium oxide crystal phase. When the oxide sintered body contains a crystal phase of titanium oxide, the resulting film may lack uniformity in physical properties such as specific resistance. In the oxide sintered body of the present invention, since the value of Ti / (Zn + Ti) described above is 0.1 or less, titanium oxide usually reacts completely with zinc oxide, and titanium oxide is contained in the oxide sintered body. A crystalline phase is unlikely to occur. Examples of the crystalline phase of titanium oxide include TiO 2 , Ti 2 O 3 , and TiO, as well as substances in which other elements such as Zn are dissolved in these crystals.
　本発明の酸化物焼結体は、ガリウム、アルミニウム、錫、シリコン、ゲルマニウム、ジルコニウムおよびハフニウムからなる群より選ばれる少なくとも１種の元素（以下、「添加元素」と記載する場合がある）を、さらに含有することが好ましい。このような添加元素を含有することによって、酸化物焼結体をターゲットとして用いて形成される膜の比抵抗に加え、酸化物焼結体自体の比抵抗も低下させることができる。例えば直流スパッタリング時の成膜速度は、スパッタリングターゲットとする酸化物焼結体の比抵抗に依存し、酸化物焼結体自体の比抵抗を下げることにより、成膜時の生産性を向上させることができる。添加元素を含有する場合、その全含有量は、原子比で酸化物焼結体を構成する全金属元素の総量に対して０．０５％以下であることが好ましい。添加元素の含有量が０．０５％を超えると、酸化物焼結体をターゲットとして用いて形成される膜の比抵抗が増大するおそれがある。 The oxide sintered body of the present invention contains at least one element selected from the group consisting of gallium, aluminum, tin, silicon, germanium, zirconium and hafnium (hereinafter sometimes referred to as “additive element”), Furthermore, it is preferable to contain. By containing such an additive element, the specific resistance of the oxide sintered body itself can be reduced in addition to the specific resistance of the film formed using the oxide sintered body as a target. For example, the film formation rate during DC sputtering depends on the specific resistance of the oxide sintered body as a sputtering target, and the productivity during film formation is improved by lowering the specific resistance of the oxide sintered body itself. Can do. When it contains an additive element, it is preferable that the total content is 0.05% or less with respect to the total amount of all the metal elements which comprise oxide sinter by atomic ratio. If the content of the additive element exceeds 0.05%, the specific resistance of the film formed using the oxide sintered body as a target may increase.
　添加元素は、酸化物の形態で酸化物焼結体中に存在していてもよいし、酸化亜鉛相の亜鉛サイトに置換した（固溶した）形態で存在していてもよいし、チタン酸亜鉛化合物相のチタンサイトおよび／または亜鉛サイトに置換した（固溶した）形態で存在していてもよい。 The additive element may be present in the oxide sintered body in the form of an oxide, or may be present in a form substituted (solid solution) in the zinc site of the zinc oxide phase, or titanic acid. The zinc compound phase may exist in a form substituted (solid solution) with titanium sites and / or zinc sites.
　本発明の酸化物焼結体は、亜鉛およびチタンの必須元素や添加元素のほかに、例えば、インジウム、イリジウム、ルテニウム、レニウムなどの他の元素を、不純物として含有してもよい。不純物として含有される元素の合計含有量は、原子比で、酸化物焼結体を構成する全金属元素の総量に対して０．５％以下であることが好ましい。 The oxide sintered body of the present invention may contain other elements such as indium, iridium, ruthenium, rhenium as impurities in addition to the essential elements and additive elements of zinc and titanium. The total content of elements contained as impurities is preferably 0.5% or less in terms of atomic ratio with respect to the total amount of all metal elements constituting the oxide sintered body.
　本発明の酸化物焼結体の比抵抗は、５ｋΩ・ｃｍ以下であることが好ましい。例えば、直流スパッタリング時の成膜速度は、スパッタリングターゲットとする酸化物焼結体の比抵抗に依存するので、酸化物焼結体の比抵抗が５ｋΩ・ｃｍを超えると、直流スパッタで安定的な成膜を行えないおそれがある。成膜時の生産性を考慮すると、本発明の酸化物焼結体の比抵抗は低いほど好ましく、具体的には１００Ω・ｃｍ以下であるのがよい。 The specific resistance of the oxide sintered body of the present invention is preferably 5 kΩ · cm or less. For example, the deposition rate during direct current sputtering depends on the specific resistance of the oxide sintered body as a sputtering target. Therefore, if the specific resistance of the oxide sintered body exceeds 5 kΩ · cm, the direct current sputtering is stable. There is a risk that film formation cannot be performed. Considering the productivity at the time of film formation, the specific resistance of the oxide sintered body of the present invention is preferably as low as possible. Specifically, it should be 100 Ω · cm or less.
　本発明の酸化物焼結体は、後述する本発明に係る酸化物焼結体の製造方法によって好ましく得られるが、これらの製造方法により得られたものに限定されるわけではない。例えば、チタン金属と酸化亜鉛粉もしくは水酸化亜鉛粉とを組み合わせたものや、酸化チタンと亜鉛金属とを組み合わせたものを原料粉末として得られたものであってもよい。通常、酸化物焼結体を還元雰囲気にて焼結した場合は、酸素欠損の導入により、酸化物焼結体の比抵抗は低くなり、酸化雰囲気にて焼結した場合は、比抵抗は高くなる。 The oxide sintered body of the present invention is preferably obtained by a method for producing an oxide sintered body according to the present invention described later, but is not limited to those obtained by these production methods. For example, a combination of titanium metal and zinc oxide powder or zinc hydroxide powder, or a combination of titanium oxide and zinc metal may be obtained as a raw material powder. Normally, when the oxide sintered body is sintered in a reducing atmosphere, the specific resistance of the oxide sintered body is reduced by introducing oxygen deficiency, and when the oxide sintered body is sintered in an oxidizing atmosphere, the specific resistance is high. Become.
　（酸化物焼結体の製造方法）
　本発明に係る酸化物焼結体の製造方法は、以下の（Ａ）および／または（Ｂ）を含む原料粉末を成形した後、得られた成形体を焼結することにより、上記本発明の酸化物焼結体を得る方法である。
（Ａ）酸化チタン粉と酸化亜鉛粉との混合粉もしくは酸化チタン粉と水酸化亜鉛粉との混合粉
（Ｂ）チタン酸亜鉛化合物粉 (Oxide sintered body manufacturing method)
The method for producing an oxide sintered body according to the present invention includes forming the raw material powder containing the following (A) and / or (B), and then sintering the obtained molded body, This is a method for obtaining an oxide sintered body.
(A) Mixed powder of titanium oxide powder and zinc oxide powder or mixed powder of titanium oxide powder and zinc hydroxide powder (B) Zinc titanate compound powder
　原料粉末としては、酸化チタン粉と酸化亜鉛粉との混合粉もしくは酸化チタン粉と水酸化亜鉛粉との混合粉か、またはチタン酸亜鉛化合物粉を含むものであればよく、酸化チタン粉と酸化亜鉛粉とチタン酸亜鉛化合物粉との混合粉もしくは酸化チタン粉と水酸化亜鉛粉とチタン酸亜鉛化合物粉との混合粉であってもよい。好ましくは、酸化チタン粉と酸化亜鉛粉との混合粉もしくは酸化チタン粉と水酸化亜鉛粉との混合粉を含むものがよい。上述のように、例えば、チタン金属と酸化亜鉛粉もしくは水酸化亜鉛粉とを組み合わせたものや、酸化チタンと亜鉛金属とを組み合わせたものを原料粉末としても、本発明の酸化物焼結体は得られるが、その場合、酸化物焼結体中にチタンや亜鉛の金属粒が存在しやすくなり、これをターゲットとして成膜すると、成膜中にターゲット表面の金属粒が溶融してしまいターゲットから放出されず、得られる膜の組成とターゲットの組成とが大きく異なる傾向がある。 The raw material powder may be a mixed powder of titanium oxide powder and zinc oxide powder, a mixed powder of titanium oxide powder and zinc hydroxide powder, or a powder containing zinc titanate compound powder. It may be a mixed powder of zinc powder and zinc titanate compound powder or a mixed powder of titanium oxide powder, zinc hydroxide powder and zinc titanate compound powder. It is preferable to include a mixed powder of titanium oxide powder and zinc oxide powder or a mixed powder of titanium oxide powder and zinc hydroxide powder. As described above, for example, even if a combination of titanium metal and zinc oxide powder or zinc hydroxide powder or a combination of titanium oxide and zinc metal is used as the raw material powder, the oxide sintered body of the present invention is In that case, titanium or zinc metal particles are likely to be present in the oxide sintered body, and when this is used as a target, the metal particles on the surface of the target melt during the film formation. There is a tendency that the composition of the obtained film and the composition of the target are largely different without being released.
　酸化チタン粉としては、４価のチタンからなる酸化チタン（ＴｉＯ2）、３価のチタンからなる酸化チタン（Ｔｉ2Ｏ3）、２価のチタンからなる酸化チタン（ＴｉＯ）等の粉末を用いることができ、特にＴｉ2Ｏ3の粉末を用いるのが好ましい。なぜなら、Ｔｉ2Ｏ3の結晶構造は三方晶であり、これと混合する酸化亜鉛は六方晶のウルツ鉱型構造を有するため、結晶構造の対称性が一致し、固相焼結する際に置換固溶しやすいと考えることができるからである。酸化チタン粉の純度は、好ましくは９９重量％以上である。 As the titanium oxide powder, titanium oxide (TiO 2 ) made of tetravalent titanium, titanium oxide (Ti 2 O 3 ) made of trivalent titanium, titanium oxide (TiO) made of divalent titanium, or the like is used. In particular, it is preferable to use Ti 2 O 3 powder. Because the crystal structure of Ti 2 O 3 is trigonal and the zinc oxide mixed with it has a hexagonal wurtzite structure, the symmetry of the crystal structure is the same, and it is replaced when solid-phase sintering is performed. It is because it can be considered that it dissolves easily. The purity of the titanium oxide powder is preferably 99% by weight or more.
　低原子価酸化チタンとは、ＴｉＯ（II）、Ｔｉ2Ｏ3（III）という整数の原子価を有するものばかりでなく、Ｔｉ3Ｏ5、Ｔｉ4Ｏ7、Ｔｉ6Ｏ11、Ｔｉ5Ｏ9、Ｔｉ8Ｏ15等も含む、式ＴｉＯ2-X（Ｘ＝０．１～１）で表される範囲のものである。式ＴｉＯ2-X（Ｘ＝０．１～１）で示される低原子価酸化チタンは、低原子価酸化チタンの混合物であってもよい。通常、酸化チタン（ＴｉＯ2）を水素雰囲気等の還元雰囲気にて、還元剤としてカーボン等を用いて、加熱することにより作製することができる。水素濃度、還元剤としてカーボン量、加熱温度を調製することにより、低原子価酸化チタンの混合物の割合を制御することができる。この低原子価酸化チタンの構造は、Ｘ線回折装置（Ｘ－ｒａｙ　ｄｉｆｆｒａｃｔｉｏｎ、　ＸＲＤ）、Ｘ線光電子分光装置（Ｘ－ｒａｙ　Ｐｈｏｔｏｅｌｅｃｔｒｏｎ　Ｓｐｅｃｔｒｏｓｃｏｐｙ、　ＸＰＳ）などの機器分析の結果によって確認することができる。 Low valence titanium oxide includes not only those having an integer valence of TiO (II) and Ti 2 O 3 (III), but also Ti 3 O 5 , Ti 4 O 7 , Ti 6 O 11 , and Ti 5 O. 9 and Ti 8 O 15, etc., in the range represented by the formula TiO 2-X (X = 0.1 to 1). The low valence titanium oxide represented by the formula TiO 2-X (X = 0.1 to 1) may be a mixture of low valence titanium oxides. Usually, it can be produced by heating titanium oxide (TiO 2 ) in a reducing atmosphere such as a hydrogen atmosphere using carbon or the like as a reducing agent. By adjusting the hydrogen concentration, the amount of carbon as a reducing agent, and the heating temperature, the ratio of the low-valent titanium oxide mixture can be controlled. The structure of this low-valence titanium oxide can be confirmed by the results of instrumental analysis such as an X-ray diffraction apparatus (X-ray diffraction, XRD), an X-ray photoelectron spectrometer (X-ray Photoelectron Spectroscopy, XPS).
　酸化亜鉛粉としては、通常、ウルツ鉱型構造のＺｎＯ等の粉末が用いられ、さらにこのＺｎＯを予め還元雰囲気で焼成して酸素欠損を含有させたものを用いてもよい。酸化亜鉛粉の純度は、好ましくは９９重量％以上である。水酸化亜鉛粉としては、アモルファスもしくは結晶質のいずれであってもよい。チタン酸亜鉛化合物としては、ＺｎＴｉＯ3、Ｚｎ2ＴｉＯ4等の粉末を用いることができ、特に、Ｚｎ2ＴｉＯ4の粉末を用いるのが好ましい。原料粉末として各々用いる化合物（粉）の平均粒径は、それぞれ５μｍ以下であることが好ましく、１μｍ以下であることがより好ましい。なお、原料粉末のＢＥＴ比表面積は、特に限定されない。 As the zinc oxide powder, a powder of ZnO or the like having a wurtzite structure is usually used, and a powder obtained by firing this ZnO in advance in a reducing atmosphere and containing oxygen deficiency may be used. The purity of the zinc oxide powder is preferably 99% by weight or more. The zinc hydroxide powder may be either amorphous or crystalline. As the zinc titanate compound, powders of ZnTiO 3 , Zn 2 TiO 4 and the like can be used, and it is particularly preferable to use Zn 2 TiO 4 powder. The average particle size of each compound (powder) used as the raw material powder is preferably 5 μm or less, and more preferably 1 μm or less. In addition, the BET specific surface area of raw material powder is not specifically limited.
　原料粉末として、混合粉を用いる場合の各粉の混合割合は、各々用いる化合物（粉）の種類に応じて、最終的に得られる酸化物焼結体において原子数比でＴｉ／（Ｚｎ＋Ｔｉ）の値が上記の範囲となるように適宜設定すればよい。その際、亜鉛はチタンに比べて蒸気圧が高く焼結した際に揮散しやすいことを考慮して、所望する酸化物焼結体の目的組成（ＺｎとＴｉとの原子数比）よりも、予め亜鉛の量が多くなるように混合割合を設定しておくことが好ましい。具体的には、亜鉛の揮散のしやすさは、焼結する際の雰囲気によって異なり、例えば、酸化亜鉛粉を用いた場合、大気雰囲気や酸化雰囲気では酸化亜鉛粉自体の揮散しか起こらないが、還元雰囲気で焼結すると、酸化亜鉛が還元されて、酸化亜鉛よりもさらに揮散しやすい金属亜鉛となりやすいので、亜鉛の消失量が増すことになるのである（但し、後述のように、一旦焼結した後、還元雰囲気中でアニール処理を施す場合には、アニール処理を施す時点で既に複合酸化物となっているので、亜鉛が揮散しにくい）。したがって、目的組成に対してどの程度亜鉛の量を増やしておくかについては、焼結の雰囲気などを考慮して設定すればよく、例えば、大気雰囲気や酸化雰囲気で焼結する場合には所望する原子数比となる量の１．０～１．０５倍程度、還元雰囲気で焼結する場合には所望する原子数比となる量の１．１～１．３倍程度とすればよい。原料粉末として各々用いる化合物（粉）は、それぞれ１種のみであってもよく、２種以上を併用してもよい。 When using mixed powder as the raw material powder, the mixing ratio of each powder is Ti / (Zn + Ti) in atomic ratio in the finally obtained oxide sintered body, depending on the type of compound (powder) used. What is necessary is just to set suitably so that a value may become said range. At that time, considering that zinc has a higher vapor pressure than titanium and is likely to be volatilized when sintered, the desired composition of the desired oxide sintered body (atomic ratio of Zn and Ti), It is preferable to set the mixing ratio in advance so that the amount of zinc increases. Specifically, the easiness of volatilization of zinc varies depending on the atmosphere during sintering.For example, when zinc oxide powder is used, only the volatilization of zinc oxide powder itself occurs in an air atmosphere or an oxidizing atmosphere. When sintered in a reducing atmosphere, zinc oxide is reduced, and it becomes easier to volatilize metal zinc than zinc oxide, so the amount of zinc lost increases (however, as described later, it is once sintered) After that, when annealing is performed in a reducing atmosphere, zinc is already difficult to evaporate because it is already a complex oxide at the time of annealing. Therefore, the amount of zinc to be increased with respect to the target composition may be set in consideration of the sintering atmosphere or the like. For example, it is desirable when sintering is performed in an air atmosphere or an oxidizing atmosphere. About 1.0 to 1.05 times as much as the atomic ratio, and when sintering in a reducing atmosphere, it may be about 1.1 to 1.3 times as large as the desired atomic ratio. Each of the compounds (powder) used as the raw material powder may be only one kind, or two or more kinds may be used in combination.
　原料粉末を成形する際の方法は、特に制限されず、例えば、原料粉末を混合し、得られた混合物を成形すればよい。混合は、例えば、ボールミル、振動ミル、アトライター、ダイノミル、ダイナミックミルなどの公知の混合方法を用いて行うことができる。湿式の場合、原料粉末と水系溶媒とを混合し、得られたスラリーを十分に混合した後、固液分離し、乾燥し、造粒し、得られた造粒物を成形すればよい。湿式混合は、例えば、硬質ＺｒＯ2ボール等を用いた湿式ボールミルや振動ミルにより行えばよく、湿式ボールミルや振動ミルを用いた場合の混合時間は、１２時間～７８時間程度が好ましい。なお、原料粉末をそのまま乾式混合してもよいが、湿式混合の方がより好ましい。固液分離、乾燥および造粒については、それぞれ公知の方法を採用すればよい。得られた造粒物を成形する際には、例えば、造粒物を型枠に入れ、冷間プレスや冷間静水圧プレス（ＣＩＰ）などの冷間成形機、一軸プレスなどを用いて１ｔｏｎ／ｃｍ2以上の圧力をかけて成形することができる。このとき、ホットプレスなどを用いて熱間で成形を行うと、製造コストの面で不利となるとともに、大型焼結体が得にくくなる。なお、成形体として造粒物を得る際には、乾燥後、公知の方法で造粒すればよく、その場合、原料粉末とともにバインダーも混合することが好ましい。バインダーとしては、例えば、ポリビニルアルコール、酢酸ビニル等が挙げられる。 The method for molding the raw material powder is not particularly limited, and for example, the raw material powder may be mixed and the obtained mixture may be molded. The mixing can be performed using a known mixing method such as a ball mill, a vibration mill, an attritor, a dyno mill, or a dynamic mill. In the case of the wet method, the raw material powder and the aqueous solvent are mixed, and the obtained slurry is sufficiently mixed, then solid-liquid separated, dried and granulated, and the obtained granulated product may be formed. The wet mixing may be performed by, for example, a wet ball mill using a hard ZrO 2 ball or a vibration mill, and the mixing time in the case of using a wet ball mill or a vibration mill is preferably about 12 to 78 hours. In addition, although raw material powder may be dry-mixed as it is, wet mixing is more preferable. Known methods may be employed for solid-liquid separation, drying, and granulation. When the obtained granulated product is molded, for example, the granulated product is put into a mold and 1 ton using a cold forming machine such as a cold press or a cold isostatic press (CIP), a uniaxial press or the like. It can be formed by applying a pressure of / cm 2 or more. At this time, when hot forming is performed using a hot press or the like, it is disadvantageous in terms of manufacturing cost and it is difficult to obtain a large-sized sintered body. In addition, when obtaining a granulated material as a molded object, what is necessary is just to granulate by a well-known method after drying. In that case, it is preferable to mix a raw material powder and a binder. Examples of the binder include polyvinyl alcohol and vinyl acetate.
　得られた成形体の焼結は、不活性雰囲気（窒素、アルゴン、ヘリウム、ネオン等）、真空、還元雰囲気（二酸化炭素、水素、アンモニア等）、大気雰囲気および酸化雰囲気（大気よりも酸素濃度が高い雰囲気）のいずれかの雰囲気中、６００℃～１５００℃で行なう。そして、大気雰囲気中あるいは酸化雰囲気中で焼結した場合には、その後さらに不活性雰囲気中、真空中または還元雰囲気中でアニール処理を施すことが好ましい。この大気雰囲気中あるいは酸化雰囲気中で焼結した後に施す不活性雰囲気中、真空中または還元雰囲気中でのアニール処理は、酸化物焼結体に酸素欠損を生じさせ、比抵抗を低下させるために行なうものである。したがって、不活性雰囲気中、真空中または還元雰囲気中で焼結した際にも、さらなる比抵抗の低下を所望する場合には、焼結後、アニール処理を施すのが好ましい。 Sintering of the obtained compact is performed in an inert atmosphere (nitrogen, argon, helium, neon, etc.), vacuum, reducing atmosphere (carbon dioxide, hydrogen, ammonia, etc.), air atmosphere and oxidizing atmosphere (oxygen concentration is higher than air). High atmosphere) at 600 ° C. to 1500 ° C. When sintering is performed in an air atmosphere or an oxidizing atmosphere, it is preferable to perform an annealing process in an inert atmosphere, a vacuum, or a reducing atmosphere. An annealing treatment in an inert atmosphere, a vacuum, or a reducing atmosphere applied after sintering in an air atmosphere or an oxidizing atmosphere causes oxygen deficiency in the oxide sintered body and lowers the specific resistance. To do. Therefore, even if sintering is performed in an inert atmosphere, a vacuum, or a reducing atmosphere, if it is desired to further reduce the specific resistance, it is preferable to perform annealing after the sintering.
　いずれの雰囲気中で焼結する際も、焼結温度は、好ましくは６００℃～１７００℃、より好ましくは６００℃～１５００℃、さらに好ましくは１０００℃～１５００℃、最も好ましくは１０００℃～１３００℃とする。焼結温度が６００℃未満であると、焼結が十分に進行しないので、ターゲット密度が低くなり、一方、１５００℃を超えると、酸化亜鉛自体が分解して消失する。成形体を前記焼結温度まで昇温する際には、昇温速度を、１０００℃までは５℃／分～１０℃／分とし、１０００℃を超え１５００℃までは１℃／分～４℃／分とすることが、焼結密度を均一にする点で好ましい。 In sintering in any atmosphere, the sintering temperature is preferably 600 ° C. to 1700 ° C., more preferably 600 ° C. to 1500 ° C., further preferably 1000 ° C. to 1500 ° C., and most preferably 1000 ° C. to 1300 ° C. And If the sintering temperature is lower than 600 ° C., the sintering does not proceed sufficiently, so that the target density is lowered. On the other hand, if it exceeds 1500 ° C., zinc oxide itself decomposes and disappears. When the molded body is heated to the sintering temperature, the rate of temperature increase is 5 ° C./min to 10 ° C./min up to 1000 ° C., and 1 ° C./min to 4 ° C. over 1000 ° C. to 1500 ° C. / Min is preferable in terms of making the sintered density uniform.
　焼結は、例えば、成形体をＺｎＯ粉体内に埋めた状態で分解を防止しながら行なうことにより、得られる焼結体の密度を、好ましくは８０％以上、より好ましくは９０％の高密度とすることが好ましい。高密度の焼結体からなるターゲットは、膜品質の低下、すなわち、特にｆｓ－ＰＬＤ法の場合の結晶性および表面モホロジーの低下を招く可能性のあるアブレーションプルーム内の微粒子を低減するうえで好ましい。 Sintering is performed, for example, by preventing the decomposition in a state where the molded body is buried in the ZnO powder, whereby the density of the obtained sintered body is preferably 80% or more, more preferably 90%. It is preferable to do. A target composed of a high-density sintered body is preferable for reducing fine particles in the ablation plume, which may cause deterioration in film quality, that is, crystallinity and surface morphology, particularly in the case of the fs-PLD method. .
　焼結時間（すなわち、焼結温度での保持時間）は、好ましくは０．５～４８時間、より好ましくは３～１５時間である。 The sintering time (that is, the holding time at the sintering temperature) is preferably 0.5 to 48 hours, more preferably 3 to 15 hours.
　焼結は、特に制限されるものではなく、電気炉、ガス炉、還元炉などを用いて行ってもよく、常圧焼成法、ホットプレス法、熱間等圧プレス（ＨＩＰ）法、放電プラズマ焼結（ＳＰＳ）法、冷間等圧プレス（ＣＩＰ）法など公知の方法を採用することができる。 Sintering is not particularly limited, and may be performed using an electric furnace, a gas furnace, a reduction furnace, or the like. Atmospheric pressure firing method, hot press method, hot isobaric press (HIP) method, discharge plasma Known methods such as a sintering (SPS) method and a cold isostatic pressing (CIP) method can be employed.
　アニール処理を施す際の雰囲気としては、窒素、アルゴン、ヘリウム、二酸化炭素および水素からなる群より選ばれる少なくとも１種からなる雰囲気ならびに真空が挙げられる。アニール処理の方法としては、例えば、窒素、アルゴン、ヘリウム、二酸化炭素、水素などの非酸化性ガスを導入しながら常圧で加熱する方法や、真空（好ましくは、２Ｐａ以下）下で加熱する方法等により行うことができるが、製造コストの観点からは、前者の常圧で行う方法が有利である。 Examples of the atmosphere in performing the annealing treatment include an atmosphere made of at least one selected from the group consisting of nitrogen, argon, helium, carbon dioxide and hydrogen, and a vacuum. As a method of annealing treatment, for example, a method of heating at normal pressure while introducing a non-oxidizing gas such as nitrogen, argon, helium, carbon dioxide, hydrogen, or a method of heating under vacuum (preferably 2 Pa or less) However, the former method is advantageous from the viewpoint of production cost.
　アニール温度（加熱温度）は、好ましくは１０００℃～１４００℃、より好ましくは１１００℃～１３００℃である。アニール時間（加熱時間）は、好ましくは７時間～１５時間、より好ましくは８時間～１２時間である。アニール温度が１０００℃未満であると、アニール処理による酸素欠損の導入が不十分になるおそれがある。一方、１４００℃を超えると、亜鉛が揮散しやすくなり、得られる酸化物焼結体の組成（ＺｎとＴｉとの原子数比）が所望の比率と異なってしまうおそれがある。 The annealing temperature (heating temperature) is preferably 1000 ° C. to 1400 ° C., more preferably 1100 ° C. to 1300 ° C. The annealing time (heating time) is preferably 7 hours to 15 hours, more preferably 8 hours to 12 hours. If the annealing temperature is less than 1000 ° C., introduction of oxygen vacancies by annealing may be insufficient. On the other hand, when it exceeds 1400 ° C., zinc is likely to be volatilized, and the composition of the obtained oxide sintered body (atom ratio of Zn and Ti) may be different from a desired ratio.
　（酸化物混合体）
　本発明の酸化物混合体は、酸化亜鉛と酸化チタンとからなる。すなわち、本発明の酸化物混合体は、実質的に亜鉛、チタンおよび酸素からなる混合体である。ここで、「実質的」とは、酸化物混合体を構成する全原子の９９％以上が亜鉛、チタンまたは酸素からなることを意味する。 (Oxide mixture)
The oxide mixture of the present invention comprises zinc oxide and titanium oxide. That is, the oxide mixture of the present invention is a mixture substantially consisting of zinc, titanium and oxygen. Here, “substantially” means that 99% or more of all atoms constituting the oxide mixture are composed of zinc, titanium, or oxygen.
　本発明の酸化物混合体は、亜鉛とチタンの合計に対するチタンの原子数比Ｔｉ／（Ｚｎ＋Ｔｉ）が０．０２を超え０．１以下である。Ｔｉ／（Ｚｎ＋Ｔｉ）の値が０．０２以下の場合、この酸化物混合体をターゲットとして用いて形成された膜の耐薬品性など化学的耐久性が不十分となる。前記原子数比は、好ましくはＴｉ／（Ｚｎ＋Ｔｉ）＝０．０２５～０．０９、より好ましくはＴｉ／（Ｚｎ＋Ｔｉ）＝０．０３～０．０９、さらに好ましくはＴｉ／（Ｚｎ＋Ｔｉ）＝０．０３～０．０８、最も好ましくはＴｉ／（Ｚｎ＋Ｔｉ）＝０．０４～０．０８である。 In the oxide mixture of the present invention, the atomic ratio Ti / (Zn + Ti) of titanium to the total of zinc and titanium is more than 0.02 and 0.1 or less. When the value of Ti / (Zn + Ti) is 0.02 or less, chemical durability such as chemical resistance of a film formed using this oxide mixture as a target becomes insufficient. The atomic ratio is preferably Ti / (Zn + Ti) = 0.025 to 0.09, more preferably Ti / (Zn + Ti) = 0.03 to 0.09, and further preferably Ti / (Zn + Ti) = 0. 03 to 0.08, most preferably Ti / (Zn + Ti) = 0.04 to 0.08.
　酸化チタンとしては、上述の酸化チタン粉を用いることができる。酸化亜鉛は、通常、ウルツ鉱型構造を有する。本発明の酸化物混合体は、酸化亜鉛粉と酸化チタン粉とを混合し、これを成形、例えば一軸プレス成形等して得られる。酸化物混合体の機械的強度を増すために、成形した酸化物混合体を６００℃未満で加熱してもよい。酸化亜鉛と酸化チタンは６００℃未満であれば、焼結して複合酸化物等を生成することはない。 As the titanium oxide, the above-described titanium oxide powder can be used. Zinc oxide usually has a wurtzite structure. The oxide mixture of the present invention is obtained by mixing zinc oxide powder and titanium oxide powder and molding the mixture, for example, uniaxial press molding. In order to increase the mechanical strength of the oxide mixture, the shaped oxide mixture may be heated below 600 ° C. If zinc oxide and titanium oxide are less than 600 ° C., they are not sintered to produce a composite oxide or the like.
　酸化チタン（III）は酸素が存在する雰囲気中（大気雰囲気および酸化雰囲気）で、４００℃以上に加熱すると酸化され、酸化チタン（IV）に変化する。しかし、酸素が存在しない還元雰囲気および不活性雰囲気で、加熱温度が６００℃未満であれば、焼結せずに混合体として存在することができる。酸素が存在する雰囲気（酸化雰囲気および大気雰囲気）であれば、４００℃未満で加熱するのが好ましい。このように加熱することにより酸化物混合体の機械的強度を高くすることができる。混合体自体の強度が増すので、例えばターゲットとして過酷な条件（高電力など）で成膜してもクラックを生じにくい。 Titanium (III) oxide is oxidized in an atmosphere containing oxygen (air atmosphere and oxidizing atmosphere) and heated to 400 ° C. or higher to change to titanium (IV) oxide. However, if the heating temperature is less than 600 ° C. in a reducing atmosphere and an inert atmosphere in which oxygen is not present, it can exist as a mixture without sintering. If the atmosphere contains oxygen (oxidizing atmosphere and air atmosphere), it is preferable to heat at less than 400 ° C. By heating in this way, the mechanical strength of the oxide mixture can be increased. Since the strength of the mixture itself increases, for example, even if a film is formed under severe conditions (high power, etc.) as a target, cracks are hardly generated.
　本発明の酸化物混合体は、上述の添加元素や不純物を含有していてもよい。添加元素や不純物の含有量は、上述の通りである。 The oxide mixture of the present invention may contain the above-described additive elements and impurities. The contents of additive elements and impurities are as described above.
　（酸化物混合体の製造方法）
　本発明の酸化物混合体の製造方法は、酸化チタン粉と酸化亜鉛粉との混合粉もしくは酸化チタン粉と水酸化亜鉛粉との混合粉を成形することにより、上記本発明の酸化物混合体を得る方法である。原料粉末としては、酸化チタン粉と酸化亜鉛粉との混合粉もしくは酸化チタン粉と水酸化亜鉛粉との混合粉であればよい。好ましくは、酸化チタン粉と酸化亜鉛粉との混合粉もしくは酸化チタン粉と水酸化亜鉛粉との混合粉を含むものがよい。これらの酸化チタン粉、酸化亜鉛粉および水酸化亜鉛粉としては、上述の酸化物焼結体と同様のものを使用することができる。 (Method for producing oxide mixture)
The method for producing the oxide mixture of the present invention comprises forming the mixed powder of titanium oxide powder and zinc oxide powder or the mixed powder of titanium oxide powder and zinc hydroxide powder, thereby forming the oxide mixture of the present invention. Is the way to get. The raw material powder may be a mixed powder of titanium oxide powder and zinc oxide powder or a mixed powder of titanium oxide powder and zinc hydroxide powder. It is preferable to include a mixed powder of titanium oxide powder and zinc oxide powder or a mixed powder of titanium oxide powder and zinc hydroxide powder. As these titanium oxide powder, zinc oxide powder and zinc hydroxide powder, those similar to the above-mentioned oxide sintered body can be used.
　原料粉末として酸化チタン粉と酸化亜鉛粉との混合粉もしくは酸化チタン粉と水酸化亜鉛粉との混合粉を用いる場合の各粉の混合割合は、各々用いる化合物（粉）の種類に応じて、最終的に得られる酸化物混合体において原子数比でＴｉ／（Ｚｎ＋Ｔｉ）の値が上述の範囲となるように適宜設定すればよい。 When using a mixed powder of titanium oxide powder and zinc oxide powder or a mixed powder of titanium oxide powder and zinc hydroxide powder as the raw material powder, the mixing ratio of each powder depends on the type of compound (powder) used, What is necessary is just to set suitably so that the value of Ti / (Zn + Ti) may become the above-mentioned range by atomic ratio in the oxide mixture finally obtained.
　原料粉末を成形する際の方法は、特に制限されず、例えば、上記酸化物焼結体と同様の方法で行われる。 The method for forming the raw material powder is not particularly limited, and is performed, for example, by the same method as that for the oxide sintered body.
　得られた成形体は、機械的強度を高くするため、加熱してアニール処理が行われる。アニールは、常圧アニール法、ホットプレス法、ＨＩＰ法、ＳＰＳ法、ＣＩＰ法など公知の方法で行われる。例えば、大気雰囲気、不活性雰囲気、真空、還元雰囲気などの雰囲気（例えば、窒素、アルゴン、ヘリウム、二酸化炭素、真空（好ましくは２Ｐａ以下）、水素等）または酸化雰囲気（大気よりも酸素濃度が高い雰囲気）のいずれかの雰囲気中、５０℃以上６００℃未満で行なう。そして、酸化雰囲気または大気雰囲気中でアニールした場合、４００℃以下で行うことが望ましい。ＴｉＯ，Ｔｉ2Ｏ3がＴｉＯ2に酸化されてしまうからである。酸化チタンとしてＴｉＯ2を用いた場合、６００℃未満であれば、上記雰囲気のいずれでも構わない。また、製造コストの観点から、アニールは、常圧で行う方法が有利である。アニールすることにより、混合成形体の機械的強度を高めることができる。いずれの雰囲気中でアニールする際も、アニール時間（すなわち、アニール温度での保持時間）は、１時間～１５時間とすることが好ましい。アニール時間が１時間未満であると、機械的強度の向上が十分ではない。 The obtained molded body is heated and annealed to increase the mechanical strength. Annealing is performed by a known method such as an atmospheric annealing method, a hot press method, an HIP method, an SPS method, or a CIP method. For example, an atmosphere (for example, nitrogen, argon, helium, carbon dioxide, vacuum (preferably 2 Pa or less), hydrogen, etc.) such as an air atmosphere, an inert atmosphere, a vacuum, a reducing atmosphere, or an oxidizing atmosphere (oxygen concentration higher than air) (Atmosphere) is performed at 50 ° C or higher and lower than 600 ° C. When annealing is performed in an oxidizing atmosphere or an air atmosphere, it is desirable that the annealing be performed at 400 ° C. or lower. This is because TiO and Ti 2 O 3 are oxidized to TiO 2 . When TiO 2 is used as titanium oxide, any of the above atmospheres may be used as long as it is lower than 600 ° C. Further, from the viewpoint of manufacturing cost, annealing is advantageously performed at normal pressure. By annealing, the mechanical strength of the mixed molded body can be increased. When annealing in any atmosphere, the annealing time (that is, the holding time at the annealing temperature) is preferably 1 hour to 15 hours. If the annealing time is less than 1 hour, the mechanical strength is not sufficiently improved.
　（ターゲット）
　本発明のターゲットは、例えば、パルスレーザ堆積法（ＰＬＤ法）、スパッタリング法、イオンプレーティング法またはエレクトロンビーム（ＥＢ）蒸着法による成膜に用いられるターゲットである。なお、このような成膜の際に用いる固形材料のことを「タブレット」と称する場合もあるが、本発明においてはこれらを含め「ターゲット」と記載する。さらに、真空蒸着法などの他の真空成膜法、化学気相成長法、ミストＣＶＤ法、ゾルゲル法等の一般的な成膜方法により成膜することも可能である。 (target)
The target of the present invention is a target used for film formation by, for example, a pulse laser deposition method (PLD method), a sputtering method, an ion plating method, or an electron beam (EB) evaporation method. In addition, although the solid material used at the time of such film-forming may be called a "tablet", in this invention, these are described as a "target." Furthermore, it is also possible to form a film by a general film forming method such as another vacuum film forming method such as a vacuum vapor deposition method, a chemical vapor deposition method, a mist CVD method, or a sol-gel method.
　本発明のターゲットは、上述した本発明の酸化物焼結体または酸化物混合体を所定の形状および所定の寸法に加工してなる。加工方法は、特に制限されず、適宜公知の方法を採用すればよい。例えば、酸化物焼結体または酸化物混合体に平面研削等を施した後、所定の寸法に切断してから、支持台に貼着することにより、本発明のターゲットを得ることができる。また、必要に応じて、複数枚の酸化物焼結体または酸化物混合体を分割形状にならべて、大面積のターゲット（複合ターゲット）としてもよい。 The target of the present invention is obtained by processing the above-described oxide sintered body or oxide mixture of the present invention into a predetermined shape and predetermined dimensions. A processing method in particular is not restrict | limited, What is necessary is just to employ | adopt a well-known method suitably. For example, the surface of the oxide sintered body or the oxide mixture is subjected to surface grinding and the like, then cut to a predetermined size, and then attached to a support base, whereby the target of the present invention can be obtained. Further, if necessary, a plurality of oxide sintered bodies or oxide mixtures may be divided into divided shapes to form a large area target (composite target).
　（パルスレーザ堆積法（ＰＬＤ法））
　本発明の酸化亜鉛系透明導電膜の形成方法は、ＰＬＤ法が採用され得る。具体的手法や条件などについては、上述のターゲット（膜形成材料）を用いること以外、特に制限はなく、公知の手法や条件を適宜採用すればよい。以下、ＰＬＤ法について説明するが、これらに限定されない。 (Pulse laser deposition method (PLD method))
The PLD method can be adopted as the method for forming the zinc oxide-based transparent conductive film of the present invention. The specific method and conditions are not particularly limited except that the above-described target (film forming material) is used, and known methods and conditions may be appropriately employed. Hereinafter, although PLD method is demonstrated, it is not limited to these.
　ＰＬＤ法は、ターゲット等の膜形成材料の上にパルスレーザビームを集光させ、集光されたレーザパルスの高いパワー密度により、ターゲットの表面上の膜形成材料（酸化チタン、酸化亜鉛の混合体）を融除させてプラズマを形成させ、これを基板表面上に堆積させるものである。このとき、ターゲットと基板は両方とも高真空室内に設置されており、フィードスルー機構によってその動作を制御されている。 In the PLD method, a pulse laser beam is focused on a film forming material such as a target, and the film forming material (a mixture of titanium oxide and zinc oxide) on the surface of the target is obtained by the high power density of the focused laser pulse. ) Is ablated to form plasma, which is deposited on the substrate surface. At this time, both the target and the substrate are installed in a high vacuum chamber, and their operations are controlled by a feedthrough mechanism.
　ＰＬＤ法で最も幅広く使用されているパルスレーザ源は、エキシマレーザである。エキシマレーザは、数ナノ秒（ｎｓ）のパルス幅と、ＵＶ領域内の波長とを備えている。その典型的なフルエンス（エネルギー範囲密度）は、典型的な１０ｍｍ2の集光スポットについて数Ｊ／ｃｍ2である。但し、ナノ秒レーザＰＬＤ法では、数ミクロンの寸法の大型液滴が発生することになるので、工業的なナノ秒ＰＬＤの幅広い使用には適さない。そこで、ＰＬＤ法で使用するアブレーションのエネルギー源（パルスレーザ源）としては、フェムト秒レーザまたは類似の超短パルスレーザを使用することが好ましい。ナノ秒レーザパルスと比べて、フェムト秒～ピコ秒のレーザパルスは、その超短のパルス幅のためにピークパワーが遥かに高く、また、アブレーション機構もナノ秒レーザアブレーションのものとは本質的に異なる。基本的な違いは、フェムト秒パルス幅中、ターゲットの内部には無視できる程度の熱伝導しか生じないため、アブレーションは基本的に非溶融状況において発生する。したがって、フェムト秒ＰＬＤ法（ｆｓ－ＰＬＤ法）を用いれば、液滴が生じない薄膜が得られるので好ましい。 The most widely used pulse laser source in the PLD method is an excimer laser. The excimer laser has a pulse width of several nanoseconds (ns) and a wavelength in the UV region. Its typical fluence (energy range density) is a few J / cm 2 for a typical 10 mm 2 focused spot. However, the nanosecond laser PLD method generates large droplets having a size of several microns, and is not suitable for a wide range of industrial nanosecond PLDs. Therefore, it is preferable to use a femtosecond laser or a similar ultrashort pulse laser as an ablation energy source (pulse laser source) used in the PLD method. Compared to nanosecond laser pulses, femtosecond to picosecond laser pulses have a much higher peak power due to their ultrashort pulse width, and the ablation mechanism is essentially that of nanosecond laser ablation. Different. The basic difference is that during the femtosecond pulse width, only negligible heat conduction occurs inside the target, so ablation basically occurs in an unmelted situation. Therefore, it is preferable to use the femtosecond PLD method (fs-PLD method) because a thin film in which no droplet is generated can be obtained.
　フェムト秒ＰＬＤ法により成膜を行う際には、使用するフェムト秒パルスレーザのレーザビームのパルス幅は、通常１０ｆｓ～１ｐｓとし、パルスエネルギーは通常２μＪ～１００ｍＪとする。最初に、ビームを顕微鏡で１０倍に拡大し、その後、集光レンズでターゲット表面上に集光する。これを小さく集光することで、集光スポットにおけるフルエンス（エネルギー密度）を、４００μｍ2のスポット寸法で最大２５０Ｊ／ｃｍ2まで変化できる。超短パルスの非常に高いピークパワー（＞５×１０6Ｗ）のために、フェムト秒レーザを使用したときの膜形成材料（Ｔｉ含有ＺｎＯ）の融除の閾値は、ナノ秒パルスレーザの場合と比べて比較的低い。Ｔｉ含有ＺｎＯターゲットを融除し、アブレーションプラズマを生成するためには、フルエンスは１Ｊ／ｃｍ2よりも高ければ十分である。しかし、プラズマプルーム中の粒子数を減少させるためには、最大５Ｊ／ｃｍ2の高いフルエンスが好ましい。 When film formation is performed by the femtosecond PLD method, the pulse width of the laser beam of the femtosecond pulse laser to be used is usually 10 fs to 1 ps, and the pulse energy is usually 2 μJ to 100 mJ. First, the beam is magnified 10 times with a microscope, and then condensed on the target surface with a condenser lens. By condensing this small, the fluence (energy density) at the focused spot can be changed to a maximum of 250 J / cm 2 with a spot size of 400 μm 2 . Due to the very high peak power (> 5 × 10 6 W) of ultrashort pulses, the ablation threshold of the film-forming material (Ti-containing ZnO) when using a femtosecond laser is the case for a nanosecond pulse laser Is relatively low. A fluence higher than 1 J / cm 2 is sufficient to ablate the Ti-containing ZnO target and generate ablation plasma. However, a high fluence of up to 5 J / cm 2 is preferred to reduce the number of particles in the plasma plume.
　パルスレーザ源と、パルスレーザの波長に対して透明な基板と、基板に照射して加熱するための連続波（ＣＷ）赤外線レーザと、マルチターゲットシステムとを装備している装置を用いれば、透明な基板上に透明な薄膜をパルスレーザ堆積したり、多層周期構造を直接堆積したりすることができる。例えば、基板の裏面からパルスレーザを入射し、基板を貫通してターゲット上に集光させると、ターゲットから融除された膜形成材料が、ターゲットと対向した基板の表面上に付着する。その際、基板をターゲットに対して並進移動させることで、基板からターゲットまでの距離を変更できる。基板をターゲットから遠ざければ、大面積薄膜を成膜できる。基板をターゲットに極接近させれば、基板／ターゲット間の短い距離と、その基部におけるアブレーションプルームの狭い角度分布とによって、基板上にレーザの集光スポットと同程度の寸法の微細パターンを成膜することができる。基板を横方向に並進移動させれば、パターン構造（例えば、周期的なライン、格子、ドット）を成膜できる。基板／ターゲット間の長い距離と短い距離のそれぞれにて、異なる材料を用いて、２つの成膜プロセスを交互に実施すれば、多層の周期的誘電体構造を成膜できる。 Using a device equipped with a pulse laser source, a substrate transparent to the wavelength of the pulse laser, a continuous wave (CW) infrared laser for irradiating and heating the substrate, and a multi-target system, it is transparent A transparent thin film can be deposited by pulse laser on a simple substrate, or a multilayer periodic structure can be deposited directly. For example, when a pulse laser is incident from the back surface of the substrate and is focused on the target through the substrate, the film forming material ablated from the target adheres to the surface of the substrate facing the target. At that time, the distance from the substrate to the target can be changed by translating the substrate relative to the target. If the substrate is away from the target, a large area thin film can be formed. When the substrate is very close to the target, a fine pattern with the same size as the laser focused spot is formed on the substrate due to the short distance between the substrate and the target and the narrow angular distribution of the ablation plume at the base. can do. If the substrate is translated in the lateral direction, a pattern structure (for example, periodic lines, lattices, dots) can be formed. A multilayer periodic dielectric structure can be deposited by alternately performing two deposition processes using different materials at each of a long distance and a short distance between the substrate and the target.
　基板は、最高９００℃にまで加熱できる基板ヒータに搭載される。そして、基板マニピュレータが基板の表面に横方向及び回転的な動作を与え、該基板マニピュレータを使用して基板とターゲットの間の距離を調整できる。また、真空系は、ターボ分子ポンプで真空排気されることにより、１．５×１０-8Ｔｏｒｒのベース圧力で動作する。膜の成長中には、吸気口と排気口から別のガスを室に充填することもでき、例えば、室を０．１～２０ミリＴｏｒｒの酸素で充填することができる。 The substrate is mounted on a substrate heater that can be heated up to 900 ° C. The substrate manipulator then applies lateral and rotational motion to the surface of the substrate, and the substrate manipulator can be used to adjust the distance between the substrate and the target. The vacuum system is operated at a base pressure of 1.5 × 10 −8 Torr by being evacuated by a turbo molecular pump. During film growth, different gases can be filled into the chamber from the inlet and outlet, for example, the chamber can be filled with 0.1-20 milliTorr of oxygen.
　レーザアブレーションは、レーザビームがターゲット表面上に集光された際に生じる。膜の成長中に、レーザ集光スポットが固定される一方で、ディスク型のターゲットがその表面垂直軸の周囲で回転されて、その表面に沿って、横方向に行ったり来たりの並進運動を行う。これは、ターゲット表面にわたるレーザビームの走査に相当する。このとき、回転の角速度は通常１ｒｅｖ／秒程度である。横方向への並進運動速度は通常０．３ｍｍ／秒程度であり、フルエンスは通常２０Ｊ／ｃｍ-2程度である。パルス繰り返し周波数は１ｋＨｚに保つ。 Laser ablation occurs when a laser beam is focused on the target surface. During film growth, the laser focused spot is fixed, while the disk-type target is rotated around its surface vertical axis to perform lateral translation back and forth along its surface. Do. This corresponds to scanning the laser beam across the target surface. At this time, the angular velocity of rotation is usually about 1 rev / sec. The translational velocity in the lateral direction is usually about 0.3 mm / second, and the fluence is usually about 20 J / cm −2 . The pulse repetition frequency is kept at 1 kHz.
　レーザビームをターゲット表面上に集光させる前には、予め、基板を最高６００℃に加熱してガスを放出させておいた後、基板を酸素プラズマで約５分間処理することにより、基板から炭化水素による汚れを除去することが好ましい。また、レーザビームをターゲット表面上に集光させる前には、予め、約２０分間かけてターゲット表面のプレアブレーション（事前融除）を行うことが好ましい。プレアブレーションの目的は、製造過程で汚れたターゲット表面を洗浄することである。プレアブレーションの最中には、ターゲットと基板の間にシャッタが挿入し、基板表面を保護する。 Before condensing the laser beam on the target surface, the substrate is heated to a maximum of 600 ° C. to release the gas, and then the substrate is treated with oxygen plasma for about 5 minutes to carbonize the substrate. It is preferable to remove the contamination due to hydrogen. In addition, it is preferable to perform pre-ablation (pre-ablation) of the target surface in advance for about 20 minutes before condensing the laser beam on the target surface. The purpose of pre-ablation is to clean the target surface that is dirty during the manufacturing process. During pre-ablation, a shutter is inserted between the target and the substrate to protect the substrate surface.
　（スパッタリング法）
　本発明の酸化亜鉛系透明導電膜の形成方法は、スパッタリング法が採用され得る。具体的手法や条件などについては、上述の膜形成材料を用いること以外、特に制限はなく、公知のスパッタリング法の手法や条件を適宜採用すればよい。 (Sputtering method)
A sputtering method may be employed as the method for forming the zinc oxide-based transparent conductive film of the present invention. The specific method and conditions are not particularly limited except that the above-described film forming materials are used, and a known sputtering method and conditions may be appropriately employed.
　スパッタリング法による成膜は、例えば、ターゲットをスパッタリング装置内に設置し、この装置内にスパッタリングガスを導入し、直流（ｄｃ）または高周波（ｒｆ）あるいは双方の電界を印可してスパッタリングを行うことにより、基板上に薄膜を形成することができる。 Film formation by sputtering is performed, for example, by placing a target in a sputtering apparatus, introducing a sputtering gas into the apparatus, and applying a direct current (dc) or a high frequency (rf) electric field or performing sputtering. A thin film can be formed on the substrate.
　スパッタリングガスとしては、通常、不活性ガス（例えば、Ａｒなど）が濃度９９．９９５％以上で用いられる。必要に応じて、酸化性ガスや還元性ガスを併用することもできる。しかし、質的に酸素を含まないことが好ましく、酸素濃度は、例えば好ましくは０．０５％未満である。スパッタリング法による成膜条件は、特に制限されないが、例えば、圧力は通常０．1～１０Ｐａ、基板温度は通常２５～３００℃で行うことができる。 As the sputtering gas, an inert gas (for example, Ar) is usually used at a concentration of 99.995% or more. If necessary, an oxidizing gas or a reducing gas can be used in combination. However, it is preferable not to contain oxygen qualitatively, and the oxygen concentration is preferably less than 0.05%, for example. The film formation conditions by the sputtering method are not particularly limited. For example, the pressure is usually 0.1 to 10 Pa, and the substrate temperature is usually 25 to 300 ° C.
　スパッタリングの方式は、特に制限されるものではなく、例えば、ＤＣスパッタリング法（直流スパッタリング法）、ＲＦスパッタリング法（高周波スパッタリング法）、ＡＣスパッタリング法（交流スパッタリング法）またはこれらを組み合わせた方法の中から、使用するターゲットの比抵抗等に応じて適宜採用することができる。例えば、ＤＣスパッタリング法は、他の方式に比べて成膜速度が速く、スパッタリング効率に優れ、しかもＤＣスパッタリング装置は、安価で、制御が容易であり、電力消費量も少ないという利点がある。しかし、これらの方法は、ターゲットが絶縁体であると採用できない。これに対して、ＲＦスパッタリング法では、ターゲットがたとえ絶縁体であっても採用することができる。 The method of sputtering is not particularly limited. For example, the sputtering method (direct current sputtering method), the RF sputtering method (high frequency sputtering method), the AC sputtering method (alternating current sputtering method), or a combination of these methods can be used. Depending on the specific resistance of the target to be used, etc., it can be appropriately employed. For example, the DC sputtering method has an advantage that the film forming speed is higher than other methods, the sputtering efficiency is excellent, and the DC sputtering apparatus is inexpensive, easy to control, and consumes less power. However, these methods cannot be employed when the target is an insulator. In contrast, the RF sputtering method can be used even if the target is an insulator.
　（イオンプレーティング法）
　さらに、本発明の酸化亜鉛系透明導電膜の形成方法は、イオンプレーティング法が採用され得る。イオンプレーティング法は、成膜室に配設した電極部としてのハース等に、膜形成材料（蒸着材料）を配置し、この蒸着材料に例えばアルゴンプラズマを照射して蒸着材料を加熱し、蒸発させ、プラズマを通過した蒸着材料の各粒子をハース等に対向する位置に置かれた基板に成膜させる方法である。イオンプレーティング法の具体的手法や条件などについては、上述の膜形成材料を用いること以外、特に制限はなく、公知のイオンプレーティング法の手法や条件を適宜採用すればよい。 (Ion plating method)
Furthermore, an ion plating method can be adopted as the method for forming the zinc oxide-based transparent conductive film of the present invention. In the ion plating method, a film forming material (evaporation material) is arranged on a hearth as an electrode portion disposed in a film forming chamber, and the evaporation material is heated by irradiating, for example, argon plasma to the evaporation material. Then, each particle of the vapor deposition material that has passed through the plasma is formed on a substrate placed at a position facing the hearth or the like. The specific method and conditions of the ion plating method are not particularly limited except that the film forming material described above is used, and a known method and conditions of the ion plating method may be appropriately employed.
　以下、イオンプレーティング法の一実施形態について図面を用いて説明する。図１は、イオンプレーティング法を実施するのに好適なイオンプレーティング装置の一例を示す。イオンプレーティング装置１０は、成膜室である真空容器１２と、真空容器１２中にプラズマビームＰＢを供給するプラズマ源であるプラズマガン（プラズマビーム発生器）１４と、真空容器１２内の底部に配置されてプラズマビームＰＢが入射する陽極部材１６と、成膜の対象である基板Ｗを保持する基板保持部材ＷＨを陽極部材１６の上方で適宜移動させる搬送機構１８とを備える。 Hereinafter, an embodiment of the ion plating method will be described with reference to the drawings. FIG. 1 shows an example of an ion plating apparatus suitable for performing the ion plating method. The ion plating apparatus 10 includes a vacuum vessel 12 that is a film forming chamber, a plasma gun (plasma beam generator) 14 that is a plasma source that supplies a plasma beam PB into the vacuum vessel 12, and a bottom portion in the vacuum vessel 12. An anode member 16 that is disposed and on which the plasma beam PB is incident is provided, and a transport mechanism 18 that appropriately moves a substrate holding member WH that holds a substrate W to be deposited above the anode member 16.
　プラズマガン１４は、圧力勾配型であり、その本体部分は真空容器１２の側壁に備えられる。プラズマガン１４の陰極１４ａ、中間電極１４ｂ、１４ｃ、電磁石コイル１４ｄおよびステアリングコイル１４ｅへの給電を調整することにより、真空容器１２中に供給されるプラズマビームＰＢの強度や分布状態が制御される。なお、参照符号２０ａは、プラズマビームＰＢのもととなる、Ａｒ等の不活性ガスからなるキャリアガスの導入路を示す。陽極部材１６は、プラズマビームＰＢを下方に導く主陽極であるハース１６ａと、その周囲に配置された環状の補助陽極１６ｂとからなる。 The plasma gun 14 is a pressure gradient type, and its main body is provided on the side wall of the vacuum vessel 12. By adjusting the power supply to the cathode 14a, the intermediate electrodes 14b and 14c, the electromagnet coil 14d and the steering coil 14e of the plasma gun 14, the intensity and distribution state of the plasma beam PB supplied into the vacuum vessel 12 are controlled. Reference numeral 20a indicates a carrier gas introduction path made of an inert gas such as Ar, which is the source of the plasma beam PB. The anode member 16 includes a hearth 16a as a main anode for guiding the plasma beam PB downward, and an annular auxiliary anode 16b disposed around the hearth 16a.
　ハース１６ａは、適当な正電位に制御されており、プラズマガン１４から出射したプラズマビームＰＢを下方に吸引する。ハース１６ａは、プラズマビームＰＢが入射する中央部に貫通孔ＴＨが形成されており、貫通孔ＴＨに蒸着材料２２が装填されている。蒸着材料２２は、柱状若しくは棒状に成形されたタブレットであり、プラズマビームＰＢからの電流によって加熱されて昇華し、蒸着物質を生成する。ハース１６ａは蒸着材料２２を徐々に上昇させる構造を有しており、蒸着材料２２の上端は常に一定量だけハース１６ａの貫通孔ＴＨから突出している。 The hearth 16a is controlled to an appropriate positive potential and sucks the plasma beam PB emitted from the plasma gun 14 downward. In the hearth 16a, a through hole TH is formed at a central portion where the plasma beam PB is incident, and a vapor deposition material 22 is loaded in the through hole TH. The vapor deposition material 22 is a tablet formed into a columnar shape or a rod shape, and is heated and sublimated by an electric current from the plasma beam PB to generate a vapor deposition material. The hearth 16a has a structure for gradually raising the vapor deposition material 22, and the upper end of the vapor deposition material 22 always protrudes from the through hole TH of the hearth 16a by a certain amount.
　補助陽極１６ｂは、ハース１６ａの周囲に同心に配置された環状の容器で構成され、容器内には、永久磁石２４ａとコイル２４ｂとが収容されている。これら永久磁石２４ａおよびコイル２４ｂは、磁場制御部材であり、ハース１６ａの直上にカスプ状磁場を形成し、これにより、ハース１６ａに入射するプラズマビームＰＢの向きが制御され、修正される。 The auxiliary anode 16b is composed of an annular container arranged concentrically around the hearth 16a, and a permanent magnet 24a and a coil 24b are accommodated in the container. The permanent magnet 24a and the coil 24b are magnetic field control members, and form a cusp-like magnetic field directly above the hearth 16a, whereby the direction of the plasma beam PB incident on the hearth 16a is controlled and corrected.
　搬送機構１８は、搬送路１８ａ内に水平方向に等間隔で配列されて基板保持部材ＷＨを支持する多数のコロ１８ｂと、コロ１８ｂを回転させて基板保持部材ＷＨを所定の速度で水平方向に移動させる図示しない駆動装置とを備える。基板保持部材ＷＨに基板Ｗが保持される。この場合、基板Ｗを搬送する搬送機構１８を設けることなく、真空容器１２の内部の上方に基板Ｗを固定して配置してもよい。 The transport mechanism 18 has a large number of rollers 18b arranged in the transport path 18a at equal intervals in the horizontal direction to support the substrate holding member WH, and rotates the rollers 18b to move the substrate holding member WH horizontally at a predetermined speed. And a drive device (not shown) to be moved. The substrate W is held by the substrate holding member WH. In this case, the substrate W may be fixedly disposed above the inside of the vacuum vessel 12 without providing the transport mechanism 18 for transporting the substrate W.
　真空容器１２には、酸素ガス容器１９中の酸素ガスがマスフローメータ２１によって流量を所定量に調整されながら供給される。なお、参照符号２０ｂは酸素以外の雰囲気ガスを供給するための供給路を示し、また、参照符号２０ｃはＡｒ等の不活性ガスをハース１６ａに供給するための供給路を示し、また、参照符号２０ｄは排気系を示す。 The oxygen gas in the oxygen gas container 19 is supplied to the vacuum container 12 while the flow rate is adjusted to a predetermined amount by the mass flow meter 21. Reference numeral 20b indicates a supply path for supplying an atmospheric gas other than oxygen, and reference numeral 20c indicates a supply path for supplying an inert gas such as Ar to the hearth 16a. Reference numeral 20d denotes an exhaust system.
　図１のイオンプレーティング装置１０を用いたイオンプレーティング方法を説明する。まず、真空容器１２の下部に配置されたハース１６ａの貫通孔ＴＨに蒸着材料２２を装着する。一方、ハース１６ａの上方の対向する位置に基板Ｗを配置する。次に、成膜条件に応じたプロセスガスを真空容器１２の内部に導入する。プラズマガン１４の陰極１４ａおよびハース１６ａ間に直流電圧を印加する。そして、プラズマガン１４の陰極１４ａとハース１６ａとの間で放電を生じさせ、これにより、プラズマビームＰＢを生成する。プラズマビームＰＢは、ステアリングコイル１４と補助陽極１６ｂ内の永久磁石２４ａ等とによって決定される磁界に案内されてハース１６ａに到達する。この際、蒸材料２２の周囲にアルゴンガスが供給されるので、容易にプラズマビームＰＢがハース１６ａに引き寄せられる。 An ion plating method using the ion plating apparatus 10 of FIG. 1 will be described. First, the vapor deposition material 22 is attached to the through hole TH of the hearth 16a disposed at the lower part of the vacuum vessel 12. On the other hand, the substrate W is disposed at an opposing position above the hearth 16a. Next, a process gas corresponding to the film forming conditions is introduced into the vacuum vessel 12. A DC voltage is applied between the cathode 14a of the plasma gun 14 and the hearth 16a. Then, a discharge is generated between the cathode 14a of the plasma gun 14 and the hearth 16a, thereby generating a plasma beam PB. The plasma beam PB reaches the hearth 16a by being guided by a magnetic field determined by the steering coil 14 and the permanent magnet 24a in the auxiliary anode 16b. At this time, since argon gas is supplied around the steamed material 22, the plasma beam PB is easily attracted to the hearth 16a.
　プラズマに曝された蒸着材料２２は、徐々に加熱される。蒸着材料２２が十分に加熱されると、蒸着材料２２が昇華し、蒸着物質が蒸発（出射）する。蒸着物質は、プラズマビームＰＢによりイオン化され、基板Ｗに付着（入射）し、成膜される。なお、永久磁石２４ａおよびコイル２４ｂによってハース１６ａの上方の磁場を制御することにより、蒸着物質の飛行方向を制御することができるため、ハース１６ａの上方におけるプラズマの活性度分布や基板Ｗの反応性分布に合わせて基板Ｗの上の成膜速度分布を調整でき、広い面積にわたって均一な膜質の薄膜を得ることができる。 The vapor deposition material 22 exposed to the plasma is gradually heated. When the vapor deposition material 22 is sufficiently heated, the vapor deposition material 22 sublimates and the vapor deposition material evaporates (emits). The vapor deposition material is ionized by the plasma beam PB, adheres (incides) to the substrate W, and is formed into a film. In addition, since the flight direction of the vapor deposition material can be controlled by controlling the magnetic field above the hearth 16a by the permanent magnet 24a and the coil 24b, the plasma activity distribution and the reactivity of the substrate W above the hearth 16a. The film formation speed distribution on the substrate W can be adjusted in accordance with the distribution, and a thin film having a uniform film quality can be obtained over a wide area.
　真空容器１２の酸素分圧は、特に制限されないが、０．０１２Ｐａ以下に調整することが好ましい。また、必要に応じて、プラズマビームを複数個用意して、区画された複数の真空室で、連続的に成膜を行うこともできる。 The oxygen partial pressure of the vacuum vessel 12 is not particularly limited, but is preferably adjusted to 0.012 Pa or less. Further, if necessary, a plurality of plasma beams can be prepared, and film formation can be continuously performed in a plurality of partitioned vacuum chambers.
　（エレクトロンビーム（ＥＢ）蒸着法）
　本発明の酸化亜鉛系透明導電膜の形成方法は、エレクトロンビーム（ＥＢ）蒸着法が採用され得る。具体的手法や条件などについては、上述の膜形成材料を用いること以外、特に制限はなく、公知のエレクトロンビーム（ＥＢ）蒸着法の手法や条件を適宜採用すればよい。エレクトロンビーム（ＥＢ）蒸着法では、原料ターゲット（タブレット）に電子ビームを真空中で照射することにより加熱蒸発させて、対向した透明基板上にこれを堆積させ蒸着を行い、透明導電膜を透明基板上に作製することができる。 (Electron beam (EB) evaporation method)
An electron beam (EB) vapor deposition method can be adopted as the method for forming the zinc oxide-based transparent conductive film of the present invention. The specific method and conditions are not particularly limited except that the above-described film forming material is used, and a known electron beam (EB) vapor deposition method and conditions may be appropriately employed. In the electron beam (EB) vapor deposition method, a raw material target (tablet) is heated and evaporated by irradiating an electron beam in a vacuum, and this is deposited on an opposing transparent substrate for vapor deposition. Can be made on top.
　（酸化亜鉛系透明導電膜）
　本発明の酸化亜鉛系透明導電膜は、上述の酸化亜鉛系透明導電膜の形成方法により形成されたチタンドープ酸化亜鉛からなる透明導電膜である。本発明の酸化亜鉛系透明導電膜中に含まれるチタンと亜鉛の原子数比（Ｔｉ／（Ｚｎ＋Ｔｉ））は、上記の通りである。これにより、チタンのドープ効果により優れた導電性を発現しうるとともに、化学的耐久性にも優れた膜となる。この酸化亜鉛系透明導電膜は、チタンが酸化亜鉛のウルツ鉱の結晶構造の亜鉛サイトに置換固溶したものある。 (Zinc oxide transparent conductive film)
The zinc oxide-based transparent conductive film of the present invention is a transparent conductive film made of titanium-doped zinc oxide formed by the above-described method for forming a zinc oxide-based transparent conductive film. The atomic ratio (Ti / (Zn + Ti)) of titanium and zinc contained in the zinc oxide-based transparent conductive film of the present invention is as described above. As a result, the film can exhibit excellent conductivity due to the doping effect of titanium, and has excellent chemical durability. In this zinc oxide-based transparent conductive film, titanium is substituted and dissolved in zinc sites of a zinc oxide wurtzite crystal structure.
　本発明の酸化亜鉛系透明導電膜は、良好な透明性を有し、かつ、上述のように優れた導電性と化学的耐久性（耐熱性、耐湿性、耐薬品性（耐アルカリ性、耐酸性）など）を兼ね備えたものである。詳しくは、本発明の酸化亜鉛系透明導電膜は、従来の酸化亜鉛系透明導電膜（すなわち、本発明の如く特定量のチタンを含有しない酸化亜鉛系透明導電膜）における最大の欠点であった化学的耐久性を、透明性および導電性を損なうことなく改善したものである。具体的には、従来の酸化亜鉛系透明導電膜は、膜厚に依存するが、耐熱性については、２００℃の大気雰囲気で３０分間加熱すると比抵抗は急激に増大し、耐湿性については、恒温恒湿雰囲気（温度６０℃、相対湿度９０％）に１０時間保持すると比抵抗が約１０倍増大し、１０００時間保持すると絶縁体になってしまうものであった。また、従来の酸化亜鉛系透明導電膜の耐薬品性は、例えば４０℃の３％塩酸水溶液や４０℃の３％水酸化ナトリウム溶液に浸漬すると１０分後には完全に消失してしまうものであった。 The zinc oxide-based transparent conductive film of the present invention has good transparency and has excellent conductivity and chemical durability (heat resistance, moisture resistance, chemical resistance (alkali resistance, acid resistance) as described above. ) Etc.). Specifically, the zinc oxide-based transparent conductive film of the present invention is the biggest drawback of the conventional zinc oxide-based transparent conductive film (that is, the zinc oxide-based transparent conductive film not containing a specific amount of titanium as in the present invention). Chemical durability is improved without impairing transparency and conductivity. Specifically, although the conventional zinc oxide-based transparent conductive film depends on the film thickness, with respect to heat resistance, the specific resistance increases rapidly when heated in an air atmosphere at 200 ° C. for 30 minutes. When held in a constant temperature and humidity atmosphere (temperature 60 ° C., relative humidity 90%) for 10 hours, the specific resistance increased about 10 times, and when held for 1000 hours, it became an insulator. In addition, the chemical resistance of the conventional zinc oxide-based transparent conductive film disappears completely after 10 minutes when immersed in a 3% hydrochloric acid aqueous solution at 40 ° C. or a 3% sodium hydroxide solution at 40 ° C., for example. It was.
　本発明の酸化亜鉛系透明導電膜の膜厚は、用途に応じて適宜設定すればよく、特に制限されないが、好ましくは５０ｎｍ～６００ｎｍ、より好ましくは１００ｎｍ～５００ｎｍである。５０ｎｍ未満であると、十分な比抵抗が確保できないおそれがあり、一方、６００ｎｍを超えると膜に着色が生じてしまうおそれがある。 The film thickness of the zinc oxide-based transparent conductive film of the present invention may be appropriately set according to the application, and is not particularly limited, but is preferably 50 nm to 600 nm, more preferably 100 nm to 500 nm. If the thickness is less than 50 nm, sufficient specific resistance may not be ensured. On the other hand, if the thickness exceeds 600 nm, the film may be colored.
　（透明導電性基板）
　本発明の透明導電性基板は、透明基材上に、上述の酸化亜鉛系透明導電膜を備えるものである。 (Transparent conductive substrate)
The transparent conductive substrate of the present invention comprises the above-described zinc oxide-based transparent conductive film on a transparent base material.
　透明基材は、種々の成膜方法において形状を維持しうるものであれば、特に限定されない。例えば、各種ガラス等の無機材料、熱可塑性樹脂や熱硬化性樹脂（例えば、エポキシ樹脂、ポリメチルメタクリレート、ポリカーボネート、ポリスチレン、ポリエチレンサルファイド、ポリエーテルスルホン、ポリオレフィン、ポリエチレンテレフタレート、ポリエチレンナフタレート、トリアセチルセルロース、ポリイミドなどのプラスチック類）等の樹脂などで形成された板状物、シート状物、フィルム状物等を用いることができるが、特に、ガラス板、樹脂フィルム又は樹脂シートであるのが好ましい。透明基材の可視光透過率は、通常、９０％以上、好ましくは９５％以上であるのがよい。 The transparent substrate is not particularly limited as long as it can maintain the shape in various film forming methods. For example, inorganic materials such as various glasses, thermoplastic resins and thermosetting resins (for example, epoxy resin, polymethyl methacrylate, polycarbonate, polystyrene, polyethylene sulfide, polyethersulfone, polyolefin, polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose) In addition, a plate-like material, a sheet-like material, a film-like material or the like formed of a resin such as a plastic such as polyimide can be used, and a glass plate, a resin film, or a resin sheet is particularly preferable. The visible light transmittance of the transparent substrate is usually 90% or more, preferably 95% or more.
　透明基材として樹脂フィルムや樹脂シートを用いる場合、成膜で受けるダメージを分散均一化するために、工業的に行われているロールツーロールの成膜方法で、巻き出し速度と巻取り速度をコントロールしながら引張応力をかけた状態で成膜することが好ましい。さらに、あらかじめ樹脂フィルムまたは樹脂シートを加熱した状態で成膜してもよいし、成膜最中に樹脂フィルムまたは樹脂シートを冷却するようにしてもよい。また、成膜でダメージを受ける時間を短縮するため、樹脂フィルムまたは樹脂シートの搬送速度の高速化（例えば１．０ｍ／分以上で）を図ることも効果的であり、この場合は、例えば成膜する樹脂フィルムまたは樹脂シートとターゲットとの距離が短くても成膜が可能となり、工業的プロセスとしては有利である。 When using a resin film or resin sheet as the transparent substrate, in order to disperse and homogenize the damage caused by the film formation, the roll-to-roll film formation method used in the industry is used. It is preferable to form a film in a state where a tensile stress is applied while being controlled. Further, the resin film or the resin sheet may be formed in a heated state in advance, or the resin film or the resin sheet may be cooled during the film formation. It is also effective to increase the speed of transporting the resin film or resin sheet (for example, at 1.0 m / min or more) in order to reduce the time for damage during film formation. Film formation is possible even if the distance between the target resin film or resin sheet and the target is short, which is advantageous as an industrial process.
　透明基材には、必要に応じて、単層または多層からなる絶縁層、半導体層、ガスバリア層または保護層のいずれかが形成されていてもよい。絶縁層としては、酸化珪素膜や窒化酸化珪素膜などが挙げられる。半導体層としては、薄膜トランジスター（ＴＦＴ）などが挙げられ、主にガラス基板に形成される。ガスバリア層としては、酸化珪素膜、窒化酸化珪素膜、アルミニウム酸マグネシウム膜などが挙げられ、水蒸気バリア膜などとして樹脂板もしくは樹脂フィルムに形成される。保護層は、基材の表面を傷や衝撃から守るためのものであり、Ｓｉ系、Ｔｉ系、アクリル樹脂系など各種コーティング層が挙げられる。 The transparent base material may be formed with any of a single layer or multiple layers of an insulating layer, a semiconductor layer, a gas barrier layer, or a protective layer as required. Examples of the insulating layer include a silicon oxide film and a silicon nitride oxide film. Examples of the semiconductor layer include a thin film transistor (TFT), and the semiconductor layer is mainly formed on a glass substrate. Examples of the gas barrier layer include a silicon oxide film, a silicon nitride oxide film, and a magnesium aluminate film, and the gas barrier layer is formed on a resin plate or a resin film as a water vapor barrier film. A protective layer is for protecting the surface of a base material from a damage | wound and an impact, and various coating layers, such as Si type | system | group, Ti type | system | group, and an acrylic resin type | system | group, are mentioned.
　本発明の酸化亜鉛系透明導電性基板の比抵抗は、通常２×１０-3Ω・ｃｍ以下、好ましくは１×１０-4Ω・ｃｍ以下、より好ましくは８×１０-4Ω・ｃｍ以下である。また、その表面抵抗（シート抵抗）は、用途によって異なるが、通常５～１００００Ω／□、好ましくは５～３００Ω／□、より好ましくは１０～３００Ω／□である。なお、比抵抗および表面抵抗は、例えば実施例で後述する方法によって測定することができる。 The specific resistance of the zinc oxide based transparent conductive substrate of the present invention is usually 2 × 10 −3 Ω · cm or less, preferably 1 × 10 −4 Ω · cm or less, more preferably 8 × 10 −4 Ω · cm or less. It is. The surface resistance (sheet resistance) is usually 5 to 10000 Ω / □, preferably 5 to 300 Ω / □, more preferably 10 to 300 Ω / □, although it varies depending on the application. In addition, specific resistance and surface resistance can be measured by the method mentioned later in an Example, for example.
　本発明の酸化亜鉛系透明導電性基板の透過率は、可視光領域で、通常８５％以上、好ましくは９０％以上である。また、その全光線透過率は、好ましくは８０％以上、より好ましくは８５％以上であり、そのヘイズ値は、好ましくは１０％以下、より好ましくは５％以下であるのがよい。なお、透過率は、例えば実施例で後述する方法によって測定することができる。 The transmittance of the zinc oxide-based transparent conductive substrate of the present invention is usually 85% or more, preferably 90% or more in the visible light region. The total light transmittance is preferably 80% or more, more preferably 85% or more, and the haze value is preferably 10% or less, more preferably 5% or less. The transmittance can be measured by, for example, a method described later in the examples.
　本発明の透明導電性基板には、必要に応じて、最外層として、保護膜、反射防止膜、フィルター等の役割や、液晶の視野角の調整、曇り止め等の機能を発揮する任意の樹脂または無機化合物の層を、１層または２層以上積層することができる。 In the transparent conductive substrate of the present invention, if necessary, as an outermost layer, any resin that functions as a protective film, an antireflection film, a filter, etc., functions of adjusting the viewing angle of liquid crystal, preventing fogging, etc. Alternatively, one layer or two or more layers of inorganic compounds can be stacked.
　（酸化亜鉛系透明導電膜形成材料）
　本発明の酸化亜鉛系透明導電膜形成材料は、亜鉛とチタンとの合計に対するチタンの原子数比Ｔｉ／（Ｚｎ＋Ｔｉ）が０．０２を越え０．１以下であり、酸化亜鉛を主成分とし、ガリウムおよびアルミニウムのうち少なくとも一方の酸化物と、酸化チタンとを含む酸化物混合体または酸化物焼結体からなる。 (Zinc oxide-based transparent conductive film forming material)
In the zinc oxide-based transparent conductive film-forming material of the present invention, the atomic ratio Ti / (Zn + Ti) of titanium with respect to the total of zinc and titanium is more than 0.02 and not more than 0.1, and the main component is zinc oxide. It consists of an oxide mixture or oxide sintered body containing at least one oxide of gallium and aluminum and titanium oxide.
　前記原子数比が０．０２以下の場合、この材料をターゲットとして用いて形成された膜の耐薬品性など化学的耐久性が不十分となる。一方、前記原子数比が０．１を超える場合、チタンが亜鉛サイトに十分置換固溶できなくなり、この材料をターゲットとして用いて形成された膜の導電性や透明性が低下する傾向にある。前記原子数比は、好ましくはＴｉ／（Ｚｎ＋Ｔｉ）＝０．０２５～０．０９、より好ましくはＴｉ／（Ｚｎ＋Ｔｉ）＝０．０３～０．０９、さらに好ましくはＴｉ／（Ｚｎ＋Ｔｉ）＝０．０３～０．０８、最も好ましくはＴｉ／（Ｚｎ＋Ｔｉ）＝０．０４～０．０８である。 When the atomic ratio is 0.02 or less, chemical durability such as chemical resistance of a film formed using this material as a target becomes insufficient. On the other hand, when the atomic ratio exceeds 0.1, titanium cannot be sufficiently substituted and dissolved in the zinc site, and the conductivity and transparency of a film formed using this material as a target tend to decrease. The atomic ratio is preferably Ti / (Zn + Ti) = 0.025 to 0.09, more preferably Ti / (Zn + Ti) = 0.03 to 0.09, and further preferably Ti / (Zn + Ti) = 0. 03 to 0.08, most preferably Ti / (Zn + Ti) = 0.04 to 0.08.
　また、ガリウムまたはアルミニウムの原子数の割合は、全金属原子数に対して０．５％以上６％以下である。ガリウムまたはアルミニウムの原子数の割合が０．５％未満の場合、導電性の向上効果が不十分となる。一方、６％を超える場合、ガリウムまたはアルミニウムが亜鉛サイトに置換固溶解しきれなくなり、結晶粒界に析出し、導電性の低下、透過率の低下を招くこととなる。なお、ＡｌとＧａは、両方を用いても構わない。その場合、それらの合計量で前記した０．５％以上６％以下の条件を満たせばよい。ここでいう酸化物混合体や酸化物焼結体の製造方法としては、原料粉末として、酸化アルミニウム粉または酸化ガリウム粉をさらに加えた混合粉を用いる以外は、既に述べた酸化物混合体や酸化物焼結体の製造方法と同様である。 Further, the ratio of the number of atoms of gallium or aluminum is 0.5% or more and 6% or less with respect to the total number of metal atoms. When the ratio of the number of atoms of gallium or aluminum is less than 0.5%, the effect of improving conductivity is insufficient. On the other hand, when it exceeds 6%, gallium or aluminum cannot be completely substituted and dissolved in the zinc site and is precipitated at the crystal grain boundary, resulting in a decrease in conductivity and a decrease in transmittance. Both Al and Ga may be used. In that case, what is necessary is just to satisfy the above-mentioned conditions of 0.5% or more and 6% or less in the total amount thereof. As the manufacturing method of the oxide mixture or oxide sintered body here, the oxide mixture or oxidation described above is used except that a mixed powder further added with aluminum oxide powder or gallium oxide powder is used as the raw material powder. This is the same as the manufacturing method of the sintered product.
　また、ガリウムまたはアルミニウムの原子数の割合は、全金属原子数に対して０．５％以上６％以下である。ガリウムまたはアルミニウムの原子数の割合が０．５％未満の場合、導電性の向上効果が不十分となる。一方、６％を超える場合、ガリウムまたはアルミニウムが亜鉛サイトに置換固溶解しきれなくなり、結晶粒界に析出し、導電性の低下、透過率の低下を招くこととなる。なお、ＡｌとＧａは、両方を用いても構わない。その場合、それらの合計量で前記した１％以上６％以下の条件を満たせばよい。酸化物混合体、酸化物焼結体とは、酸化亜鉛粉と酸化チタン粉と酸化アルミニウム粉とを混合するか、または酸化亜鉛粉と酸化チタン粉と酸化ガリウム粉とを混合し、プレス成形したものである。酸化チタン粉は、上述の通りであり、３価の酸化チタン（III）または２価の酸化チタン（II）が好ましい。また、酸化チタンの結晶相とは、具体的には、Ｔｉ2Ｏ3（III）、ＴｉＯ（II）とする。 Moreover, the ratio of the number of atoms of gallium or aluminum is 0.5% or more and 6% or less with respect to the total number of metal atoms. When the ratio of the number of atoms of gallium or aluminum is less than 0.5%, the effect of improving conductivity is insufficient. On the other hand, when it exceeds 6%, gallium or aluminum cannot be completely substituted and dissolved in the zinc site and is precipitated at the crystal grain boundary, leading to a decrease in conductivity and a decrease in transmittance. Both Al and Ga may be used. In that case, what is necessary is just to satisfy the above-mentioned conditions of 1% or more and 6% or less in the total amount thereof. The oxide mixture and oxide sintered body are prepared by mixing zinc oxide powder, titanium oxide powder and aluminum oxide powder, or mixing zinc oxide powder, titanium oxide powder and gallium oxide powder, and press-molding. Is. The titanium oxide powder is as described above, and trivalent titanium oxide (III) or divalent titanium oxide (II) is preferable. The crystal phase of titanium oxide is specifically Ti 2 O 3 (III) and TiO (II).
　本発明の酸化亜鉛系透明導電膜形成材料は、上述の添加元素（但し、ガリウムおよびアルミニウムを除く）や不純物を含有していてもよい。添加元素や不純物の含有量は、上述の通りである。特に、添加元素を含有することによって、形成される透明導電膜の比抵抗が低下し、導電性を向上させることができる。添加元素の含有量が０．０５％を超える場合、得られる酸化亜鉛系透明導電膜形成材料から形成される膜の比抵抗が増大するおそれがある。 The zinc oxide-based transparent conductive film-forming material of the present invention may contain the above-described additive elements (however, excluding gallium and aluminum) and impurities. The contents of additive elements and impurities are as described above. In particular, by containing an additive element, the specific resistance of the formed transparent conductive film is reduced, and the conductivity can be improved. When the content of the additive element exceeds 0.05%, the specific resistance of a film formed from the obtained zinc oxide-based transparent conductive film forming material may increase.
　また、添加元素は、酸化物の形態で酸化物混合体、酸化物焼結体中に存在していてもよいし、酸化亜鉛相の亜鉛サイトに置換した（固溶した）形態で存在していてもよいし、酸化チタン相のチタンサイトに置換した（固溶した）形態で存在していてもよい。 Further, the additive element may be present in the oxide mixture or oxide sintered body in the form of an oxide, or is present in the form substituted (solid solution) in the zinc site of the zinc oxide phase. Alternatively, it may be present in a form substituted (solid solution) in the titanium site of the titanium oxide phase.
　本発明の酸化亜鉛系透明導電膜形成材料を構成する酸化物焼結体は、好ましくは９３％以上の相対密度、より好ましくは９５％～１００％の相対密度を有する。ここで、相対密度とは、酸化物焼結体の密度を理論密度で除し、１００を掛けたものと定義される。相対密度が９３％未満であると、焼結体の特徴である、成膜速度が速いという特徴を損なわれるおそれがある。 The oxide sintered body constituting the zinc oxide-based transparent conductive film forming material of the present invention preferably has a relative density of 93% or more, more preferably 95% to 100%. Here, the relative density is defined as the density of the oxide sintered body divided by the theoretical density and multiplied by 100. If the relative density is less than 93%, the characteristic of the sintered body, that is, the high film formation rate may be impaired.
　酸化物混合体および酸化物焼結体は、特に限定されず、例えば上述の方法で製造される。 The oxide mixture and the oxide sintered body are not particularly limited, and are manufactured by the above-described method, for example.
　本発明の酸化亜鉛系透明導電膜形成材料は、例えば、スパッタリング法、イオンプレーティング法、パルスレーザ堆積法（ＰＬＤ法）またはエレクトロンビーム（ＥＢ）蒸着法による成膜に用いられるターゲットに加工される。この加工されたターゲットを用いて、例えば、酸化亜鉛系透明導電膜が形成され、この導電膜を透明基板上に形成することにより、透明導電性基板が得られる。 The zinc oxide-based transparent conductive film forming material of the present invention is processed into a target used for film formation by, for example, sputtering, ion plating, pulse laser deposition (PLD), or electron beam (EB) evaporation. . For example, a zinc oxide-based transparent conductive film is formed using the processed target, and a transparent conductive substrate is obtained by forming the conductive film on the transparent substrate.
　（パターニング方法）
　本発明のパターニング方法においては、以上のような酸化亜鉛系薄膜を酸によりエッチングする。 (Patterning method)
In the patterning method of the present invention, the zinc oxide thin film as described above is etched with an acid.
　本発明において用いることのできるエッチング液は、酸を含むものであれば、特に制限されるものではなく、例えばＩＴＯ膜など従来の透明導電膜のパターニングに使用されるエッチング液を用いることができる。酸としては、具体的には、例えば、塩酸、硫酸、硝酸、ハロゲン化水素酸（例えばヨウ化水素酸や臭化水素酸など）、これらの混合物（例えば王水など）等の無機酸や、シュウ酸、酢酸、ギ酸、プロピオン酸、コハク酸、マロン酸、酪酸、クエン酸等の有機酸が挙げられ、これらを含むエッチング液は、通常、適当な溶媒に溶解させた（水）溶液として用いられるが、酸そのものであってもよい。また、エッチング液には、例えば、硫酸アンモニウム、塩化第二鉄などの各種塩を溶解させることもできる。エッチング液は、１種のみを用いてもよいし、２種以上を併用してもよい。 The etching solution that can be used in the present invention is not particularly limited as long as it contains an acid. For example, an etching solution used for patterning a conventional transparent conductive film such as an ITO film can be used. Specific examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrohalic acid (such as hydroiodic acid and hydrobromic acid), and mixtures thereof (such as aqua regia), Examples include organic acids such as oxalic acid, acetic acid, formic acid, propionic acid, succinic acid, malonic acid, butyric acid, citric acid. Etching solutions containing these are usually used as (water) solutions dissolved in a suitable solvent. The acid itself may be used. Also, various salts such as ammonium sulfate and ferric chloride can be dissolved in the etching solution. Only 1 type may be used for etching liquid and it may use 2 or more types together.
　前記エッチング液の濃度は、特に制限されるものではなく、所望のエッチングレートになるように、エッチング液の液温や膜の硬化レベル等に応じて、適宜設定すればよい。前記エッチング液の液温は、１０℃～１５０℃とすることが好ましく、より好ましくは２０℃～１００℃とするのがよい。エッチング液の液温が１０℃未満であると、エッチングできなくなるおそれがあり、一方、１５０℃を超えると、水等の溶媒が揮発しやすくなり、エッチング液の濃度管理が困難となるおそれがある。 The concentration of the etching solution is not particularly limited, and may be set as appropriate according to the liquid temperature of the etching solution, the curing level of the film, and the like so as to obtain a desired etching rate. The temperature of the etching solution is preferably 10 ° C. to 150 ° C., more preferably 20 ° C. to 100 ° C. If the temperature of the etching solution is less than 10 ° C., etching may not be possible. On the other hand, if the temperature exceeds 150 ° C., a solvent such as water tends to volatilize and it may be difficult to control the concentration of the etching solution. .
　前記エッチング液を用いてエッチングを行う際の処理方法は、特に制限はなく、例えば、前記酸化亜鉛系薄膜の上に所望のパターンを有するレジスト膜を形成し、該レジスト膜に覆われていない部分、すなわち該レジスト膜から露出した部分をエッチング液を用いて除去し、その後、レジスト膜を適当な溶剤（例えばメチルセロソルブアセテート等）を用いて剥離、除去することにより、所望のパターンを形成することができる。レジスト膜の形成や除去、エッチング液による露出部の除去を行う際の具体的な手法や条件については、特に制限はなく、例えば、ＩＴＯ膜など従来の透明導電膜に適用されるウェットエッチング処理における手法や条件に準じて適宜行えばよい。 There is no particular limitation on the processing method when performing etching using the etching solution. For example, a portion in which a resist film having a desired pattern is formed on the zinc oxide thin film and is not covered with the resist film. That is, a portion exposed from the resist film is removed using an etching solution, and then the resist film is removed using an appropriate solvent (for example, methyl cellosolve acetate) to form a desired pattern. Can do. There are no particular restrictions on the specific method and conditions for forming and removing the resist film and removing the exposed portion with the etching solution. For example, in a wet etching process applied to a conventional transparent conductive film such as an ITO film. What is necessary is just to carry out suitably according to a method and conditions.
　本発明によりパターニングされた薄膜は、高い導電性を有するものであり、例えば、前記酸化亜鉛系薄膜を前記透明基材上に形成してパターニングすることにより得られる透明導電性基板は、比抵抗が、通常２×１０-3Ω・ｃｍ以下、好ましくは１×１０-3Ω・ｃｍ以下、より好ましくは８×１０-4Ω・ｃｍ以下である。また、その表面抵抗（シート抵抗）は、用途によって異なるが、通常５～１００００Ω／□、好ましくは１０～３００Ω／□であるのが好ましい。 The thin film patterned according to the present invention has high conductivity. For example, the transparent conductive substrate obtained by forming and patterning the zinc oxide thin film on the transparent substrate has a specific resistance. Usually, it is 2 × 10 −3 Ω · cm or less, preferably 1 × 10 −3 Ω · cm or less, more preferably 8 × 10 −4 Ω · cm or less. The surface resistance (sheet resistance) varies depending on the application, but is usually 5 to 10,000 Ω / □, preferably 10 to 300 Ω / □.
　本発明によりパターニングされた薄膜は、通常、透明性にも優れるものであり、例えば、前記酸化亜鉛系薄膜を前記透明基材上に形成してパターニングすることにより得られる透明導電性基板は、透過率が、可視光領域で、通常８５％以上、好ましくは９０％以上である。また、その全光線透過率は、好ましくは８０％以上、より好ましくは８５％以上であり、そのヘイズ値は、好ましくは１０％以下、より好ましくは５％以下である。 The thin film patterned by the present invention is usually excellent in transparency. For example, a transparent conductive substrate obtained by forming and patterning the zinc oxide thin film on the transparent base material is transparent. The rate is usually 85% or more, preferably 90% or more in the visible light region. The total light transmittance is preferably 80% or more, more preferably 85% or more, and the haze value is preferably 10% or less, more preferably 5% or less.
　本発明の酸化物焼結体もしくは酸化物混合体または本発明のターゲットを用いて形成された透明導電膜は、優れた導電性と化学的耐久性（耐熱性、耐湿性、耐薬品性（耐アルカリ性、耐酸性）など）とを兼ね備えたものであるので、例えば、液晶ディスプレイ、プラズマディスプレイ、無機ＥＬ（エレクトロルミネセンス）ディスプレイ、有機ＥＬディスプレイ、電子ペーパーなどの透明電極、太陽電池の光電変換素子の窓電極、透明タッチパネル等の入力装置の電極、電磁シールドの電磁遮蔽膜等の用途に好適に用いられる。さらに、本発明の酸化物焼結体もしくは酸化物混合体または本発明のターゲットを用いて形成された透明導電膜は、透明電波吸収体、紫外線吸収体、さらには透明半導体デバイスとして、他の金属膜や金属酸化膜と組み合わせて活用することもできる。 The transparent conductive film formed using the oxide sintered body or oxide mixture of the present invention or the target of the present invention has excellent conductivity and chemical durability (heat resistance, moisture resistance, chemical resistance (resistance to resistance). For example, liquid crystal display, plasma display, inorganic EL (electroluminescence) display, organic EL display, transparent electrode such as electronic paper, solar cell photoelectric conversion element, etc. It is suitably used for applications such as a window electrode, an electrode of an input device such as a transparent touch panel, and an electromagnetic shielding film of an electromagnetic shield. Furthermore, the transparent conductive film formed using the oxide sintered body or oxide mixture of the present invention or the target of the present invention is used as a transparent radio wave absorber, an ultraviolet absorber, and a transparent semiconductor device as another metal. It can also be used in combination with a film or a metal oxide film.
　本発明によりパターニングされた薄膜は、エッチングレートを十分に制御して得られるものであるので、形成されたパターン形状が正確である。 Since the thin film patterned by the present invention is obtained by sufficiently controlling the etching rate, the formed pattern shape is accurate.
　以下、実施例により本発明をより詳細に説明するが、本発明は、かかる実施例により限定されるものではない。
　＜比抵抗＞
　比抵抗は、抵抗率計（三菱化学（株）製「ＬＯＲＥＳＴＡ－ＧＰ、ＭＣＰ－Ｔ６１０」)を用いて、四端子四探針法により測定した。詳しくは、サンプルに４本の針状の電極を直線上に置き、外側の二探針間に一定の電流を流し、内側の二探針間に一定電流を流し、内側の二探針間に生じる電位差を測定し、抵抗を求めた。
　＜表面抵抗＞
　表面抵抗（Ω／□）は、比抵抗（Ω・ｃｍ）を膜厚（ｃｍ）で除することにより算出した。
　＜透過率＞
　透過率は、紫外可視近赤外分光光度計（日本分光（株）製「Ｖ－６７０」）を用いて測定した。
　＜耐湿性＞
　透明導電性基板を、温度６０℃、相対湿度９０％の雰囲気中に１０００時間保持する耐湿試験に付した後、表面抵抗を測定した。耐湿試験後の表面抵抗が、耐湿試験前の表面抵抗の２倍以下であると、耐湿性に優れると言える。
　＜耐熱性＞
　透明導電性基板を、温度２００℃の大気中に５時間保持する耐熱試験に付した後、表面抵抗を測定した。耐熱試験後の表面抵抗が、耐熱試験前の表面抵抗の１．５倍以下であると、耐熱性に優れると言える。
　＜耐アルカリ性＞
　透明導電性基板を、３％のＮａＯＨ水溶液（４０℃）中に１０分間浸漬し、浸漬前後の基板上の膜質の変化の有無を目視にて確認した。
　＜耐酸性＞
　透明導電性基板を、３％のＨＣｌ水溶液（４０℃）中に１０分間浸漬し、浸漬前後の基板上の膜質の変化の有無を目視にて確認した。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this Example.
<Specific resistance>
The specific resistance was measured by a four-terminal four-probe method using a resistivity meter (“LORESTA-GP, MCP-T610” manufactured by Mitsubishi Chemical Corporation). Specifically, four needle-shaped electrodes are placed on a straight line on the sample, a constant current is passed between the two outer probes, a constant current is passed between the two inner probes, and the two probes are inner. The resulting potential difference was measured to determine the resistance.
<Surface resistance>
The surface resistance (Ω / □) was calculated by dividing the specific resistance (Ω · cm) by the film thickness (cm).
<Transmissivity>
The transmittance was measured using an ultraviolet visible near infrared spectrophotometer (“V-670” manufactured by JASCO Corporation).
<Moisture resistance>
The transparent conductive substrate was subjected to a moisture resistance test in which the transparent conductive substrate was held in an atmosphere at a temperature of 60 ° C. and a relative humidity of 90% for 1000 hours, and then the surface resistance was measured. It can be said that the surface resistance after the moisture resistance test is excellent in moisture resistance when the surface resistance before the moisture resistance test is twice or less.
<Heat resistance>
The transparent conductive substrate was subjected to a heat resistance test in which the transparent conductive substrate was held in the atmosphere at a temperature of 200 ° C. for 5 hours, and then the surface resistance was measured. When the surface resistance after the heat test is 1.5 times or less than the surface resistance before the heat test, it can be said that the heat resistance is excellent.
<Alkali resistance>
The transparent conductive substrate was immersed in a 3% NaOH aqueous solution (40 ° C.) for 10 minutes, and the presence or absence of a change in film quality on the substrate before and after immersion was confirmed visually.
<Acid resistance>
The transparent conductive substrate was immersed in a 3% HCl aqueous solution (40 ° C.) for 10 minutes, and the presence or absence of a change in film quality on the substrate before and after immersion was confirmed visually.
　（実施例１）
＜酸化物混合体の製造＞
　酸化亜鉛粉（ＺｎＯ粉末；純度９９．９％、平均粒径１μｍ以下、和光純薬工業（株）製）および酸化チタン粉（Ｔｉ2Ｏ3粉末；純度９９．９％、平均粒径１μｍ以下、（株）高純度化学研究所製）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９４：６となる割合で樹脂製ポットに入れ、湿式ボールミル混合法により湿式混合した。湿式混合は、ボールとして硬質ＺｒＯ2ボールを用い、混合時間を１８時間として行った。
　次いで、混合後の原料粉末スラリーを取り出し、乾燥、造粒した後、冷間静水圧プレスにて１ｔｏｎ／ｃｍ2の圧力をかけて成形し、直径１００ｍｍ、厚さ８ｍｍの円盤状成形体を得た。 Example 1
<Production of oxide mixture>
Zinc oxide powder (ZnO powder; purity 99.9%, average particle size 1 μm or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (Ti 2 O 3 powder; purity 99.9%, average particle size 1 μm or less) , Manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, these were put in a resin pot at a ratio of the atomic ratio of Zn: Ti of 94: 6 and wet mixed by a wet ball mill mixing method. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
Next, the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
　次に、得られた成形体を、大気雰囲気中、３００℃にて１時間保持することによりアニール処理を施して、酸化物混合体（１）を得た。
　得られた酸化物混合体（１）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９４：６であった（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０６）。この酸化物混合体（１）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）と酸化チタン（Ｔｉ2Ｏ3）の結晶相の混合物であった。 Next, the obtained molded body was annealed by holding it in an air atmosphere at 300 ° C. for 1 hour to obtain an oxide mixture (1).
When the obtained oxide mixture (1) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 94. : 6 (Ti / (Zn + Ti) = 0.06). When the crystal structure of the oxide mixture (1) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), the crystal phase of zinc oxide (ZnO) and titanium oxide (Ti 2 O 3 ) It was a mixture.
　次に、得られた酸化物混合体（１）を５０ｍｍφの円盤状に加工して、スパッタリング用ターゲットを得、これを用いてスパッタリング法により透明導電膜を成膜し、透明導電性基板を作製した。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記スパッタリング用ターゲットおよび膜形成用基板（石英ガラス基板）を設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力７５Ｗ、基板温度２５０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの透明導電膜を形成した。 Next, the obtained oxide mixture (1) is processed into a disk shape of 50 mmφ to obtain a sputtering target, and a transparent conductive film is formed by sputtering using the sputtering target to produce a transparent conductive substrate. did. That is, the sputtering target and the film forming substrate (quartz glass substrate) were placed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar Pure gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of 500 nm on the substrate.
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９４：６であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 94: 6. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は５．８×１０-4Ω・ｃｍであり、表面抵抗は１１．６Ω／□であった。なお、透明導電性基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．１倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 5.8 × 10 −4 Ω · cm, and the surface resistance was 11.6 Ω / □. The specific resistance distribution on the transparent conductive substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例２）
＜酸化物混合体の製造＞
　酸化亜鉛粉（ＺｎＯ粉末；純度９９．９％、平均粒径１μｍ以下、和光純薬工業（株）製）および酸化チタン粉（Ｔｉ2Ｏ3粉末；純度９９．９％、平均粒径１μｍ以下、（株）高純度化学研究所製）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９５：５となる割合で樹脂製ポットに入れ、湿式ボールミル混合法により湿式混合した。湿式混合は、ボールとして硬質ＺｒＯ2ボールを用い、混合時間を１８時間として行った。
　次いで、混合後の原料粉末スラリーを取り出し、乾燥、造粒した後、冷間静水圧プレスにて１ｔｏｎ／ｃｍ2の圧力をかけて成形し、直径１００ｍｍ、厚さ８ｍｍの円盤状成形体を得た。 (Example 2)
<Production of oxide mixture>
Zinc oxide powder (ZnO powder; purity 99.9%, average particle size 1 μm or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (Ti 2 O 3 powder; purity 99.9%, average particle size 1 μm or less) , Manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, these were put in a resin pot at a ratio of the atomic ratio of Zn: Ti of 95: 5 and wet mixed by a wet ball mill mixing method. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
Next, the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
　次に、得られた成形体を、不活性雰囲気（１００％Ａｒ雰囲気）中、５００℃で１時間保持することによりアニール処理を施して、酸化物混合体（２）を得た。
　得られた酸化物混合体（２）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９５：５であった（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０５）。この酸化物混合体（２）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）と酸化チタン（Ｔｉ2Ｏ3）の結晶相の混合物であった。 Next, the obtained compact was annealed by holding it at 500 ° C. for 1 hour in an inert atmosphere (100% Ar atmosphere) to obtain an oxide mixture (2).
When the obtained oxide mixture (2) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 95. : 5 (Ti / (Zn + Ti) = 0.05). When the crystal structure of this oxide mixture (2) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), the crystal phase of zinc oxide (ZnO) and titanium oxide (Ti 2 O 3 ) It was a mixture.
　次に、得られた酸化物混合体（２）を５０ｍｍφの円盤状に加工して、スパッタリング用ターゲットを得、これを用いて、実施例１と同様にして、スパッタリング法により膜厚５００ｎｍの透明導電膜を成膜し、透明導電性基板を作製した。 Next, the obtained oxide mixture (2) was processed into a disk shape of 50 mmφ to obtain a sputtering target. Using this, a transparent film having a film thickness of 500 nm was formed by a sputtering method in the same manner as in Example 1. A conductive film was formed to produce a transparent conductive substrate.
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、実施例１と同様にして、蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９５：５であった。また、この透明導電膜について、実施例１と同様にして、Ｘ線回折を行うとともに、亜鉛へのチタンのドープ状態および結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed using a calibration curve by the fluorescent X-ray method in the same manner as in Example 1. As a result, Zn: Ti (atomic ratio) = 95. : 5. Further, the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は４．９×１０-4Ω・ｃｍであり、表面抵抗は９．８Ω／□であった。なお、透明導電性基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の透過率は、可視領域、赤外領域とも実施例１と同じである。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.9 × 10 −4 Ω · cm, and the surface resistance was 9.8 Ω / □. The specific resistance distribution on the transparent conductive substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). The transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（比較例１）
＜酸化物混合体の製造＞
　酸化亜鉛粉（ＺｎＯ粉末；純度９９．９％、平均粒径１μｍ以下、和光純薬工業（株）製）および酸化チタン粉（Ｔｉ2Ｏ3粉末；純度９９．９％、平均粒径１・ｍ以下、（株）高純度化学研究所製）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９９：１となる割合で樹脂製ポットに入れ、湿式ボールミル混合法により湿式混合した。湿式混合は、ボールとして硬質ＺｒＯ2ボールを用い、混合時間を１８時間として行った。
　次いで、混合後の原料粉末スラリーを取り出し、乾燥、造粒した後、冷間静水圧プレスにて１ｔｏｎ／ｃｍ2の圧力をかけて成形し、直径１００ｍｍ、厚さ８ｍｍの円盤状成形体を得た。 (Comparative Example 1)
<Production of oxide mixture>
Zinc oxide powder (ZnO powder; purity 99.9%, average particle size 1 μm or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (Ti 2 O 3 powder; purity 99.9%, average particle size 1 · m or less (manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, these were put in a resin pot at a ratio of the Zn: Ti atomic number ratio of 99: 1, and wet mixed by a wet ball mill mixing method. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
Next, the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
　次に、得られた成形体を、不活性雰囲気（１００％Ａｒ雰囲気）中、５００℃で１時間保持することによりアニール処理を施して、酸化物混合体（Ｃ１）を得た。
　得られた酸化物混合体（Ｃ１）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９９：１であった（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０１）。 Next, the obtained compact was annealed by holding it at 500 ° C. for 1 hour in an inert atmosphere (100% Ar atmosphere) to obtain an oxide mixture (C1).
When the obtained oxide mixture (C1) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 99. 1 (Ti / (Zn + Ti) = 0.01).
　次に、得られた酸化物混合体（Ｃ１）を５０ｍｍφの円盤状に加工して、スパッタリング用ターゲットを得、これを用いて、実施例１と同様にして、スパッタリング法により透明導電膜を成膜し、透明導電性基板を作製した。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記スパッタリング用ターゲットおよび膜形成用基板（石英ガラス基板）を設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力１００Ｗ、基板温度２５０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの透明導電膜を形成した。 Next, the obtained oxide mixture (C1) was processed into a disk shape of 50 mmφ to obtain a sputtering target, and using this, a transparent conductive film was formed by sputtering in the same manner as in Example 1. A transparent conductive substrate was prepared. That is, the sputtering target and the film forming substrate (quartz glass substrate) were placed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar Pure gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 100 W, and a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of 500 nm on the substrate.
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、実施例１と同様にして、蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９９：１であった。また、この透明導電膜について、実施例１と同様にして、Ｘ線回折を行うとともに、亜鉛へのチタンのドープ状態および結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed using a calibration curve by the fluorescent X-ray method in the same manner as in Example 1. As a result, Zn: Ti (atomic ratio) = 99. : 1. Further, the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は１．２×１０-3Ω・ｃｍであり、表面抵抗は２４Ω／□であった。なお、透明導電性基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均７０％であった。なお、成膜前の石英ガラス基板の透過率は、可視領域、赤外領域とも実施例１と同じである。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の２．３倍であり、耐湿性に劣ることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の２．０倍であり、耐熱性に劣ることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬後には膜は完全に溶解し、消失していた。また、得られた透明導電性基板の耐酸性を評価したところ、膜は完全に溶解し、消失していた。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗ではあるが、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）に劣る透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 1.2 × 10 −3 Ω · cm, and the surface resistance was 24 Ω / □. The specific resistance distribution on the transparent conductive substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 70% on average in the infrared region (780 nm to 2700 nm). The transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 2.3 times the surface resistance before the moisture resistance test, and the moisture resistance was inferior. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 2.0 times the surface resistance before the heat test, and the heat resistance was poor.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared after immersion. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film which is transparent and has low resistance but inferior in chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). Is clear.
　（実施例３）
＜酸化物焼結体の製造＞
　実施例１と同様にして得た円盤状成形体を、大気雰囲気中、１０００℃までを５℃／分で、１０００℃を超え１５００℃までを１℃／分で昇温し、焼結温度である１５００℃で５時間保持することにより焼結し、その後、不活性雰囲気（１００％Ａｒ雰囲気）にて１３００℃で５時間アニール処理を行い、酸化物焼結体（３）を得た。
　得られた酸化物焼結体（３）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９３：７であった（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０７）。この酸化物焼結体（３）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 3)
<Manufacture of oxide sinter>
The disk-shaped molded body obtained in the same manner as in Example 1 was heated up to 1000 ° C. at 5 ° C./min, over 1000 ° C. up to 1500 ° C. at 1 ° C./min, and sintered at the sintering temperature. Sintering was performed by holding at 1500 ° C. for 5 hours, and then annealing treatment was performed at 1300 ° C. for 5 hours in an inert atmosphere (100% Ar atmosphere) to obtain an oxide sintered body (3).
When the obtained oxide sintered body (3) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 93: 7 (Ti / (Zn + Ti) = 0.07). When the crystal structure of the oxide sintered body (3) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（３）を５０ｍｍφの円盤状に加工して、スパッタリング用ターゲットを得、これを用いて実施例１と同様にして、スパッタリング法により基板上に膜厚５００ｎｍの透明導電膜を形成した。
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、実施例１と同様にして、蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９３：７であった。また、この透明導電膜について、実施例１と同様にして、Ｘ線回折を行うとともに、亜鉛へのチタンのドープ状態を調べところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 Next, the obtained oxide sintered body (3) was processed into a disk shape of 50 mmφ to obtain a sputtering target, and using this, a film thickness was formed on the substrate by sputtering as in Example 1. A 500 nm transparent conductive film was formed.
The composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed using a calibration curve by the fluorescent X-ray method in the same manner as in Example 1. As a result, Zn: Ti (atomic ratio) = 93. : 7. Further, this transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and the state of doping of titanium into zinc was examined. As a result, it was a wurtzite single phase with C-axis orientation, and titanium was zinc. It was found that the solid solution was substituted.
　得られた透明導電性基板上の透明導電膜の比抵抗は６．２×１０-4Ω・ｃｍであり、表面抵抗は１２．４Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の透過率は、可視領域、赤外領域とも実施例１と同じである。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．１倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 6.2 × 10 −4 Ω · cm, and the surface resistance was 12.4 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). The transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例４）
＜酸化物焼結体の製造＞
　実施例２と同様にして得た円盤状成形体を、不活性雰囲気（１００％Ａｒ雰囲気）中、１０００℃までを５℃／分で、１０００℃を超え１３００℃までを１℃／分で昇温し、焼結温度である１３００℃で５時間保持することにより焼結し、酸化物焼結体（４）を得た。
　得られた酸化物焼結体（４）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９４：６であった（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０６）。この酸化物焼結体（４）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 Example 4
<Manufacture of oxide sinter>
The disc-shaped molded body obtained in the same manner as in Example 2 was heated up to 1000 ° C. at 5 ° C./min, in excess of 1000 ° C. to 1300 ° C. at 1 ° C./min in an inert atmosphere (100% Ar atmosphere). The oxide was sintered by being heated and held at a sintering temperature of 1300 ° C. for 5 hours to obtain an oxide sintered body (4).
When the obtained oxide sintered body (4) was analyzed with an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 94: 6 (Ti / (Zn + Ti) = 0.06). When the crystal structure of the oxide sintered body (4) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（４）を５０ｍｍφの円盤状に加工して、スパッタリング用ターゲットを得、これを用いて、実施例１と同様にして、スパッタリング法により膜厚５００ｎｍの透明導電膜を成膜し、透明導電基板を作製した。
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、実施例１と同様にして、蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９４：６であった。また、この透明導電膜について、実施例１と同様にして、Ｘ線回折を行うとともに、亜鉛へのチタンのドープ状態および結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 Next, the obtained oxide sintered body (4) was processed into a disk shape of 50 mmφ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by a sputtering method in the same manner as in Example 1. A transparent conductive film was formed to produce a transparent conductive substrate.
The composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed using a calibration curve by the fluorescent X-ray method in the same manner as in Example 1. As a result, Zn: Ti (atomic ratio) = 94. : 6. Further, the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は５．８×１０-4Ω・ｃｍであり、表面抵抗は１１．６Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の透過率は、可視領域、赤外領域とも実施例１と同じである。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．１倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 5.8 × 10 −4 Ω · cm, and the surface resistance was 11.6 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). The transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（比較例２）
＜酸化物焼結体の製造＞
　比較例１と同様にして得た円盤状成形体を、不活性雰囲気（１００％Ａｒ雰囲気）中、１０００℃までを５℃／分で、１０００℃を超え１３００℃までを１℃／分で昇温し、焼結温度である１３００℃で５時間保持することにより焼結し、酸化物焼結体（Ｃ２）を得た。
　得られた酸化物焼結体（Ｃ２）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９８．５：１．５であった（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０１５）。 (Comparative Example 2)
<Manufacture of oxide sinter>
The disc-shaped molded body obtained in the same manner as in Comparative Example 1 was heated in an inert atmosphere (100% Ar atmosphere) up to 1000 ° C. at 5 ° C./min, over 1000 ° C. to 1300 ° C. at 1 ° C./min. The oxide was sintered by being heated and held at a sintering temperature of 1300 ° C. for 5 hours to obtain an oxide sintered body (C2).
When the obtained oxide sintered body (C2) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 98.5: 1.5 (Ti / (Zn + Ti) = 0.015).
　次に、得られた酸化物焼結体（Ｃ２）を５０ｍｍφの円盤状に加工して、スパッタリング用ターゲットを得、これを用いて、実施例１と同様にして、スパッタリング法により膜厚５００ｎｍの透明導電膜を成膜し、透明導電基板を作製した。
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、実施例１と同様にして、蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９８．５：１．５であった。また、この透明導電膜について、実施例１と同様にして、Ｘ線回折を行うとともに、亜鉛へのチタンのドープ状態および結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 Next, the obtained oxide sintered body (C2) was processed into a disk shape of 50 mmφ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by a sputtering method in the same manner as in Example 1. A transparent conductive film was formed to produce a transparent conductive substrate.
The composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed using a calibration curve by the fluorescent X-ray method in the same manner as in Example 1. As a result, Zn: Ti (atomic ratio) = 98. .5: 1.5. Further, the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は８．０×１０-4Ω・ｃｍであり、表面抵抗は１６Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均７０％であった。なお、成膜前の石英ガラス基板の透過率は、可視領域、赤外領域とも実施例１と同じである。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の２．１倍であり、耐湿性に劣ることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．８倍であり、耐熱性に劣ることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬後には膜は完全に溶解し、消失していた。また、得られた透明導電性基板の耐酸性を評価したところ、膜は完全に溶解し、消失していた。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗ではあるが、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）に劣る透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 8.0 × 10 −4 Ω · cm, and the surface resistance was 16Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 70% in the infrared region (780 nm to 2700 nm). The transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 2.1 times the surface resistance before the moisture resistance test, and the moisture resistance was poor. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.8 times the surface resistance before the heat test, which is inferior in heat resistance.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared after immersion. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film which is transparent and has low resistance but inferior in chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). Is clear.
　（実施例５）
＜酸化物焼結体の製造（ホットプレス法）＞
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化チタン（ＴｉＯ（II）、（株）高純度化学研究所製）を、亜鉛元素とチタン元素の元素数比が９７．０：３．０となるように秤量し、ポリプロピレン製の容器に入れ、更に２ｍｍφジルコニア製ボールと混合溶媒としてエタノールを入れた。これをボールミルにより混合し、混合粉末を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（５）を得た。 (Example 5)
<Manufacture of oxide sinter (hot press method)>
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.), the element number ratio of zinc element to titanium element is 97.0: 3.0 Were weighed so as to be, put in a polypropylene container, and further 2 mmφ zirconia balls and ethanol as a mixed solvent were added. This was mixed by a ball mill to obtain a mixed powder.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (5).
　得られた酸化物焼結体（５）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９７：３であった（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）。この酸化物焼結体（５）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 When the obtained oxide sintered body (5) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 97: 3 (Ti / (Zn + Ti) = 0.03). When the crystal structure of the oxide sintered body (5) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
　次に、得られた酸化物焼結体（５）を５０ｍｍφの円盤状に加工して、スパッタリング用ターゲットを得、これを用いて、実施例１と同様にして、スパッタリング法により膜厚５００ｎｍの透明導電膜を成膜し、透明導電基板を作製した。
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、実施例１と同様にして、蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９７：３であった。また、この透明導電膜について、実施例１と同様にして、Ｘ線回折を行うとともに、亜鉛へのチタンのドープ状態および結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 Next, the obtained oxide sintered body (5) was processed into a disk shape of 50 mmφ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by sputtering in the same manner as in Example 1. A transparent conductive film was formed to produce a transparent conductive substrate.
The composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed using a calibration curve by the fluorescent X-ray method in the same manner as in Example 1. As a result, Zn: Ti (atomic ratio) = 97. : 3. Further, the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は４．２×１０-4Ω・ｃｍであり、表面抵抗は８．４Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の透過率は、可視領域、赤外領域とも実施例１と同じである。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 × 10 −4 Ω · cm, and the surface resistance was 8.4 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). The transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例６）
＜酸化物焼結体の製造（ホットプレス法）＞
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化チタン（Ｔｉ2Ｏ3（III）、（株）高純度化学研究所製）を、亜鉛元素とチタン元素の元素数比が９７．０：３．０となるように秤量し、ポリプロピレン製の容器に入れ、更に２ｍｍφジルコニア製ボールと混合溶媒としてエタノールを入れた。これをボールミルにより混合し、混合粉末を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（６）を得た。 (Example 6)
<Manufacture of oxide sinter (hot press method)>
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), titanium oxide (Ti 2 O 3 (III), manufactured by Kojundo Chemical Laboratory Co., Ltd.), the ratio of the number of elements of zinc element and titanium element is 97.0: It weighed so that it might be set to 3.0, it put into the container made from a polypropylene, and also ethanol was added as a 2 mm diameter zirconia ball | bowl and a mixed solvent. This was mixed by a ball mill to obtain a mixed powder.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (6).
　得られた酸化物焼結体（６）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９７：３であった（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）。この酸化物焼結体（６）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 When the obtained oxide sintered body (6) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 97: 3 (Ti / (Zn + Ti) = 0.03). When the crystal structure of this oxide sintered body (6) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
　次に、得られた酸化物焼結体（６）を５０ｍｍφの円盤状に加工して、スパッタリング用ターゲットを得、これを用いて、実施例１と同様にして、スパッタリング法により膜厚５００ｎｍの透明導電膜を成膜し、透明導電基板を作製した。
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、実施例１と同様にして、蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９７：３であった。また、この透明導電膜について、実施例１と同様にして、Ｘ線回折を行うとともに、亜鉛へのチタンのドープ状態および結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 Next, the obtained oxide sintered body (6) was processed into a disk shape of 50 mmφ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by sputtering in the same manner as in Example 1. A transparent conductive film was formed to produce a transparent conductive substrate.
The composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed using a calibration curve by the fluorescent X-ray method in the same manner as in Example 1. As a result, Zn: Ti (atomic ratio) = 97. : 3. Further, the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は４．４×１０-4Ω・ｃｍであり、表面抵抗は８．８Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の透過率は、可視領域、赤外領域とも実施例１と同じである。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.4 × 10 −4 Ω · cm, and the surface resistance was 8.8Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). The transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例７）
＜酸化物焼結体の製造（ＴｉＯ（II）の常圧焼結法）＞
　酸化亜鉛粉（ＺｎＯ粉末；純度９９．９％、平均粒径１・ｍ以下、和光純薬工業（株）製）および酸化チタン粉（ＴｉＯ（II）粉末；純度９９．９％、平均粒径１・ｍ以下、（株）高純度化学研究所製）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９７：３となる割合で樹脂製ポットに入れ、湿式ボールミル混合法により湿式混合した。湿式混合は、ボールとして硬質ＺｒＯ2ボールを用い、混合時間を１８時間として行った。
　次いで、混合後の原料粉末スラリーを取り出し、乾燥、造粒した後、冷間静水圧プレスにて１ｔｏｎ／ｃｍ2の圧力をかけて成形し、直径１００ｍｍ、厚さ８ｍｍの円盤状成形体を得た。 (Example 7)
<Manufacture of oxide sintered body (pressureless sintering method of TiO (II))>
Zinc oxide powder (ZnO powder; purity 99.9%, average particle size 1 · m or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (TiO (II) powder; purity 99.9%, average particle size) 1 · m or less, manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, put them in a resin pot at a Zn: Ti atomic ratio of 97: 3, and wet-mixed by a wet ball mill mixing method did. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
Next, the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
　次に得られた円盤状成形体を、不活性雰囲気（１００％Ａｒ雰囲気）中、１０００℃までを５℃／分で、１０００℃を超え１３００℃までを１℃／分で昇温し、焼結温度である１３００℃で５時間保持することにより焼結し、酸化物焼結体（７）を得た。
　得られた酸化物焼結体（７）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９７：３であった（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）。この酸化物焼結体（７）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 Next, the obtained disk-shaped molded body was heated in an inert atmosphere (100% Ar atmosphere) up to 1000 ° C. at 5 ° C./min, over 1000 ° C. to 1300 ° C. at 1 ° C./min, and baked. The oxide sintered body (7) was obtained by sintering by holding at 1300 ° C., which is a sintering temperature, for 5 hours.
When the obtained oxide sintered body (7) was analyzed with an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 97: 3 (Ti / (Zn + Ti) = 0.03). When the crystal structure of the oxide sintered body (7) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
　次に、得られた酸化物焼結体（７）を５０ｍｍφの円盤状に加工して、スパッタリング用ターゲットを得、これを用いて、実施例１と同様にして、スパッタリング法により膜厚５００ｎｍの透明導電膜を成膜し、透明導電基板を作製した。
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、実施例１と同様にして、蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９７：３であった。また、この透明導電膜について、実施例１と同様にして、Ｘ線回折を行うとともに、亜鉛へのチタンのドープ状態および結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 Next, the obtained oxide sintered body (7) was processed into a disk shape of 50 mmφ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by sputtering in the same manner as in Example 1. A transparent conductive film was formed to produce a transparent conductive substrate.
The composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed using a calibration curve by the fluorescent X-ray method in the same manner as in Example 1. As a result, Zn: Ti (atomic ratio) = 97. : 3. Further, the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は４．２×１０-4Ω・ｃｍであり、表面抵抗は８．４Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の透過率は、可視領域、赤外領域とも実施例１と同じである。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 × 10 −4 Ω · cm, and the surface resistance was 8.4 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). The transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（比較例３）
＜酸化物焼結体の製造（ＴｉＯ（II）の常圧焼結法）＞
　酸化亜鉛粉（ＺｎＯ粉末；純度９９．９％、平均粒径１μｍ以下、和光純薬工業（株）製）および酸化チタン粉（ＴｉＯ（II）粉末；純度９９．９％、平均粒径１μｍ以下、（株）高純度化学研究所製）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が８８：１２となる割合で樹脂製ポットに入れ、湿式ボールミル混合法により湿式混合した。湿式混合は、ボールとして硬質ＺｒＯ2ボールを用い、混合時間を１８時間として行った。
　次いで、混合後の原料粉末スラリーを取り出し、乾燥、造粒した後、冷間静水圧プレスにて１ｔｏｎ／ｃｍ2の圧力をかけて成形し、直径１００ｍｍ、厚さ８ｍｍの円盤状成形体を得た。 (Comparative Example 3)
<Manufacture of oxide sintered body (pressureless sintering method of TiO (II))>
Zinc oxide powder (ZnO powder; purity 99.9%, average particle size 1 μm or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (TiO (II) powder; purity 99.9%, average particle size 1 μm or less) , Manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, these were put in a resin pot at a ratio of atomic ratio of Zn: Ti of 88:12 and wet mixed by a wet ball mill mixing method. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
Next, the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
　次に得られた円盤状成形体を、不活性雰囲気（１００％Ａｒ雰囲気）中、１０００℃までを５℃／分で、１０００℃を超え１３００℃までを１℃／分で昇温し、焼結温度である１３００℃で５時間保持することにより焼結し、酸化物焼結体（Ｃ３）を得た。
　得られた酸化物焼結体（Ｃ３）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝８８：１２であった（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．１２）。この酸化物焼結体（Ｃ３）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 Next, the obtained disk-shaped molded body was heated in an inert atmosphere (100% Ar atmosphere) up to 1000 ° C. at 5 ° C./min, over 1000 ° C. to 1300 ° C. at 1 ° C./min, and baked. The oxide sintered body (C3) was obtained by sintering at 1300 ° C. which is a sintering temperature for 5 hours.
When the obtained oxide sintered body (C3) was analyzed with an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 88:12 (Ti / (Zn + Ti) = 0.12). When the crystal structure of the oxide sintered body (C3) was examined by an X-ray diffraction apparatus (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
　次に、得られた酸化物焼結体（Ｃ３）を５０ｍｍφの円盤状に加工して、スパッタリング用ターゲットを得、これを用いて、実施例１と同様にして、スパッタリング法により膜厚５００ｎｍの透明導電膜を成膜し、透明導電基板を作製した。
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、実施例１と同様にして、蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝８８：１２であった。また、この透明導電膜について、実施例１と同様にして、Ｘ線回折を行うとともに、亜鉛へのチタンのドープ状態および結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 Next, the obtained oxide sintered body (C3) was processed into a disk shape of 50 mmφ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by a sputtering method in the same manner as in Example 1. A transparent conductive film was formed to produce a transparent conductive substrate.
The composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed using a calibration curve by the fluorescent X-ray method in the same manner as in Example 1. Zn: Ti (atomic ratio) = 88 : 12. Further, the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は２．１×１０-2Ω・ｃｍであり、表面抵抗は４２０．０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６６％であった。なお、成膜前の石英ガラス基板の透過率は、可視領域、赤外領域とも実施例１と同じである。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．１倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．１倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であるが高抵抗であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.1 × 10 −2 Ω · cm, and the surface resistance was 420.0Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 66% in the infrared region (780 nm to 2700 nm). The transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.1 times that before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film having both transparency and chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance), but high resistance. It is clear.
　（実施例８）
＜酸化物焼結体の製造（ＴｉＯ（II）の常圧焼結法）＞
　酸化亜鉛粉（ＺｎＯ粉末；純度９９．９％、平均粒径１μｍ以下、和光純薬工業（株）製）および酸化チタン粉（ＴｉＯ（II）粉末；純度９９．９％、平均粒径１μｍ以下、（株）高純度化学研究所製）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９３：７となる割合で樹脂製ポットに入れ、湿式ボールミル混合法により湿式混合した。湿式混合は、ボールとして硬質ＺｒＯ2ボールを用い、混合時間を１８時間として行った。
　次いで、混合後の原料粉末スラリーを取り出し、乾燥、造粒した後、冷間静水圧プレスにて１ｔｏｎ／ｃｍ2の圧力をかけて成形し、直径１００ｍｍ、厚さ８ｍｍの円盤状成形体を得た。 (Example 8)
<Manufacture of oxide sintered body (pressureless sintering method of TiO (II))>
Zinc oxide powder (ZnO powder; purity 99.9%, average particle size 1 μm or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (TiO (II) powder; purity 99.9%, average particle size 1 μm or less) , Manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, these were put into a resin pot at a ratio of the Zn: Ti atomic ratio of 93: 7, and wet mixed by a wet ball mill mixing method. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
Next, the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
　次に得られた円盤状成形体を、不活性雰囲気（１００％Ａｒ雰囲気）中、１０００℃までを５℃／分で、１０００℃を超え１３００℃までを１℃／分で昇温し、焼結温度である１３００℃で５時間保持することにより焼結し、酸化物焼結体（８）を得た。
　得られた酸化物焼結体（８）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９３：７であった（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０７）。この酸化物焼結体（８）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 Next, the obtained disk-shaped molded body was heated in an inert atmosphere (100% Ar atmosphere) up to 1000 ° C. at 5 ° C./min, over 1000 ° C. to 1300 ° C. at 1 ° C./min, and baked. The oxide sintered body (8) was obtained by sintering by holding at 1300 ° C., which is a sintering temperature, for 5 hours.
When the obtained oxide sintered body (8) was analyzed with an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 93: 7 (Ti / (Zn + Ti) = 0.07). When the crystal structure of this oxide sintered body (8) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（８）を５０ｍｍφの円盤状に加工して、スパッタリング用ターゲットを得、これを用いて、実施例１と同様にして、スパッタリング法により膜厚５００ｎｍの透明導電膜を成膜し、透明導電基板を作製した。
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、実施例１と同様にして、蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９３：７であった。また、この透明導電膜について、実施例１と同様にして、Ｘ線回折を行うとともに、亜鉛へのチタンのドープ状態および結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 Next, the obtained oxide sintered body (8) was processed into a disk shape of 50 mmφ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by sputtering in the same manner as in Example 1. A transparent conductive film was formed to produce a transparent conductive substrate.
The composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed using a calibration curve by the fluorescent X-ray method in the same manner as in Example 1. As a result, Zn: Ti (atomic ratio) = 93. : 7. Further, the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は５．９×１０-4Ω・ｃｍであり、表面抵抗は１１．８Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の透過率は、可視領域、赤外領域とも実施例１と同じである。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．１倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 5.9 × 10 −4 Ω · cm, and the surface resistance was 11.8 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). The transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例９）
＜酸化物焼結体の製造（ＴｉＯ（II）の常圧焼結法）＞
　酸化亜鉛粉（ＺｎＯ粉末；純度９９．９％、平均粒径１μｍ以下、和光純薬工業（株）製）および酸化チタン粉（ＴｉＯ（II）粉末；純度９９．９％、平均粒径１μｍ以下、（株）高純度化学研究所製）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９１：９となる割合で樹脂製ポットに入れ、湿式ボールミル混合法により湿式混合した。湿式混合は、ボールとして硬質ＺｒＯ2ボールを用い、混合時間を１８時間として行った。
　次いで、混合後の原料粉末スラリーを取り出し、乾燥、造粒した後、冷間静水圧プレスにて１ｔｏｎ／ｃｍ2の圧力をかけて成形し、直径１００ｍｍ、厚さ８ｍｍの円盤状成形体を得た。 Example 9
<Manufacture of oxide sintered body (pressureless sintering method of TiO (II))>
Zinc oxide powder (ZnO powder; purity 99.9%, average particle size 1 μm or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (TiO (II) powder; purity 99.9%, average particle size 1 μm or less) , Manufactured by Kojundo Chemical Laboratory Co., Ltd.) as raw material powders, these were put into a resin pot at a ratio of the atomic ratio of Zn: Ti of 91: 9, and wet mixed by a wet ball mill mixing method. Wet mixing was performed using hard ZrO 2 balls as balls and mixing time of 18 hours.
Next, the mixed raw material powder slurry is taken out, dried and granulated, and then molded by applying a pressure of 1 ton / cm 2 with a cold isostatic press to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. It was.
　次に得られた円盤状成形体を、不活性雰囲気（１００％Ａｒ雰囲気）中、１０００℃までを５℃／分で、１０００℃を超え１３００℃までを１℃／分で昇温し、焼結温度である１３００℃で５時間保持することにより焼結し、酸化物焼結体（９）を得た。
　得られた酸化物焼結体（９）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９１：９であった（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０９）。この酸化物焼結体（９）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 Next, the obtained disk-shaped molded body was heated in an inert atmosphere (100% Ar atmosphere) up to 1000 ° C. at 5 ° C./min, over 1000 ° C. to 1300 ° C. at 1 ° C./min, and baked. Sintering was carried out by holding at 1300 ° C., which is a sintering temperature, for 5 hours to obtain an oxide sintered body (9).
When the obtained oxide sintered body (9) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 91: 9 (Ti / (Zn + Ti) = 0.09). When the crystal structure of the oxide sintered body (9) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（９）を５０ｍｍφの円盤状に加工して、スパッタリング用ターゲットを得、これを用いて、実施例１と同様にして、スパッタリング法により膜厚５００ｎｍの透明導電膜を成膜し、透明導電基板を作製した。
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、実施例１と同様にして、蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９１：９であった。また、この透明導電膜について、実施例１と同様にして、Ｘ線回折を行うとともに、亜鉛へのチタンのドープ状態および結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 Next, the obtained oxide sintered body (9) was processed into a disk shape of 50 mmφ to obtain a sputtering target, and using this, a film thickness of 500 nm was formed by sputtering in the same manner as in Example 1. A transparent conductive film was formed to produce a transparent conductive substrate.
The composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed using a calibration curve by the fluorescent X-ray method in the same manner as in Example 1. As a result, Zn: Ti (atomic ratio) = 91. : 9. Further, the transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 1, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は２．２×１０-3Ω・ｃｍであり、表面抵抗は４４．０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６５％であった。なお、成膜前の石英ガラス基板の透過率は、可視領域、赤外領域とも実施例１と同じである。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．１倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.2 × 10 −3 Ω · cm, and the surface resistance was 44.0 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 65% in the infrared region (780 nm to 2700 nm). The transmittance of the quartz glass substrate before film formation is the same as that in Example 1 in both the visible region and the infrared region.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例１０）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９６：４となる割合で混合し、原料粉末の混合物を得た。次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（１０１．３２５ｋＰａ）のアルゴン雰囲気下、４００℃で３時間アニールして、酸化物混合体（１０）を得た。
　得られた酸化物混合体（１０）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９６：４（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０４）であった。この酸化物混合体（１０）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）と酸化チタン（Ｔｉ2Ｏ3）の結晶相の混合物であった。 (Example 10)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was annealed at 400 ° C. for 3 hours in an argon atmosphere at normal pressure (101.325 kPa) to obtain an oxide mixture (10).
When the obtained oxide mixture (10) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 96. : 4 (Ti / (Zn + Ti) = 0.04). When the crystal structure of the oxide mixture (10) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), the crystal phase of zinc oxide (ZnO) and titanium oxide (Ti 2 O 3 ) It was a mixture.
　次に、得られた酸化物混合体（１０）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により透明導電膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力７５Ｗ、基板温度２５０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの透明導電膜を形成した。 Next, the obtained oxide mixture (10) was processed into a disk shape of 50 mmφ to prepare a target, and a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive substrate. . That is, the above-mentioned target and a transparent substrate (quartz glass substrate) were respectively installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of 500 nm on the substrate.
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９６：４（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０４）であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) = 96: 4 (Ti / (Zn + Ti) = 0.04). The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は５．１×１０-4Ω・ｃｍであり、表面抵抗は１０．２Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 5.1 × 10 −4 Ω · cm, and the surface resistance was 10.2 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例１１）
　実施例１０で得た酸化物混合体（１０）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により透明導電膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（アクリル系透明樹脂シート）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力１００Ｗ、基板温度１３０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの透明導電膜を形成した。 (Example 11)
A target was prepared by processing the oxide mixture (10) obtained in Example 10 into a disk shape of 50 mmφ, and a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive substrate. . That is, the target and the transparent base material (acrylic transparent resin sheet) were installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), respectively, and Ar gas (purity 99.9995% or more, Ar pure gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 100 W, and a substrate temperature of 130 ° C. to form a transparent conductive film having a thickness of 500 nm on the substrate.
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９６：４（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０４）であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) = 96: 4 (Ti / (Zn + Ti) = 0.04). The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は７．２×１０-4Ω・ｃｍであり、表面抵抗は１４.４Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８８％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前のアクリル系透明樹脂シートの可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９３％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９３％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．６倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．４倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.2 × 10 −4 Ω · cm, and the surface resistance was 14.4 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 88% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). The transmittance in the visible region (380 nm to 780 nm) of the acrylic transparent resin sheet before film formation averaged 93%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 93%.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.6 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.4 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例１２）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９６：４となる割合で混合し、原料粉末の混合物を得た。次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を、まず常圧（１０１．３２５ｋＰａ）の大気雰囲気下、５００℃で３時間アニールして、酸化物混合体（１１）を得た。 (Example 12)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was first annealed at 500 ° C. for 3 hours in an atmospheric atmosphere of normal pressure (101.325 kPa) to obtain an oxide mixture (11).
　得られた酸化物混合体（１１）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９６：４（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０４）であった。この酸化物混合体（１１）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）と酸化チタンの結晶相の混合物であった。
　次に、得られた酸化物混合体（１１）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により透明導電膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力１００Ｗ、基板温度１３０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの透明導電膜を形成した。 When the obtained oxide mixture (11) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 96. : 4 (Ti / (Zn + Ti) = 0.04). When the crystal structure of the oxide mixture (11) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), it was a mixture of crystal phases of zinc oxide (ZnO) and titanium oxide.
Next, the obtained oxide mixture (11) was processed into a disk shape of 50 mmφ to prepare a target, and a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive substrate. . That is, the above-mentioned target and a transparent substrate (quartz glass substrate) were respectively installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 100 W, and a substrate temperature of 130 ° C. to form a transparent conductive film having a thickness of 500 nm on the substrate.
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９６：４（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０４）であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) = 96: 4 (Ti / (Zn + Ti) = 0.04). The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は８．０×１０-4Ω・ｃｍであり、表面抵抗は１６Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６２％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．６倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．４倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 8.0 × 10 −4 Ω · cm, and the surface resistance was 16Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 62% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.6 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.4 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例１３）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９７：３となる割合で混合し、原料粉末の混合物を得た。次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（１．０１３２５×１０2ｋＰａ）のアルゴン雰囲気下、８００℃で４時間焼結して、酸化物焼結体（１２）を得た。
　得られた酸化物焼結体（１２）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。この酸化物焼結体（１２）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 13)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 800 ° C. for 4 hours in an argon atmosphere at normal pressure (1.01325 × 10 2 kPa) to obtain an oxide sintered body (12).
When the obtained oxide sintered body (12) was analyzed with an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 97: 3 (Ti / (Zn + Ti) = 0.03). When the crystal structure of the oxide sintered body (12) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（１２）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により透明導電膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力７５Ｗ、基板温度２５０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの透明導電膜を形成した。 Next, by processing the obtained oxide sintered body (12) into a disk shape of 50 mmφ, a target is prepared, and a transparent conductive film is formed by sputtering using this to obtain a transparent conductive substrate. It was. That is, the above-mentioned target and a transparent substrate (quartz glass substrate) were respectively installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of 500 nm on the substrate.
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) = 97: 3 (Ti / (Zn + Ti) = 0.03). The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は４．４×１０-4Ω・ｃｍであり、表面抵抗は８．８Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.4 × 10 −4 Ω · cm, and the surface resistance was 8.8Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（比較例４）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９９：１となる割合で混合し、原料粉末の混合物を得た。次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（１０１．３２５ｋＰａ）のアルゴン雰囲気下、４００℃で３時間アニールして、酸化物混合体（Ｃ４）を得た。
　得られた酸化物混合体（Ｃ４）をエネルギー分散型蛍光Ｘ線装置（島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９９：１（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０１）であった。 (Comparative Example 4)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. A mixture of raw material powders was obtained by mixing at a ratio of the Zn: Ti atomic ratio of 99: 1. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was annealed at 400 ° C. for 3 hours in an argon atmosphere at normal pressure (101.325 kPa) to obtain an oxide mixture (C4).
When the obtained oxide mixture (C4) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 99: 1 ( Ti / (Zn + Ti) = 0.01).
　次に、得られた酸化物混合体（Ｃ４）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により透明導電膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力１００Ｗ、基板温度１３０℃の条件下でスパッタリングを行い、基板上に膜厚２００ｎｍの透明導電膜を形成した。 Next, the target was prepared by processing the obtained oxide mixture (C4) into a disk shape of 50 mmφ, and a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive substrate. . That is, the above-mentioned target and a transparent substrate (quartz glass substrate) were respectively installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 100 W, and a substrate temperature of 130 ° C. to form a transparent conductive film having a thickness of 200 nm on the substrate.
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９９：１（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０１）であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). Zn: Ti (atomic ratio) = 99: 1 (Ti / (Zn + Ti) = 0.01). The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は２．５×１０-3Ω・ｃｍであり、表面抵抗は１２５Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均７０％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の２．６倍であり、耐湿性に劣ることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の２．０倍であり、耐熱性に劣ることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬後には膜は完全に溶解し、消失していた。また、得られた透明導電性基板の耐酸性を評価したところ、膜は完全に溶解し、消失していた。
　以上のことから、得られた透明導電性基板上の膜は、透明ではあるが、高抵抗であり、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）には劣る透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.5 × 10 −3 Ω · cm, and the surface resistance was 125 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 70% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the moisture resistance test was 2.6 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was inferior. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 2.0 times the surface resistance before the heat test, and the heat resistance was poor.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared after immersion. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared.
From the above, the obtained film on the transparent conductive substrate is transparent, but has high resistance and poor chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that
　（比較例５）
　平均粒径が１μｍの酸化亜鉛粉末９７．７重量部と、平均粒径が０．２μｍの酸化アルミニウム粉末２．３重量部とを、ポリエチレン製ポットに入れ、乾式ボールミルを用いて７２時間混合し、原料粉末の混合物を得た。得られた混合物を金型に入れ、成形圧３００ｋｇ／ｃｍ2の圧力でプレスを行い、成形体を得た。この成形体に３ｔｏｎ／ｃｍ2の圧力でＣＩＰによる緻密化処理を施した後、以下の条件で焼結して、アルミニウムドープ酸化亜鉛の酸化物焼結体（Ｃ５）を得た。 
　　焼結温度：１５００℃
　　昇温速度：５０℃／時間
　　保持時間：５時間
　　焼結雰囲気：大気中
　得られた酸化物焼結体（Ｃ５）は、Ｘ線回折で分析したところ、ＺｎＯとＺｎＡｌ2Ｏ4との２相の混合組織であった。 (Comparative Example 5)
97.7 parts by weight of zinc oxide powder having an average particle diameter of 1 μm and 2.3 parts by weight of aluminum oxide powder having an average particle diameter of 0.2 μm are placed in a polyethylene pot and mixed for 72 hours using a dry ball mill. A raw material powder mixture was obtained. The obtained mixture was put in a mold and pressed at a molding pressure of 300 kg / cm 2 to obtain a molded body. The compact was subjected to a densification treatment by CIP at a pressure of 3 ton / cm 2 and then sintered under the following conditions to obtain an oxide sintered body (C5) of aluminum-doped zinc oxide.
Sintering temperature: 1500 ° C
Temperature rising rate: 50 ° C./hour Holding time: 5 hours Sintering atmosphere: in the air The obtained oxide sintered body (C5) was analyzed by X-ray diffraction. As a result, two phases of ZnO and ZnAl 2 O 4 were obtained. Of mixed tissue.
　次に、得られた酸化物焼結体（Ｃ５）を４インチφ、６ｍｍｔの形状に加工し、インジウム半田を用いて無酸素銅製バッキングプレートにボンディングすることにより、ターゲットを作製した。そして、このターゲットを用いて、以下の条件でスパッタリング法による成膜を行い、透明基材（石英ガラス基板）上に膜厚３００ｎｍの透明導電膜を形成し、透明導電性基板を得た。形成した膜中のＡｌ含有量は２．３重量％であった。
　　装置　　　　　　　　：ｄｃマグネトロンスパッタ装置
　　磁界強度　　　　　　：１０００Ｇａｕｓｓ（ターゲット直上、水平成分）
　　基板温度　　　　　　：２００℃
　　到達真空度　　　　　：５×１０-5Ｐａ
　　スパッタリングガス　：Ａｒ
　　スパッタリングガス圧：０．５Ｐａ
　　ＤＣパワー　　　　　：３００Ｗ Next, the obtained oxide sintered body (C5) was processed into a shape of 4 inches φ and 6 mmt, and bonded to an oxygen-free copper backing plate using indium solder to prepare a target. And using this target, the film-forming by sputtering method was performed on condition of the following, the transparent conductive film with a film thickness of 300 nm was formed on the transparent base material (quartz glass substrate), and the transparent conductive substrate was obtained. The Al content in the formed film was 2.3% by weight.
Equipment: dc magnetron sputtering equipment Magnetic field strength: 1000 Gauss (horizontal component directly above the target)
Substrate temperature: 200 ° C
Ultimate vacuum: 5 × 10 −5 Pa
Sputtering gas: Ar
Sputtering gas pressure: 0.5 Pa
DC power: 300W
　得られた透明導電性基板上の透明導電膜の比抵抗は７．６×１０-4Ω・ｃｍであり、表面抵抗は２５．３Ω／□であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８８％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５５％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の３．２倍であり、耐湿性に劣ることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の７．０倍であり、耐熱性に劣ることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬後には膜は完全に溶解し、消失していた。また、得られた透明導電性基板の耐酸性を評価したところ、膜は完全に溶解し、消失していた。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗ではあるが、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）には劣る透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.6 × 10 −4 Ω · cm, and the surface resistance was 25.3 Ω / □.
The transmittance of the obtained transparent conductive substrate was an average of 88% in the visible region (380 nm to 780 nm) and an average of 55% in the infrared region (780 nm to 2700 nm).
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 3.2 times the surface resistance before the moisture resistance test, and the moisture resistance was poor. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 7.0 times the surface resistance before the heat test, and it was found that the heat resistance was poor.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared after immersion. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared.
From the above, the obtained film on the transparent conductive substrate is transparent and low resistance, but is a transparent conductive film inferior in chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear.
　（実施例１４）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（ＴｉＯ（II）；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９７：３となる割合で混合し、原料粉末の混合物を得た。次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（１．０１３２５×１０2ｋＰａ）のアルゴン雰囲気下、１０００℃で４時間焼結して、酸化物焼結体（１３）を得た。
　得られた酸化物焼結体（１３）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。この酸化物混合体（１３）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 14)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 1000 ° C. for 4 hours in an argon atmosphere at normal pressure (1.01325 × 10 2 kPa) to obtain an oxide sintered body (13).
When the obtained oxide sintered body (13) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 97: 3 (Ti / (Zn + Ti) = 0.03). When the crystal structure of the oxide mixture (13) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), the crystal phase of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) And no titanium oxide was present.
　次に、得られた酸化物焼結体（１３）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により透明導電膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力７５Ｗ、基板温度２５０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの透明導電膜を形成した。 Next, the obtained oxide sintered body (13) is processed into a disk shape of 50 mmφ to prepare a target, and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate. It was. That is, the above-mentioned target and a transparent substrate (quartz glass substrate) were respectively installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of 500 nm on the substrate.
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) = 97: 3 (Ti / (Zn + Ti) = 0.03). The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は４．２×１０-4Ω・ｃｍであり、表面抵抗は８．４Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 × 10 −4 Ω · cm, and the surface resistance was 8.4 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例１５）
　実施例１４と同様にして、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（１４）を得た（ホットプレス法）。
　得られた酸化物焼結体（１４）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。この酸化物焼結体（１４）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 15)
In the same manner as in Example 14, a mixture of raw material powders was obtained. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. And a disk-shaped oxide sintered body (14) was obtained (hot pressing method).
When the obtained oxide sintered body (14) was analyzed with an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 97: 3 (Ti / (Zn + Ti) = 0.03). When the crystal structure of the oxide sintered body (14) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
　次に、得られた酸化物焼結体（１４）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により透明導電膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力７５Ｗ、基板温度２５０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの透明導電膜を形成した。 Next, by processing the obtained oxide sintered body (14) into a disk shape of 50 mmφ, a target is prepared, and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate. It was. That is, the above-mentioned target and a transparent substrate (quartz glass substrate) were respectively installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of 500 nm on the substrate.
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) = 97: 3 (Ti / (Zn + Ti) = 0.03). The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は４．２×１０-4Ω・ｃｍであり、表面抵抗は８．４Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 × 10 −4 Ω · cm, and the surface resistance was 8.4 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例１６）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3（III）；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９７：３となる割合で混合し、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（１５）を得た（ホットプレス法）。
　得られた酸化物焼結体（１５）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。この酸化物焼結体（１５）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 16)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 (III); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. These were mixed in such a ratio that the Zn: Ti atomic ratio was 97: 3 to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (15) (hot pressing method).
When the obtained oxide sintered body (15) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 97: 3 (Ti / (Zn + Ti) = 0.03). When the crystal structure of the oxide sintered body (15) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
　次に、得られた酸化物焼結体（１５）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により透明導電膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力７５Ｗ、基板温度２５０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの透明導電膜を形成した。 Next, the obtained oxide sintered body (15) is processed into a disk shape of 50 mmφ to prepare a target, and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate. It was. That is, the above-mentioned target and a transparent substrate (quartz glass substrate) were respectively installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of 500 nm on the substrate.
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) = 97: 3 (Ti / (Zn + Ti) = 0.03). The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は４．４×１０-4Ω・ｃｍであり、表面抵抗は８．８Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.4 × 10 −4 Ω · cm, and the surface resistance was 8.8Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（比較例６）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3（III）；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が８８：１２となる割合で混合し、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（Ｃ６）を得た。
　得られた酸化物焼結体（Ｃ６）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝８８：１２（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．１２）であった。この酸化物焼結体（Ｃ６）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Comparative Example 6)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 (III); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. These were mixed at a ratio of the Zn: Ti atomic ratio of 88:12 to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (C6).
When the obtained oxide sintered body (C6) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 88:12 (Ti / (Zn + Ti) = 0.12). When the crystal structure of this oxide sintered body (C6) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（Ｃ６）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により透明導電膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力７５Ｗ、基板温度２５０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの透明導電膜を形成した。 Next, the target oxide is produced by processing the obtained oxide sintered body (C6) into a disk shape of 50 mmφ, and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate. It was. That is, the above-mentioned target and a transparent substrate (quartz glass substrate) were respectively installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of 500 nm on the substrate.
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝８８：１２（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．１２）であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかったが、結晶性は低下していた。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 88:12 (Ti / (Zn + Ti) = 0.12). The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc, but the crystallinity was lowered.
　得られた透明導電性基板上の透明導電膜の比抵抗は２．２×１０-2Ω・ｃｍであり、表面抵抗は４４０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６６％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．１倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．１倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であるが高抵抗であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.2 × 10 −2 Ω · cm, and the surface resistance was 440 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 66% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.1 times that before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the obtained film on the transparent conductive substrate is a transparent conductive film that is transparent and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that it is a resistance.
　（比較例７）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（ＴｉＯ（II）；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が８８：１２となる割合で混合し、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（Ｃ７）を得た。
　得られた酸化物焼結体（Ｃ７）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝８８：１２（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．１２）であった。この酸化物焼結体（Ｃ７）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Comparative Example 7)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. A mixture of raw material powders was obtained by mixing the Zn: Ti at an atomic ratio of 88:12. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (C7).
When the obtained oxide sintered body (C7) was analyzed with an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 88:12 (Ti / (Zn + Ti) = 0.12). When the crystal structure of the oxide sintered body (C7) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（Ｃ７）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により透明導電膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力７５Ｗ、基板温度２５０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの透明導電膜を形成した。 Next, the target oxide is produced by processing the obtained oxide sintered body (C7) into a disk shape of 50 mmφ, and a transparent conductive film is formed by sputtering using this to obtain a transparent conductive substrate. It was. That is, the above-mentioned target and a transparent substrate (quartz glass substrate) were respectively installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of 500 nm on the substrate.
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝８８：１２（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．１２）であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかったが、結晶性は低下していた。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 88:12 (Ti / (Zn + Ti) = 0.12). The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc, but the crystallinity was lowered.
　得られた透明導電性基板上の透明導電膜の比抵抗は２．１×１０-2Ω・ｃｍであり、表面抵抗は４２０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６６％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．１倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．１倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であるが高抵抗であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.1 × 10 −2 Ω · cm, and the surface resistance was 420 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 66% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.1 times that before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the obtained film on the transparent conductive substrate is a transparent conductive film that is transparent and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that it is a resistance.
　（実施例１７）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3（III）；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９３：７となる割合で混合し、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（１６）を得た（ホットプレス法）。
　得られた酸化物焼結体（１６）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９３：７（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０７）であった。この酸化物焼結体（１６）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 17)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 (III); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. These were mixed at a ratio of the Zn: Ti atomic ratio of 93: 7 to obtain a raw material powder mixture. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (16) (hot pressing method).
When the obtained oxide sintered body (16) was analyzed by an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 93: 7 (Ti / (Zn + Ti) = 0.07). When the crystal structure of this oxide sintered body (16) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（１６）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により透明導電膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力７５Ｗ、基板温度２５０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの透明導電膜を形成した。 Next, the obtained oxide sintered body (16) is processed into a disk shape of 50 mmφ to prepare a target, and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate. It was. That is, the above-mentioned target and a transparent substrate (quartz glass substrate) were respectively installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of 500 nm on the substrate.
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９３：７（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０７）であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). Zn: Ti (atomic ratio) = 93: 7 (Ti / (Zn + Ti) = 0.07). The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は６．２×１０-4Ω・ｃｍであり、表面抵抗は１２．４Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．１倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 6.2 × 10 −4 Ω · cm, and the surface resistance was 12.4 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例１８）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（ＴｉＯ（II）；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９３：７となる割合で混合し、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（１７）を得た（ホットプレス法）。
　得られた酸化物焼結体（１７）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９３：７（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０７）であった。この酸化物焼結体（１７）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 18)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. A mixture of raw material powders was obtained by mixing the Zn: Ti at an atomic ratio of 93: 7. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (17) (hot press method).
When the obtained oxide sintered body (17) was analyzed by an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 93: 7 (Ti / (Zn + Ti) = 0.07). When the crystal structure of the oxide sintered body (17) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
　次に、得られた酸化物焼結体（１７）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により透明導電膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力７５Ｗ、基板温度２５０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの透明導電膜を形成した。 Next, the target oxide is produced by processing the obtained oxide sintered body (17) into a disk shape of 50 mmφ, and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate. It was. That is, the above-mentioned target and a transparent substrate (quartz glass substrate) were respectively installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of 500 nm on the substrate.
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９３：７（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０７）であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) = 93: 7 (Ti / (Zn + Ti) = 0.07). The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は５．９×１０-4Ω・ｃｍであり、表面抵抗は１１．８Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．１倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 5.9 × 10 −4 Ω · cm, and the surface resistance was 11.8 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例１９）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９６：４となる割合で混合し、原料粉末の混合物を得た。次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（１．０１３２５×１０2ｋＰａ）のアルゴン雰囲気下、５００℃で１時間加熱して、酸化物混合体（１８）を得た。
　得られた酸化物混合体（１８）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９６：４（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０４）であった。この酸化物混合体（１８）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）と酸化チタン（Ｔｉ2Ｏ3）の結晶相の混合物であった。 (Example 19)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was heated at 500 ° C. for 1 hour in an argon atmosphere at normal pressure (1.01325 × 10 2 kPa) to obtain an oxide mixture (18).
When the obtained oxide mixture (18) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 96. : 4 (Ti / (Zn + Ti) = 0.04). When the crystal structure of this oxide mixture (18) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), the crystal phase of zinc oxide (ZnO) and titanium oxide (Ti 2 O 3 ) It was a mixture.
　次に、得られた酸化物混合体（１８）を２０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてＰＬＤ法により透明導電膜を成膜し、透明導電基板を得た。すなわち、パルスレーザ蒸着装置（誠南工業（株）製「ＰＳ－２０００」）内に、上記ターゲットと、該ターゲットに対向させるように石英ガラス基板とを設置し、レーザ発光装置（ラムダ・フィジクス（株）製「Ｃｏｍｅｘ２０５型」）を用いて、下記の成膜条件下、成膜時間１２０分間で、膜厚３００ｎｍの透明導電膜を形成した。
＜成膜条件＞
　　Laser:ArF Excimer Laser(波長＝１９３ｎｍ)
　　Laser Energy:１８ｍＪ
　　Repetition Frequency:５Ｈｚ
　　Target to substrate Distance:４０ｎｍ
　　Substrate:Corning＃１７３７
　　Substrate Temperature(℃)：２５０℃
　　Base Pressure: ７．２×１０-4Ｐａ
　　Gas Pressure(酸素)：０．２５Ｐａ
　　Gas Flow Rate:８．６ｓｃｃｍ
　　Film thickness:３００ｎｍ Next, the target was produced by processing the obtained oxide mixture (18) into a disk shape of 20 mmφ, and a transparent conductive film was formed by using the PLD method to obtain a transparent conductive substrate. . That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
<Film formation conditions>
Laser: ArF Excimer Laser (wavelength = 193nm)
Laser Energy: 18mJ
Repetition Frequency: 5Hz
Target to substrate distance: 40nm
Substrate: Corning # 1737
Substrate Temperature (℃): 250 ℃
Base Pressure: 7.2 × 10 −4 Pa
Gas Pressure (Oxygen): 0.25Pa
Gas Flow Rate: 8.6sccm
Film thickness: 300nm
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９６：４であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の透明導電膜の比抵抗は４．４×１０-4Ω・ｃｍであり、表面抵抗は１４．７Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６５％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．６倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.4 × 10 −4 Ω · cm, and the surface resistance was 14.7 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.6 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例２０）
　実施例１９で得られた酸化物混合体（１８）を２０ｍｍφの円盤状に加工することにより、ターゲットを作製した。このターゲットを用いて、実施例１９における透明基板（石英ガラス基板）をアクリル系透明樹脂シート（８０ｍｍ×８０ｍｍ×２ｍｍｔ平板）に代えるとともに、成膜条件（Substrate Temperature）を下記通り変更したこと以外は、実施例１９と同様にして、成膜時間１２０分間でＰＬＤ法により、膜厚３００ｎｍの透明導電膜を形成した。
＜成膜条件＞
　　Laser:ArF Excimer Laser(波長＝１９３ｎｍ)
　　Laser Energy:１８ｍＪ
　　Repetition Frequency:５Ｈｚ
　　Target to substrate Distance:４０ｎｍ
　　Substrate:Corning＃１７３７
　　Substrate Temperature(℃)：１３０℃
　　Base Pressure: ７．２×１０-4Ｐａ
　　Gas Pressure(酸素)：０．２５Ｐａ
　　Gas Flow Rate:８．６ｓｃｃｍ
　　Film thickness:３００ｎｍ (Example 20)
A target was produced by processing the oxide mixture (18) obtained in Example 19 into a disk shape of 20 mmφ. Using this target, the transparent substrate (quartz glass substrate) in Example 19 was replaced with an acrylic transparent resin sheet (80 mm × 80 mm × 2 mmt flat plate), and the film formation conditions (Substrate Temperature) were changed as follows. In the same manner as in Example 19, a 300 nm-thick transparent conductive film was formed by the PLD method with a film formation time of 120 minutes.
<Film formation conditions>
Laser: ArF Excimer Laser (wavelength = 193nm)
Laser Energy: 18mJ
Repetition Frequency: 5Hz
Target to substrate distance: 40nm
Substrate: Corning # 1737
Substrate Temperature (℃): 130 ℃
Base Pressure: 7.2 × 10 −4 Pa
Gas Pressure (Oxygen): 0.25Pa
Gas Flow Rate: 8.6sccm
Film thickness: 300nm
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９６：４であった。また、この透明導電膜について、実施例１９と同様にして、Ｘ線回折を行うとともに、亜鉛へのチタンのドープ状態および結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の透明導電膜の比抵抗は６．３×１０-4Ω・ｃｍであり、表面抵抗は２１Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６５％であった。なお、成膜前の樹脂シートの可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4. Further, this transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 19, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis-oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 6.3 × 10 −4 Ω · cm, and the surface resistance was 21Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 65% in the infrared region (780 nm to 2700 nm). The transmittance in the visible region (380 nm to 780 nm) of the resin sheet before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．６倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.6 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例２１）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９６：４となる割合で混合し、原料粉末の混合物を得た。次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（１．０１３２５×１０2ｋＰａ）のアルゴン雰囲気下、８００℃で４時間焼結して、酸化物焼結体（１９）を得た。
　得られた酸化物焼結体（１９）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９６：４（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０４）であった。この酸化物焼結体（１９）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 21)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was sintered at 800 ° C. for 4 hours under an argon atmosphere at normal pressure (1.01325 × 10 2 kPa) to obtain an oxide sintered body (19).
When the obtained oxide sintered body (19) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = It was 96: 4 (Ti / (Zn + Ti) = 0.04). When the crystal structure of this oxide sintered body (19) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（１９）を２０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてＰＬＤ法により透明導電膜を成膜し、透明導電基板を得た。すなわち、パルスレーザ蒸着装置（誠南工業（株）製「ＰＳ－２０００」）内に、上記ターゲットと、該ターゲットに対向させるように石英ガラス基板とを設置し、レーザ発光装置（ラムダ・フィジクス（株）製「Ｃｏｍｅｘ２０５型」）を用いて、下記の成膜条件下、成膜時間１２０分間で、膜厚３００ｎｍの透明導電膜を形成した。
＜成膜条件＞
　　Laser:ArF Excimer Laser(波長＝１９３ｎｍ)
　　Laser Energy:１８ｍＪ
　　Repetition Frequency:５Ｈｚ
　　Target to substrate Distance:４０ｎｍ
　　Substrate:Corning＃１７３７
　　Substrate Temperature(℃)：２５０℃
　　Base Pressure: ７．２×１０-4Ｐａ
　　Gas Pressure(酸素)：０．２５Ｐａ
　　Gas Flow Rate:８．６ｓｃｃｍ
　　Film thickness:３００ｎｍ Next, the obtained oxide sintered body (19) is processed into a disk shape of 20 mmφ to produce a target, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate. It was. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
<Film formation conditions>
Laser: ArF Excimer Laser (wavelength = 193nm)
Laser Energy: 18mJ
Repetition Frequency: 5Hz
Target to substrate distance: 40nm
Substrate: Corning # 1737
Substrate Temperature (℃): 250 ℃
Base Pressure: 7.2 × 10 −4 Pa
Gas Pressure (Oxygen): 0.25Pa
Gas Flow Rate: 8.6sccm
Film thickness: 300nm
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９６：４であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の透明導電膜の比抵抗は４．４×１０-4Ω・ｃｍであり、表面抵抗は１４．７Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６５％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．６倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.4 × 10 −4 Ω · cm, and the surface resistance was 14.7 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.6 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（比較例８）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９９：１となる割合で混合し、原料粉末の混合物を得た。次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（１．０１３２５×１０2ｋＰａ）のアルゴン雰囲気下、４００℃で３時間加熱して、酸化物混合体（Ｃ８）を得た。
　得られた酸化物混合体（Ｃ８）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９９：１（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０１）であった。 (Comparative Example 8)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. A mixture of raw material powders was obtained by mixing at a ratio of the Zn: Ti atomic ratio of 99: 1. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was heated at 400 ° C. for 3 hours under an argon atmosphere at normal pressure (1.01325 × 10 2 kPa) to obtain an oxide mixture (C8).
When the obtained oxide mixture (C8) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 99. : 1 (Ti / (Zn + Ti) = 0.01).
　次に、得られた酸化物混合体（Ｃ８）を２０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いて、実施例１９と同様にして、成膜時間１２０分間でＰＬＤ法により、膜厚３２０ｎｍの透明導電膜を形成した。
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９９：１であった。また、この透明導電膜について、実施例１９と同様にして、Ｘ線回折を行うとともに、亜鉛へのチタンのドープ状態および結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の透明導電膜の比抵抗は２．３４×１０-3Ω・ｃｍであり、表面抵抗は７３．２Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％であった。なお、成膜前の石英ガラス基板の可視領域における透過率は、実施例１９と同じである。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の２．４倍であり、耐湿性に劣ることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の２．２倍であり、耐熱性に劣ることがわかった。 Next, the obtained oxide mixture (C8) was processed into a disk shape of 20 mmφ to prepare a target, and using this, the PLD method was performed in a film formation time of 120 minutes in the same manner as in Example 19. Thus, a transparent conductive film having a thickness of 320 nm was formed.
The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 99: 1. Further, this transparent conductive film was subjected to X-ray diffraction in the same manner as in Example 19, and when the doped state and crystal structure of titanium into zinc were examined, it was a C-axis-oriented wurtzite type single phase. It was found that titanium was substituted and dissolved in zinc.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.34 × 10 −3 Ω · cm, and the surface resistance was 73.2 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was 90% on average in the visible region (380 nm to 780 nm). The transmittance in the visible region of the quartz glass substrate before film formation is the same as in Example 19.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 2.4 times the surface resistance before the moisture resistance test, and the moisture resistance was poor. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 2.2 times the surface resistance before the heat test, which is inferior in heat resistance.
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬後には膜は完全に溶解し、消失していた。また、得られた透明導電性基板の耐酸性を評価したところ、膜は完全に溶解し、消失していた。
　以上のことから、得られた透明導電性基板上の膜は、透明ではあるが、抵抗が大きく導電性に劣るとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）にも劣る透明導電膜であることが明らかである。 When the alkali resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared after immersion. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared.
From the above, the film on the transparent conductive substrate obtained is transparent, but has high resistance and poor conductivity, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that the transparent conductive film is inferior.
　（実施例２２）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９７：３となる割合で混合し、原料粉末の混合物を得た。次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（１．０１３２５×１０2ｋＰａ）のアルゴン雰囲気下、８００℃で４時間焼結して、酸化物焼結体（２０）を得た。
　得られた酸化物焼結体（２０）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。この酸化物焼結体（２０）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）との結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 22)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 800 ° C. for 4 hours in an argon atmosphere at normal pressure (1.01325 × 10 2 kPa) to obtain an oxide sintered body (20).
When the obtained oxide sintered body (20) was analyzed with an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 97: 3 (Ti / (Zn + Ti) = 0.03). When the crystal structure of this oxide sintered body (20) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) It was a mixture of crystalline phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（２０）を２０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてＰＬＤ法により透明導電膜を成膜し、透明導電基板を得た。すなわち、パルスレーザ蒸着装置（誠南工業（株）製「ＰＳ－２０００」）内に、上記ターゲットと、該ターゲットに対向させるように石英ガラス基板とを設置し、レーザ発光装置（ラムダ・フィジクス（株）製「Ｃｏｍｅｘ２０５型」）を用いて、下記の成膜条件下、成膜時間１２０分間で、膜厚３００ｎｍの透明導電膜を形成した。
＜成膜条件＞
　　Laser:ArF Excimer Laser(波長＝１９３ｎｍ)
　　Laser Energy:１８ｍＪ
　　Repetition Frequency:５Ｈｚ
　　Target to substrate Distance:４０ｎｍ
　　Substrate:Corning＃１７３７
　　Substrate Temperature(℃)：２００℃
　　Base Pressure:７．２×１０-4Ｐａ
　　Gas Pressure(酸素)：０．２５Ｐａ
　　Gas Flow Rate:８．６ｓｃｃｍ
　　Film thickness:３００ｎｍ Next, by processing the obtained oxide sintered body (20) into a disk shape of 20 mmφ, a target is prepared, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate. It was. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
<Film formation conditions>
Laser: ArF Excimer Laser (wavelength = 193nm)
Laser Energy: 18mJ
Repetition Frequency: 5Hz
Target to substrate distance: 40nm
Substrate: Corning # 1737
Substrate Temperature (℃): 200 ℃
Base Pressure: 7.2 × 10 −4 Pa
Gas Pressure (Oxygen): 0.25Pa
Gas Flow Rate: 8.6sccm
Film thickness: 300nm
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９７：３であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の透明導電膜の比抵抗は４．２×１０-4Ω・ｃｍであり、表面抵抗は１４．０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６５％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．７倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．３倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 97: 3. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 × 10 −4 Ω · cm, and the surface resistance was 14.0 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.7 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.3 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例２３）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（ＴｉＯ；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９７：３となる割合で混合し、原料粉末の混合物を得た。次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（１．０１３２５×１０2ｋＰａ）のアルゴン雰囲気下、８００℃で４時間焼結して、酸化物焼結体（２１）を得た。
　得られた、酸化物焼結体（２１）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。この、酸化物焼結体（２１）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）との結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 23)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders, and these are Zn: Ti Were mixed at a ratio of 97: 3 to obtain a mixture of raw material powders. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 800 ° C. for 4 hours under an argon atmosphere at normal pressure (1.01325 × 10 2 kPa) to obtain an oxide sintered body (21).
When the obtained oxide sintered body (21) was analyzed with an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti. = 97: 3 (Ti / (Zn + Ti) = 0.03). When the crystal structure of the oxide sintered body (21) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) And no titanium oxide was present.
　次に、得られた、酸化物焼結体（２１）を２０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてＰＬＤ法により透明導電膜を成膜し、透明導電基板を得た。すなわち、パルスレーザ蒸着装置（誠南工業（株）製「ＰＳ－２０００」）内に、上記ターゲットと、該ターゲットに対向させるように石英ガラス基板とを設置し、レーザ発光装置（ラムダ・フィジクス（株）製「Ｃｏｍｅｘ２０５型」）を用いて、下記の成膜条件下、成膜時間１２０分間で、膜厚３００ｎｍの透明導電膜を形成した。
＜成膜条件＞
　　Laser:ArF Excimer Laser(波長＝１９３ｎｍ)
　　Laser Energy:１８ｍＪ
　　Repetition Frequency:５Ｈｚ
　　Target to substrate Distance:４０ｎｍ
　　Substrate:Corning＃１７３７
　　Substrate Temperature(℃)：２００℃
　　Base Pressure:７．２×１０-4Ｐａ
　　Gas Pressure(酸素)：０．２５Ｐａ
　　Gas Flow Rate:８．６ｓｃｃｍ
　　Film thickness:３００ｎｍ Next, by processing the obtained oxide sintered body (21) into a disk shape of 20 mmφ, a target is prepared, and a transparent conductive film is formed by using the PLD method to form a transparent conductive substrate. Obtained. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
<Film formation conditions>
Laser: ArF Excimer Laser (wavelength = 193nm)
Laser Energy: 18mJ
Repetition Frequency: 5Hz
Target to substrate distance: 40nm
Substrate: Corning # 1737
Substrate Temperature (℃): 200 ℃
Base Pressure: 7.2 × 10 −4 Pa
Gas Pressure (Oxygen): 0.25Pa
Gas Flow Rate: 8.6sccm
Film thickness: 300nm
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９７：３であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の透明導電膜の比抵抗は４．０×１０-4Ω・ｃｍであり、表面抵抗は１３．３Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６５％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．７倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．３倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 97: 3. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.0 × 10 −4 Ω · cm, and the surface resistance was 13.3 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.7 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.3 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例２４）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3（III）；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９７：３となる割合で混合し、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（２２）を得た（ホットプレス焼結）。得られた酸化物焼結体（２２）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。この酸化物焼結体（２２）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）との結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 24)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 (III); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. These were mixed in such a ratio that the Zn: Ti atomic ratio was 97: 3 to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (22) (hot press sintering). When the obtained oxide sintered body (22) was analyzed with an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 97: 3 (Ti / (Zn + Ti) = 0.03). When the crystal structure of this oxide sintered body (22) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) It was a mixture of crystalline phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（２２）を２０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてＰＬＤ法により透明導電膜を成膜し、透明導電基板を得た。すなわち、パルスレーザ蒸着装置（誠南工業（株）製「ＰＳ－２０００」）内に、上記ターゲットと、該ターゲットに対向させるように石英ガラス基板とを設置し、レーザ発光装置（ラムダ・フィジクス（株）社製「Ｃｏｍｅｘ２０５型」）を用いて、下記の成膜条件下、成膜時間１２０分間で、膜厚３００ｎｍの透明導電膜を形成した。
＜成膜条件＞
　　Laser:ArF Excimer Laser(波長＝１９３ｎｍ)
　　Laser Energy:１８ｍＪ
　　Repetition Frequency:５Ｈｚ
　　Target to substrate Distance:４０ｎｍ
　　Substrate:Corning＃１７３７
　　Substrate Temperature(℃)：２００℃
　　Base Pressure:７．２×１０-4Ｐａ
　　Gas Pressure(酸素)：０．２５Ｐａ
　　Gas Flow Rate:８．６ｓｃｃｍ
　　Film thickness:３００ｎｍ Next, by processing the obtained oxide sintered body (22) into a disk shape of 20 mmφ, a target is prepared, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate. It was. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the above target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( Using a “Comex 205 type” manufactured by Co., Ltd., a transparent conductive film having a film thickness of 300 nm was formed under the following film forming conditions with a film forming time of 120 minutes.
<Film formation conditions>
Laser: ArF Excimer Laser (wavelength = 193nm)
Laser Energy: 18mJ
Repetition Frequency: 5Hz
Target to substrate distance: 40nm
Substrate: Corning # 1737
Substrate Temperature (℃): 200 ℃
Base Pressure: 7.2 × 10 −4 Pa
Gas Pressure (Oxygen): 0.25Pa
Gas Flow Rate: 8.6sccm
Film thickness: 300nm
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９７：３であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の透明導電膜の比抵抗は４．２×１０-4Ω・ｃｍであり、表面抵抗は１４．０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６５％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．７倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．３倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 97: 3. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 × 10 −4 Ω · cm, and the surface resistance was 14.0 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.7 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.3 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例２５）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（ＴｉＯ（ＩＩ）；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９７：３となる割合で混合し、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（２３）を得た（ホットプレス焼結）。得られた酸化物焼結体（２３）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。この酸化物焼結体（２３）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）との結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 25)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, and heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (23) (hot press sintering). When the obtained oxide sintered body (23) was analyzed by an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 97: 3 (Ti / (Zn + Ti) = 0.03). When the crystal structure of this oxide sintered body (23) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) It was a mixture of crystalline phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（２３）を２０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてＰＬＤ法により透明導電膜を成膜し、透明導電基板を得た。すなわち、パルスレーザ蒸着装置（誠南工業（株）製「ＰＳ－２０００」）内に、上記ターゲットと、該ターゲットに対向させるように石英ガラス基板とを設置し、レーザ発光装置（ラムダ・フィジクス（株）製「Ｃｏｍｅｘ２０５型」）を用いて、下記の成膜条件下、成膜時間１２０分間で、膜厚３００ｎｍの透明導電膜を形成した。
＜成膜条件＞
　　Laser:ArF Excimer Laser(波長＝１９３ｎｍ)
　　Laser Energy:１８ｍＪ
　　Repetition Frequency:５Ｈｚ
　　Target to substrate Distance:４０ｎｍ
　　Substrate:Corning＃１７３７
　　Substrate Temperature(℃)：２００℃
　　Base Pressure:７．２×１０-4Ｐａ
　　Gas Pressure(酸素)：０．２５Ｐａ
　　Gas Flow Rate:８．６ｓｃｃｍ
　　Film thickness:３００ｎｍ Next, by processing the obtained oxide sintered body (23) into a disk shape of 20 mmφ, a target is prepared, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate. It was. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
<Film formation conditions>
Laser: ArF Excimer Laser (wavelength = 193nm)
Laser Energy: 18mJ
Repetition Frequency: 5Hz
Target to substrate distance: 40nm
Substrate: Corning # 1737
Substrate Temperature (℃): 200 ℃
Base Pressure: 7.2 × 10 −4 Pa
Gas Pressure (Oxygen): 0.25Pa
Gas Flow Rate: 8.6sccm
Film thickness: 300nm
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９７：３であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の透明導電膜の比抵抗は４．０×１０-4Ω・ｃｍであり、表面抵抗は１３．３Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６５％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．７倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．３倍であり、耐熱性に優れることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 97: 3. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.0 × 10 −4 Ω · cm, and the surface resistance was 13.3 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.7 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.3 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例２６）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（ＴｉＯ（II）；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９３：７となる割合で混合し、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（２４）を得た（ホットプレス焼結）。得られた酸化物焼結体（２４）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９３：７（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０７）であった。この酸化物焼結体（２４）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）との結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 26)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. A mixture of raw material powders was obtained by mixing the Zn: Ti at an atomic ratio of 93: 7. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (24) (hot press sintering). When the obtained oxide sintered body (24) was analyzed by an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 93: 7 (Ti / (Zn + Ti) = 0.07). When the crystal structure of this oxide sintered body (24) was examined by an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) It was a mixture of crystalline phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（２４）を２０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてＰＬＤ法により透明導電膜を成膜し、透明導電基板を得た。すなわち、パルスレーザ蒸着装置（誠南工業（株）製「ＰＳ－２０００」）内に、上記ターゲットと、該ターゲットに対向させるように石英ガラス基板とを設置し、レーザ発光装置（ラムダ・フィジクス（株）製「Ｃｏｍｅｘ２０５型」）を用いて、下記の成膜条件下、成膜時間１２０分間で、膜厚３００ｎｍの透明導電膜を形成した。
＜成膜条件＞
　　Laser:ArF Excimer Laser(波長＝１９３ｎｍ)
　　Laser Energy:１８ｍＪ
　　Repetition Frequency:５Ｈｚ
　　Target to substrate Distance:４０ｎｍ
　　Substrate:Corning＃１７３７
　　Substrate Temperature(℃)：２００℃
　　Base Pressure:７．２×１０-4Ｐａ
　　Gas Pressure(酸素)：０．２５Ｐａ
　　Gas Flow Rate:８．６ｓｃｃｍ
　　Film thickness:３００ｎｍ Next, by processing the obtained oxide sintered body (24) into a disk shape of 20 mmφ, a target is prepared, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate. It was. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
<Film formation conditions>
Laser: ArF Excimer Laser (wavelength = 193nm)
Laser Energy: 18mJ
Repetition Frequency: 5Hz
Target to substrate distance: 40nm
Substrate: Corning # 1737
Substrate Temperature (℃): 200 ℃
Base Pressure: 7.2 × 10 −4 Pa
Gas Pressure (Oxygen): 0.25Pa
Gas Flow Rate: 8.6sccm
Film thickness: 300nm
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９３：７であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の透明導電膜の比抵抗は９．０×１０-4Ω・ｃｍであり、表面抵抗は３０．０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６７％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．４倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 93: 7. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 9.0 × 10 −4 Ω · cm, and the surface resistance was 30.0 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 67% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.4 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
　（比較例９）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（ＴｉＯ（ＩＩ）；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が８８：１２となる割合で混合し、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（Ｃ９）を得た（ホットプレス焼結）。得られた酸化物焼結体（Ｃ３）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝８８：１２（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．１２）であった。この酸化物焼結体（Ｃ９）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）との結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Comparative Example 9)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. A mixture of raw material powders was obtained by mixing at a ratio of the Zn: Ti atomic ratio of 88:12. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (C9) (hot press sintering). When the obtained oxide sintered body (C3) was analyzed with an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 88:12 (Ti / (Zn + Ti) = 0.12). When the crystal structure of this oxide sintered body (C9) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) It was a mixture of crystalline phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（Ｃ９）を２０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてＰＬＤ法により透明導電膜を成膜し、透明導電基板を得た。すなわち、パルスレーザ蒸着装置（誠南工業（株）製「ＰＳ－２０００」）内に、上記ターゲットと、該ターゲットに対向させるように石英ガラス基板とを設置し、レーザ発光装置（ラムダ・フィジクス（株）製「Ｃｏｍｅｘ２０５型」）を用いて、下記の成膜条件下、成膜時間１２０分間で、膜厚３００ｎｍの透明導電膜を形成した。
＜成膜条件＞
　　Laser:ArF Excimer Laser(波長＝１９３ｎｍ)
　　Laser Energy:１８ｍＪ
　　Repetition Frequency:５Ｈｚ
　　Target to substrate Distance:４０ｎｍ
　　Substrate:Corning＃１７３７
　　Substrate Temperature(℃)：２００℃
　　Base Pressure:７．２×１０-4Ｐａ
　　Gas Pressure(酸素)：０．２５Ｐａ
　　Gas Flow Rate:８．６ｓｃｃｍ
　　Film thickness:３００ｎｍ Next, by processing the obtained oxide sintered body (C9) into a disk shape of 20 mmφ, a target is prepared, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate. It was. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
<Film formation conditions>
Laser: ArF Excimer Laser (wavelength = 193nm)
Laser Energy: 18mJ
Repetition Frequency: 5Hz
Target to substrate distance: 40nm
Substrate: Corning # 1737
Substrate Temperature (℃): 200 ℃
Base Pressure: 7.2 × 10 −4 Pa
Gas Pressure (Oxygen): 0.25Pa
Gas Flow Rate: 8.6sccm
Film thickness: 300nm
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝８８：１２であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の透明導電膜の比抵抗は１．１×１０-2Ω・ｃｍであり、表面抵抗は３６７．０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均７５％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．１倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．１倍であり、耐熱性に優れることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であるが高抵抗であることが明らかである。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 88:12. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 1.1 × 10 −2 Ω · cm, and the surface resistance was 367.0 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was 90% on average in the visible region (380 nm to 780 nm) and 75% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.1 times that before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
From the above, the obtained film on the transparent conductive substrate is a transparent conductive film that is transparent and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that it is a resistance.
　（比較例１０）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3（III）；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が８８：１２となる割合で混合し、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（Ｃ１０）を得た（ホットプレス焼結）。得られた酸化物焼結体（Ｃ１０）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝８８：１２（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．１２）であった。この酸化物焼結体（Ｃ１０）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）との結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Comparative Example 10)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 (III); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. These were mixed at a ratio of the Zn: Ti atomic ratio of 88:12 to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (C10) (hot press sintering). When the obtained oxide sintered body (C10) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 88:12 (Ti / (Zn + Ti) = 0.12). When the crystal structure of this oxide sintered body (C10) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) It was a mixture of crystalline phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（Ｃ１０）を２０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてＰＬＤ法により透明導電膜を成膜し、透明導電基板を得た。すなわち、パルスレーザ蒸着装置（誠南工業（株）製「ＰＳ－２０００」）内に、上記ターゲットと、該ターゲットに対向させるように石英ガラス基板とを設置し、レーザ発光装置（ラムダ・フィジクス（株）製「Ｃｏｍｅｘ２０５型」）を用いて、下記の成膜条件下、成膜時間１２０分間で、膜厚３００ｎｍの透明導電膜を形成した。
　＜成膜条件＞
　　Laser:ArF Excimer Laser(波長＝１９３ｎｍ)
　　Laser Energy:１８ｍＪ
　　Repetition Frequency:５Ｈｚ
　　Target to substrate Distance:４０ｎｍ
　　Substrate:Corning＃１７３７
　　Substrate Temperature(℃)：２００℃
　　Base Pressure:７．２×１０-4Ｐａ
　　Gas Pressure(酸素)：０．２５Ｐａ
　　Gas Flow Rate:８．６ｓｃｃｍ
　　Film thickness:３００ｎｍ Next, by processing the obtained oxide sintered body (C10) into a disk shape of 20 mmφ, a target is prepared, and a transparent conductive film is formed by using the PLD method to obtain a transparent conductive substrate. It was. That is, in a pulse laser deposition apparatus (“PS-2000” manufactured by Seinan Kogyo Co., Ltd.), the target and a quartz glass substrate are placed so as to face the target, and a laser light emitting device (Lambda Physics ( A 300 nm-thick transparent conductive film was formed under the following film-forming conditions with a film-forming time of 120 minutes.
<Film formation conditions>
Laser: ArF Excimer Laser (wavelength = 193nm)
Laser Energy: 18mJ
Repetition Frequency: 5Hz
Target to substrate distance: 40nm
Substrate: Corning # 1737
Substrate Temperature (℃): 200 ℃
Base Pressure: 7.2 × 10 −4 Pa
Gas Pressure (Oxygen): 0.25Pa
Gas Flow Rate: 8.6sccm
Film thickness: 300nm
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝８８：１２であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の透明導電膜の比抵抗は２．４×１０-2Ω・ｃｍであり、表面抵抗は８００．０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均７５％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．１倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．１倍であり、耐熱性に優れることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であるが高抵抗であることが明らかである。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 88:12. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.4 × 10 −2 Ω · cm, and the surface resistance was 800.0Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was 90% on average in the visible region (380 nm to 780 nm) and 75% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.1 times that before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
From the above, the obtained film on the transparent conductive substrate is a transparent conductive film that is transparent and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that it is a resistance.
　（実施例２７）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９６：４となる割合で混合し、原料粉末の混合物を得た。次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（１００Ｐａ）のアルゴン雰囲気下、５００℃で３時間アニールして、酸化物混合体（２５）を得た。
　得られた酸化物混合体（２５）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９６：４（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０４）であった。
　次に、得られた酸化物混合体（２５）を２０ｍｍφの円盤状に加工することにより、タブレットを作製し、これを用いてイオンプレーティング法により透明導電膜を成膜し、透明導電基板を得た。
　すなわち、イオンプレーティング装置（中外炉工業（株）製「ＳＵＰＬａＤＵＯ」）を用い、下記の条件でイオンプレーティングを行い、透明基材（厚み０．７ｍｍの無アルカリガラス基板）上に、膜厚２００ｎｍの透明導電膜を形成した。
　　成膜前の基板の予備加熱温度：２５０℃
　　成膜時の圧力　　　　　　　：０．３Ｐａ
　　成膜時の雰囲気ガス条件　　：アルゴン＝１６０ｓｃｃｍ、酸素＝２ｓｃｃｍ
　　成膜時の放電電流　　　　　：１００Ａ
　　成膜時間　　　　　　　　　：２００秒 (Example 27)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was annealed at 500 ° C. for 3 hours under an argon atmosphere at normal pressure (100 Pa) to obtain an oxide mixture (25).
When the obtained oxide mixture (25) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 96. : 4 (Ti / (Zn + Ti) = 0.04).
Next, a tablet is produced by processing the obtained oxide mixture (25) into a disk shape of 20 mmφ, and a transparent conductive film is formed by ion plating using this to form a transparent conductive substrate. Obtained.
That is, using an ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.), ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm). A 200 nm transparent conductive film was formed.
Preheating temperature of substrate before film formation: 250 ° C.
Pressure during film formation: 0.3 Pa
Atmospheric gas conditions during film formation: Argon = 160 sccm, Oxygen = 2 sccm
Discharge current during film formation: 100 A
Deposition time: 200 seconds
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９６：４であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は７．３×１０-4Ω・ｃｍであり、表面抵抗は３６．５Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６５％であった。なお、成膜前のガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．６倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．３倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.3 × 10 −4 Ω · cm, and the surface resistance was 36.5 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). The transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.6 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.3 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（比較例１１）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９９：１となる割合で混合し、原料粉末の混合物を得た。次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（１００Ｐａ）のアルゴン雰囲気下、４００℃で３時間アニールして、酸化物混合体（Ｃ１１）を得た。
　得られた酸化物混合体（Ｃ１１）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９９：１（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０１）であった。
　次に、得られた酸化物混合体（Ｃ１１）を２０ｍｍφの円盤状に加工することにより、タブレットを作製し、これを用いてイオンプレーティング法により透明導電膜を成膜し、透明導電基板を得た。
　すなわち、イオンプレーティング装置（中外炉工業（株）製「ＳＵＰＬａＤＵＯ」）を用い、下記の条件でイオンプレーティングを行い、透明基材（厚み０．７ｍｍの無アルカリガラス基板）上に、膜厚１５０ｎｍの透明導電膜を形成した。
　　成膜前の基板の予備加熱温度：２５０℃
　　成膜時の圧力　　　　　　　：０．３Ｐａ
　　成膜時の雰囲気ガス条件　　：アルゴン＝１６０ｓｃｃｍ、酸素＝２ｓｃｃｍ
　　成膜時の放電電流　　　　　：１００Ａ
　　成膜時間　　　　　　　　　：１５０秒 (Comparative Example 11)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. A mixture of raw material powders was obtained by mixing at a ratio of the Zn: Ti atomic ratio of 99: 1. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was annealed at 400 ° C. for 3 hours under an argon atmosphere at normal pressure (100 Pa) to obtain an oxide mixture (C11).
When the obtained oxide mixture (C11) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 99. : 1 (Ti / (Zn + Ti) = 0.01).
Next, by processing the obtained oxide mixture (C11) into a disk shape of 20 mmφ, a tablet is prepared, and a transparent conductive film is formed by ion plating using this, and a transparent conductive substrate is formed. Obtained.
That is, using an ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.), ion plating is performed under the following conditions, and the film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm). A 150 nm transparent conductive film was formed.
Preheating temperature of substrate before film formation: 250 ° C.
Pressure during film formation: 0.3 Pa
Atmospheric gas conditions during film formation: Argon = 160 sccm, Oxygen = 2 sccm
Discharge current during film formation: 100 A
Deposition time: 150 seconds
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９９：１であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 99: 1. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は７．０×１０-3Ω・ｃｍであり、表面抵抗は４６７Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９１％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均７０％であった。なお、成膜前のガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の３．１倍であり、耐湿性に劣ることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の３．０倍であり、耐熱性に劣ることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬後には膜は完全に溶解し、消失していた。また、得られた透明導電性基板の耐酸性を評価したところ、膜は完全に溶解し、消失していた。
　以上のことから、得られた透明導電性基板上の膜は、透明であるが、高抵抗であり、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）に劣る透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.0 × 10 −3 Ω · cm, and the surface resistance was 467 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 91% in the visible region (380 to 780 nm) and an average of 70% in the infrared region (780 to 2700 nm). The transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 3.1 times the surface resistance before the moisture resistance test, and the moisture resistance was inferior. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 3.0 times the surface resistance before the heat test, which is inferior in heat resistance.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared after immersion. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared.
From the above, the film on the transparent conductive substrate obtained is a transparent conductive film that is transparent but has high resistance and inferior chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例２８）
　実施例２７と同様にして得られた酸化物混合体（２５）を２０ｍｍφの円盤状に加工することにより、タブレットを作製し、これを用いてイオンプレーティング法により透明導電膜を成膜し、透明導電基板を得た。
　すなわち、イオンプレーティング装置（中外炉工業（株）製「ＳＵＰＬａＤＵＯ」）を用い、下記の条件でイオンプレーティングを行い、透明基材（厚み０．７ｍｍの無アルカリガラス基板）上に、膜厚５０ｎｍの透明導電膜を形成した。
　　成膜前の基板の予備加熱温度：２５０℃
　　成膜時の圧力　　　　　　　：０．３Ｐａ
　　成膜時の雰囲気ガス条件　　：アルゴン＝１６０ｓｃｃｍ、酸素＝２ｓｃｃｍ
　　成膜時の放電電流　　　　　：１００Ａ
　　成膜時間　　　　　　　　　：５０秒 (Example 28)
By processing the oxide mixture (25) obtained in the same manner as in Example 27 into a disk shape of 20 mmφ, a tablet was prepared, and a transparent conductive film was formed by ion plating using this, A transparent conductive substrate was obtained.
That is, using an ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.), ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm). A 50 nm transparent conductive film was formed.
Preheating temperature of substrate before film formation: 250 ° C.
Pressure during film formation: 0.3 Pa
Atmospheric gas conditions during film formation: Argon = 160 sccm, Oxygen = 2 sccm
Discharge current during film formation: 100 A
Deposition time: 50 seconds
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９６：４であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は８．０×１０-4Ω・ｃｍであり、表面抵抗は１６０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９１％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均７０％であった。なお、成膜前のガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．８倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．５倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、膜厚が１００ｎｍ以下であっても、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 8.0 × 10 −4 Ω · cm, and the surface resistance was 160Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 91% in the visible region (380 to 780 nm) and an average of 70% in the infrared region (780 to 2700 nm). The transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.8 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.5 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is transparent and low resistance even when the film thickness is 100 nm or less, and has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that this is a transparent conductive film having both properties.
　（実施例２９）
　実施例２７と同様にして得られた酸化物混合体（２５）を２０ｍｍφの円盤状に加工することにより、タブレットを作製し、これを用いてイオンプレーティング法により透明導電膜を成膜し、透明導電基板を得た。すなわち、イオンプレーティング装置（中外炉工業（株）製「ＳＵＰＬａＤＵＯ」）を用い、下記の条件でイオンプレーティングを行い、透明基材（２００℃以上で耐熱性を示す厚み０．３ｍｍの耐熱透明樹脂フィルム）上に、膜厚２００ｎｍの透明導電膜を形成した。
　　成膜前の基板の予備加熱温度：２００℃
　　成膜時の圧力　　　　　　　：０．３Ｐａ
　　成膜時の雰囲気ガス条件　　：アルゴン＝１６０ｓｃｃｍ、酸素＝２ｓｃｃｍ
　　成膜時の放電電流　　　　　：１００Ａ
　　成膜時間　　　　　　　　　：２００秒 (Example 29)
By processing the oxide mixture (25) obtained in the same manner as in Example 27 into a disk shape of 20 mmφ, a tablet was prepared, and a transparent conductive film was formed by ion plating using this, A transparent conductive substrate was obtained. That is, using an ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.), ion plating was performed under the following conditions, and a transparent base material (heat resistant transparent with a thickness of 0.3 mm showing heat resistance at 200 ° C. or higher) A transparent conductive film having a thickness of 200 nm was formed on the (resin film).
Preheating temperature of substrate before film formation: 200 ° C.
Pressure during film formation: 0.3 Pa
Atmospheric gas conditions during film formation: Argon = 160 sccm, Oxygen = 2 sccm
Discharge current during film formation: 100 A
Deposition time: 200 seconds
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９６：４であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. Was found to be substituted and dissolved in zinc.
　得られた透明導電性基板上の透明導電膜の比抵抗は８．５×１０-4Ω・ｃｍであり、表面抵抗は４２．５Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８５％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６５％であった。なお、成膜前の耐熱透明樹脂フィルムの可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９０％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９０％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．８倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．５倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、基板が耐熱性フィルムであっても、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 8.5 × 10 −4 Ω · cm, and the surface resistance was 42.5 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 85% in the visible region (380 nm to 780 nm) and an average of 65% in the infrared region (780 nm to 2700 nm). The transmittance of the heat-resistant transparent resin film before film formation in the visible region (380 nm to 780 nm) was 90% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 90% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.8 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.5 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is transparent and low resistance even when the substrate is a heat resistant film, and has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that this is a transparent conductive film having both properties.
　（実施例３０）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９６：４となる割合で混合し、原料粉末の混合物を得た。次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（１．０１３２５×１０2ｋＰａ）のアルゴン雰囲気下、８００℃で４時間焼結して、酸化物焼結体（２６）を得た。
　得られた酸化物焼結体（２６）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９６：４（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０４）であった。この酸化物焼結体（２６）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 30)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was sintered at 800 ° C. for 4 hours in an argon atmosphere at normal pressure (1.01325 × 10 2 kPa) to obtain an oxide sintered body (26).
When the obtained oxide sintered body (26) was analyzed by an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = It was 96: 4 (Ti / (Zn + Ti) = 0.04). When the crystal structure of this oxide sintered body (26) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
　次に、得られた酸化物焼結体（２６）を２０ｍｍφの円盤状に加工することにより、タブレットを作製し、これを用いてイオンプレーティング法により透明導電膜を成膜し、透明導電基板を得た。
　すなわち、イオンプレーティング装置（中外炉工業（株）製「ＳＵＰＬａＤＵＯ」）を用い、下記の条件でイオンプレーティングを行い、透明基材（厚み０．７ｍｍの無アルカリガラス基板）上に、膜厚２００ｎｍの透明導電膜を形成した。
　　成膜前の基板の予備加熱温度：２５０℃
　　成膜時の圧力　　　　　　　：０．３Ｐａ
　　成膜時の雰囲気ガス条件　　：アルゴン＝１６０ｓｃｃｍ、酸素＝２ｓｃｃｍ
　　成膜時の放電電流　　　　　：１００Ａ
　　成膜時間　　　　　　　　　：２００秒 Next, the obtained oxide sintered body (26) is processed into a disk shape of 20 mmφ to produce a tablet, and a transparent conductive film is formed by ion plating using the tablet, thereby forming a transparent conductive substrate. Got.
That is, using an ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.), ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm). A 200 nm transparent conductive film was formed.
Preheating temperature of substrate before film formation: 250 ° C.
Pressure during film formation: 0.3 Pa
Atmospheric gas conditions during film formation: Argon = 160 sccm, Oxygen = 2 sccm
Discharge current during film formation: 100 A
Deposition time: 200 seconds
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９６：４であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の透明導電膜の比抵抗は７．８×１０-4Ω・ｃｍであり、表面抵抗は３９．０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６５％であった。なお、成膜前のガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．５倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．３倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.8 × 10 −4 Ω · cm, and the surface resistance was 39.0 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). The transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.5 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.3 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例３１）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９６：４となる割合で混合し、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（２７）を得た。
　得られた酸化物焼結体（２７）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９６：４（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０４）であった。この酸化物焼結体（２７）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 31)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. Mixing was performed at a Zn: Ti atomic ratio of 96: 4 to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (27).
When the obtained oxide sintered body (27) was analyzed with an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = It was 96: 4 (Ti / (Zn + Ti) = 0.04). When the crystal structure of the oxide sintered body (27) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（２７）を２０ｍｍφの円盤状に加工することにより、タブレットを作製し、これを用いてイオンプレーティング法により透明導電膜を成膜し、透明導電基板を得た。すなわち、イオンプレーティング装置（中外炉工業（株）製「ＳＵＰＬａＤＵＯ」）を用い、下記の条件でイオンプレーティングを行い、透明基材（厚み０．７ｍｍの無アルカリガラス基板）上に、膜厚２００ｎｍの透明導電膜を形成した。
　　成膜前の基板の予備加熱温度：２５０℃
　　成膜時の圧力　　　　　　　：０．３Ｐａ
　　成膜時の雰囲気ガス条件　　：アルゴン＝１６０ｓｃｃｍ、酸素＝２ｓｃｃｍ
　　成膜時の放電電流　　　　　：１００Ａ
　　成膜時間　　　　　　　　　：２００秒 Next, by processing the obtained oxide sintered body (27) into a disk shape of 20 mmφ, a tablet is produced, and a transparent conductive film is formed by ion plating using the tablet, thereby forming a transparent conductive substrate. Got. That is, using an ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.), ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm). A 200 nm transparent conductive film was formed.
Preheating temperature of substrate before film formation: 250 ° C.
Pressure during film formation: 0.3 Pa
Atmospheric gas conditions during film formation: Argon = 160 sccm, Oxygen = 2 sccm
Discharge current during film formation: 100 A
Deposition time: 200 seconds
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９６：４であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の透明導電膜の比抵抗は７．３×１０-4Ω・ｃｍであり、表面抵抗は３６．５Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６５％であった。なお、成膜前のガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．６倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．３倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 96: 4. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.3 × 10 −4 Ω · cm, and the surface resistance was 36.5 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). The transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.6 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.3 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例３２）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（ＴｉＯ；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９７：３となる割合で混合し、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の焼結体を得た。さらに該焼結体をアルゴン雰囲気下、８００℃で４時間焼結して、酸化物焼結体（２８）を得た。
　得られた酸化物焼結体（２８）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。この酸化物焼結体（２８）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 32)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders, and these are Zn: Ti Were mixed at a ratio of 97: 3 to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped sintered body. Further, the sintered body was sintered at 800 ° C. for 4 hours in an argon atmosphere to obtain an oxide sintered body (28).
When the obtained oxide sintered body (28) was analyzed with an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 97: 3 (Ti / (Zn + Ti) = 0.03). When the crystal structure of this oxide sintered body (28) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
　次に、得られた酸化物焼結体（２８）を２０ｍｍφの円盤状に加工することにより、タブレットを作製し、これを用いてイオンプレーティング法により透明導電膜を成膜し、透明導電基板を得た。
　すなわち、イオンプレーティング装置（中外炉工業（株）製「ＳＵＰＬａＤＵＯ」）を用い、下記の条件でイオンプレーティングを行い、透明基材（厚み０．７ｍｍの無アルカリガラス基板）上に、膜厚２００ｎｍの透明導電膜を形成した。
　　成膜前の基板の予備加熱温度：２５０℃
　　成膜時の圧力　　　　　　　：０．３Ｐａ
　　成膜時の雰囲気ガス条件　　：アルゴン＝１６０ｓｃｃｍ、酸素＝２ｓｃｃｍ
　　成膜時の放電電流　　　　　：１００Ａ
　　成膜時間　　　　　　　　　：２００秒 Next, the obtained oxide sintered body (28) is processed into a disk shape of 20 mmφ to produce a tablet, and a transparent conductive film is formed by ion plating using the tablet, thereby forming a transparent conductive substrate. Got.
That is, using an ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.), ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm). A 200 nm transparent conductive film was formed.
Preheating temperature of substrate before film formation: 250 ° C.
Pressure during film formation: 0.3 Pa
Atmospheric gas conditions during film formation: Argon = 160 sccm, Oxygen = 2 sccm
Discharge current during film formation: 100 A
Deposition time: 200 seconds
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９７：３であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の透明導電膜の比抵抗は６．０×１０-4Ω・ｃｍであり、表面抵抗は３０．０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６５％であった。なお、成膜前のガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．６倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．３倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 97: 3. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 6.0 × 10 −4 Ω · cm, and the surface resistance was 30.0Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). The transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.6 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.3 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例３３）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（ＴｉＯ；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９７：３となる割合で混合し、原料粉末の混合物を得た。次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（１．０１３２５×１０2ｋＰａ）のアルゴン雰囲気下、１０００℃で４時間焼結して、酸化物焼結体（２９）を得た。
　得られた酸化物焼結体（２９）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。この酸化物焼結体（２９）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 33)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders, and these are Zn: Ti Were mixed at a ratio of 97: 3 to obtain a mixture of raw material powders. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 1000 ° C. for 4 hours under an argon atmosphere at normal pressure (1.01325 × 10 2 kPa) to obtain an oxide sintered body (29).
When the obtained oxide sintered body (29) was analyzed with an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 97: 3 (Ti / (Zn + Ti) = 0.03). When the crystal structure of the oxide sintered body (29) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
　次に、得られた酸化物焼結体（２９）を２０ｍｍφの円盤状に加工することにより、タブレットを作製し、これを用いてイオンプレーティング法により透明導電膜を成膜し、透明導電基板を得た。
　すなわち、イオンプレーティング装置（中外炉工業（株）製「ＳＵＰＬａＤＵＯ」）を用い、下記の条件でイオンプレーティングを行い、透明基材（厚み０．７ｍｍの無アルカリガラス基板）上に、膜厚２００ｎｍの透明導電膜を形成した。
　　成膜前の基板の予備加熱温度：２５０℃
　　成膜時の圧力　　　　　　　：０．３Ｐａ
　　成膜時の雰囲気ガス条件　　：アルゴン＝１６０ｓｃｃｍ、酸素＝２ｓｃｃｍ
　　成膜時の放電電流　　　　　：１００Ａ
　　成膜時間　　　　　　　　　：２００秒 Next, by processing the obtained oxide sintered body (29) into a disk shape of 20 mmφ, a tablet is produced, and a transparent conductive film is formed by ion plating using this, and a transparent conductive substrate is formed. Got.
That is, using an ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.), ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm). A 200 nm transparent conductive film was formed.
Preheating temperature of substrate before film formation: 250 ° C.
Pressure during film formation: 0.3 Pa
Atmospheric gas conditions during film formation: Argon = 160 sccm, Oxygen = 2 sccm
Discharge current during film formation: 100 A
Deposition time: 200 seconds
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９５：５であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の透明導電膜の比抵抗は６．０×１０-4Ω・ｃｍであり、表面抵抗は３０．０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６５％であった。なお、成膜前のガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．６倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．３倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 95: 5. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 6.0 × 10 −4 Ω · cm, and the surface resistance was 30.0Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). The transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.6 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.3 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（比較例１２）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（ＴｉＯ；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９８．５：１．５となる割合で混合し、原料粉末の混合物を得た。次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（１．０１３２５×１０2ｋＰａ）のアルゴン雰囲気下、１０００℃で４時間焼結して、酸化物焼結体（Ｃ１２）を得た。
　得られた酸化物焼結体（Ｃ１２）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９８．５：１．５（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０１５）であった。この酸化物焼結体（Ｃ１２）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Comparative Example 12)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders, and these are Zn: Ti Were mixed at a ratio of 98.5: 1.5 to obtain a raw material powder mixture. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 1000 ° C. for 4 hours in an argon atmosphere at normal pressure (1.01325 × 10 2 kPa) to obtain an oxide sintered body (C12).
When the obtained oxide sintered body (C12) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = It was 98.5: 1.5 (Ti / (Zn + Ti) = 0.015). When the crystal structure of the oxide sintered body (C12) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（Ｃ１２）を２０ｍｍφの円盤状に加工することにより、タブレットを作製し、これを用いてイオンプレーティング法により透明導電膜を成膜し、透明導電基板を得た。
　すなわち、イオンプレーティング装置（中外炉工業（株）製「ＳＵＰＬａＤＵＯ」）を用い、下記の条件でイオンプレーティングを行い、透明基材（厚み０．７ｍｍの無アルカリガラス基板）上に、膜厚２００ｎｍの透明導電膜を形成した。
　　成膜前の基板の予備加熱温度：２５０℃
　　成膜時の圧力　　　　　　　：０．３Ｐａ
　　成膜時の雰囲気ガス条件　　：アルゴン＝１６０ｓｃｃｍ、酸素＝２ｓｃｃｍ
　　成膜時の放電電流　　　　　：１００Ａ
　　成膜時間　　　　　　　　　：２００秒 Next, the obtained oxide sintered body (C12) was processed into a disk shape of 20 mmφ to produce a tablet, and a transparent conductive film was formed by ion plating using the tablet, thereby forming a transparent conductive substrate. Got.
That is, using an ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.), ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm). A 200 nm transparent conductive film was formed.
Preheating temperature of substrate before film formation: 250 ° C.
Pressure during film formation: 0.3 Pa
Atmospheric gas conditions during film formation: Argon = 160 sccm, Oxygen = 2 sccm
Discharge current during film formation: 100 A
Deposition time: 200 seconds
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９８．５：１．５であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の透明導電膜の比抵抗は１．２×１０-3Ω・ｃｍであり、表面抵抗は６０．０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均７０％であった。なお、成膜前のガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の２．６倍であり、耐湿性に劣ることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の２．０倍であり、耐熱性に劣ることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬後には膜は完全に溶解し、消失していた。また、得られた透明導電性基板の耐酸性を評価したところ、膜は完全に溶解し、消失していた。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるが、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）に劣る透明導電膜であることが明らかである。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 98.5: 1.5. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 1.2 × 10 −3 Ω · cm, and the surface resistance was 60.0Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 70% on average in the infrared region (780 nm to 2700 nm). The transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the moisture resistance test was 2.6 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was inferior. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 2.0 times the surface resistance before the heat test, and the heat resistance was poor.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared after immersion. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared.
From the above, the film on the obtained transparent conductive substrate is transparent and low resistance, but is a transparent conductive film inferior in chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance) Is clear.
　（比較例１３）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（ＴｉＯ；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が８８：１２となる割合で混合し、原料粉末の混合物を得た。次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（１．０１３２５×１０2ｋＰａ）のアルゴン雰囲気下、１０００℃で４時間焼結して、酸化物焼結体（Ｃ１３）を得た。
　得られた酸化物焼結体（Ｃ１３）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝８８：１２（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．１２）であった。この酸化物焼結体（Ｃ１３）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Comparative Example 13)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders, and these are Zn: Ti Were mixed at a ratio of 88:12 to obtain a mixture of raw material powders. Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 1000 ° C. for 4 hours in an argon atmosphere at normal pressure (1.01325 × 10 2 kPa) to obtain an oxide sintered body (C13).
When the obtained oxide sintered body (C13) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 88:12 (Ti / (Zn + Ti) = 0.12). When the crystal structure of this oxide sintered body (C13) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
　次に、得られた酸化物焼結体（Ｃ１３）を２０ｍｍφの円盤状に加工することにより、タブレットを作製し、これを用いてイオンプレーティング法により透明導電膜を成膜し、透明導電基板を得た。
　すなわち、イオンプレーティング装置（中外炉工業（株）製「ＳＵＰＬａＤＵＯ」）を用い、下記の条件でイオンプレーティングを行い、透明基材（厚み０．７ｍｍの無アルカリガラス基板）上に、膜厚２００ｎｍの透明導電膜を形成した。
　　成膜前の基板の予備加熱温度：２５０℃
　　成膜時の圧力　　　　　　　：０．３Ｐａ
　　成膜時の雰囲気ガス条件　　：アルゴン＝１６０ｓｃｃｍ、酸素＝２ｓｃｃｍ
　　成膜時の放電電流　　　　　：１００Ａ
　　成膜時間　　　　　　　　　：２００秒 Next, the obtained oxide sintered body (C13) is processed into a disk shape of 20 mmφ to produce a tablet, and a transparent conductive film is formed by ion plating using the tablet. Got.
That is, using an ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.), ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm). A 200 nm transparent conductive film was formed.
Preheating temperature of substrate before film formation: 250 ° C.
Pressure during film formation: 0.3 Pa
Atmospheric gas conditions during film formation: Argon = 160 sccm, Oxygen = 2 sccm
Discharge current during film formation: 100 A
Deposition time: 200 seconds
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝８８：１２であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかったが、結晶性は低下していた。
　得られた透明導電性基板上の透明導電膜の比抵抗は２．４×１０-2Ω・ｃｍであり、表面抵抗は１２００．０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均７３％であった。なお、成膜前のガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．１倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．１倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であるが高抵抗であることが明らかである。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 88:12. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc, but the crystallinity was lowered.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.4 × 10 −2 Ω · cm, and the surface resistance was 1200.0Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was 90% on average in the visible region (380 nm to 780 nm) and 73% on average in the infrared region (780 nm to 2700 nm). The transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.1 times that before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the obtained film on the transparent conductive substrate is a transparent conductive film that is transparent and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that it is a resistance.
　（実施例３４）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3（III）；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９３：７となる割合で混合し、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（３０）を得た。（ホットプレス）
　得られた酸化物焼結体（３０）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９３：７（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０７）であった。この酸化物焼結体（３０）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 34)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 (III); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. These were mixed at a ratio of the Zn: Ti atomic ratio of 93: 7 to obtain a raw material powder mixture. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (30). (hot press)
When the obtained oxide sintered body (30) was analyzed with an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 93: 7 (Ti / (Zn + Ti) = 0.07). When the crystal structure of the oxide sintered body (30) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
　次に、得られた酸化物焼結体（３０）を２０ｍｍφの円盤状に加工することにより、タブレットを作製し、これを用いてイオンプレーティング法により透明導電膜を成膜し、透明導電基板を得た。すなわち、イオンプレーティング装置（中外炉工業（株）製「ＳＵＰＬａＤＵＯ」）を用い、下記の条件でイオンプレーティングを行い、透明基材（厚み０．７ｍｍの無アルカリガラス基板）上に、膜厚２００ｎｍの透明導電膜を形成した。
　　成膜前の基板の予備加熱温度：２５０℃
　　成膜時の圧力：０．３Ｐａ
　　成膜時の雰囲気ガス条件：アルゴン＝１６０ｓｃｃｍ、酸素＝２ｓｃｃｍ
　　成膜時の放電電流：１００Ａ
　　成膜時間：２００秒 Next, by processing the obtained oxide sintered body (30) into a disk shape of 20 mmφ, a tablet is produced, and a transparent conductive film is formed by ion plating using this, and a transparent conductive substrate is formed. Got. That is, using an ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.), ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm). A 200 nm transparent conductive film was formed.
Preheating temperature of substrate before film formation: 250 ° C.
Pressure during film formation: 0.3 Pa
Atmospheric gas conditions during film formation: argon = 160 sccm, oxygen = 2 sccm
Discharge current during film formation: 100 A
Deposition time: 200 seconds
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９３：７であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の透明導電膜の比抵抗は１．１×１０-3Ω・ｃｍであり、表面抵抗は５５．０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６７％であった。なお、成膜前のガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．４倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 93: 7. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 1.1 × 10 −3 Ω · cm, and the surface resistance was 55.0Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 67% on average in the infrared region (780 nm to 2700 nm). The transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.4 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例３５）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（ＴｉＯ（II）；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９３：７となる割合で混合し、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（３１）を得た。（ホットプレス焼結）
　得られた酸化物焼結体（３１）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９３：７（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０７）であった。この酸化物焼結体（３１）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 35)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. A mixture of raw material powders was obtained by mixing the Zn: Ti at an atomic ratio of 93: 7. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (31). (Hot press sintering)
When the obtained oxide sintered body (31) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 93: 7 (Ti / (Zn + Ti) = 0.07). When the crystal structure of this oxide sintered body (31) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（３１）を２０ｍｍφの円盤状に加工することにより、タブレットを作製し、これを用いてイオンプレーティング法により透明導電膜を成膜し、透明導電基板を得た。すなわち、イオンプレーティング装置（中外炉工業（株）製「ＳＵＰＬａＤＵＯ」）を用い、下記の条件でイオンプレーティングを行い、透明基材（厚み０．７ｍｍの無アルカリガラス基板）上に、膜厚２００ｎｍの透明導電膜を形成した。
　　成膜前の基板の予備加熱温度：２５０℃
　　成膜時の圧力：０．３Ｐａ
　　成膜時の雰囲気ガス条件：アルゴン＝１６０ｓｃｃｍ、酸素＝２ｓｃｃｍ
　　成膜時の放電電流：１００Ａ
　　成膜時間：２００秒 Next, the obtained oxide sintered body (31) is processed into a disk shape of 20 mmφ to produce a tablet, and a transparent conductive film is formed by ion plating using the tablet, thereby forming a transparent conductive substrate. Got. That is, using an ion plating apparatus (“SUPLaDUO” manufactured by Chugai Furnace Co., Ltd.), ion plating is performed under the following conditions, and a film thickness is formed on a transparent substrate (a non-alkali glass substrate having a thickness of 0.7 mm). A 200 nm transparent conductive film was formed.
Preheating temperature of substrate before film formation: 250 ° C.
Pressure during film formation: 0.3 Pa
Atmospheric gas conditions during film formation: argon = 160 sccm, oxygen = 2 sccm
Discharge current during film formation: 100 A
Deposition time: 200 seconds
　形成した透明導電膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９３：７であった。また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の透明導電膜の比抵抗は９．４×１０-4Ω・ｃｍであり、表面抵抗は４７．０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６７％であった。なお、成膜前のガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．４倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。 The composition (Zn: Ti) in the formed transparent conductive film is quantitatively analyzed using a calibration curve by a fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation). As a result, Zn: Ti (atomic ratio) was 93: 7. The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 9.4 × 10 −4 Ω · cm, and the surface resistance was 47.0 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 67% on average in the infrared region (780 nm to 2700 nm). The transmittance in the visible region (380 nm to 780 nm) of the glass substrate before film formation averaged 94%, and the transmittance in the infrared region (780 nm to 2700 nm) averaged 94%.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.4 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is.
　（実施例３６）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化ガリウム（Ｇａ2Ｏ3、住友化学（株）製）、および酸化チタン（Ｔｉ2Ｏ3、（株）高純度化学研究所製）を、亜鉛元素とガリウム元素とチタン元素の元素数比が９３．０：２．０：５．０となるように秤量し、ポリプロピレン製の容器に入れ、更に２ｍｍφジルコニア製ボールと混合溶媒としてエタノールを入れた。これをボールミルにより混合し、混合粉末を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を金型に入れ、４０ＭＰａの圧力で加圧し、円盤型の成形体を得た。これを電気炉に入れ、Ａｒ雰囲気で１３００℃で加熱処理を行い、焼結体を得た。この焼結体の相対密度を焼結体のサイズから算出したところ９５．３％であった。なお、相対密度は、下記の式から求めている。得られた焼結体に研削、表面研磨を施し、５０．８ｍｍφ、厚さ３ｍｍの焼結体を得た。
　　相対密度＝１００×[（焼結体の密度）／（理論密度）]
　但し、理論密度＝（酸化亜鉛の単体密度×混合重量比＋酸化ガリウムの単体密度×混合重量比＋酸化チタンの単体密度×混合重量比） (Example 36)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the element number ratio of zinc element, gallium element, and titanium element is 93.0: 2.0: 5.0, put it in a polypropylene container, and then add ethanol as a 2mmφ zirconia ball and mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 95.3% when the relative density of this sintered compact was computed from the size of a sintered compact. The relative density is obtained from the following formula. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
Relative density = 100 × [(density of sintered body) / (theoretical density)]
However, theoretical density = (Zinc oxide simple substance density × mixing weight ratio + gallium oxide simple substance density × mixing weight ratio + titanium oxide simple substance density × mixing weight ratio)
　得られた焼結体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍφ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） The obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target size: 50.8mmφ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、４．７×１０-4Ωｃｍであった。表面抵抗は９．４Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. 0.7 × 10 −4 Ωcm. The surface resistance was 9.4Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。また、耐アルカリ性、耐酸性に優れていることから、パターニングの際には適当なエッチングレートを有することが推測される。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
　（実施例３７）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化ガリウム（Ｇａ2Ｏ3、住友化学（株）製）、および酸化チタン（Ｔｉ2Ｏ3、（株）高純度化学研究所製）を、亜鉛元素とガリウム元素とチタン元素の元素数比が９４．０：２．０：４．０となるように秤量し、ポリプロピレン製の容器に入れ、更に２ｍｍφジルコニア製ボールと混合溶媒としてエタノールを入れた。これをボールミルにより混合し、混合粉末を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を金型に入れ、４０ＭＰａの圧力で加圧し、円盤型の成形体を得た。これを電気炉に入れ、大気雰囲気中３００℃で加熱処理を行い、酸化物混合体を得た。
　得られた酸化物混合体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。 (Example 37)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the element number ratio of zinc element, gallium element, and titanium element is 94.0: 2.0: 4.0, put in a polypropylene container, and then add 2mmφ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put in an electric furnace and heat-treated at 300 ° C. in an air atmosphere to obtain an oxide mixture.
The obtained oxide mixture was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍφ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target size: 50.8mmφ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、４．６×１０-4Ω・ｃｍであった。表面抵抗は９．２Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５７％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. 0.6 × 10 −4 Ω · cm. The surface resistance was 9.2Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 57% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。また、耐アルカリ性、耐酸性に優れていることから、パターニングの際には適当なエッチングレートを有することが推測される。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
　（比較例１４）
　平均粒径が１μｍの酸化亜鉛粉末９７．７重量部と、平均粒径が０．２μ?の酸化アルミニウム粉末２．３重量部とを、ポリエチレン製ポットに入れ、乾式ボールミルを用いて７２時間混合し、原料粉末の混合物を得た。得られた混合物を金型に入れ、成形圧３００ｋｇ／ｃｍ2の圧力でプレスを行い、成形体を得た。この成形体に３ｔｏｎ／ｃｍ2の圧力でＣＩＰによる緻密化処理を施した後、以下の条件で焼結して、アルミニウムドープ酸化亜鉛の焼結体を得た。 
　　焼結温度　：１５００℃
　　昇温速度　：５０℃／時間
　　保持時間　：５時間
　　焼結雰囲気：大気中
　得られた焼結体は、Ｘ線回折で分析したところ、ＺｎＯとＺｎＡｌ2Ｏ4との２相の混合組織であった。 (Comparative Example 14)
97.7 parts by weight of zinc oxide powder having an average particle diameter of 1 μm and 2.3 parts by weight of aluminum oxide powder having an average particle diameter of 0.2 μ? Are placed in a polyethylene pot and mixed for 72 hours using a dry ball mill. Thus, a mixture of raw material powders was obtained. The obtained mixture was put in a mold and pressed at a molding pressure of 300 kg / cm 2 to obtain a molded body. The compact was subjected to densification treatment with CIP at a pressure of 3 ton / cm 2 and then sintered under the following conditions to obtain a sintered body of aluminum-doped zinc oxide.
Sintering temperature: 1500 ° C
Temperature increase rate: 50 ° C./hour Holding time: 5 hours Sintering atmosphere: in the air The obtained sintered body was analyzed by X-ray diffraction and found to have a mixed structure of two phases of ZnO and ZnAl 2 O 4. It was.
　次に、得られた焼結体を４インチφ、６ｍｍ厚の形状に加工し、インジウム半田を用いて無酸素銅製バッキングプレートにボンディングすることにより、ターゲットを作製した。そして、このターゲットを用いて、以下の条件でスパッタリング法による成膜を行い、透明基材（石英ガラス基板）上に膜厚５００ｎｍの透明導電膜を形成し、透明導電性基板を得た。形成した膜中のＡｌ含有量は２．３重量％であった。
　　スパッタリング装置：キャノンアネルバ製　「Ｅ－２００Ｓ」
　　スパッタ方式：ＤＣマグネトロンスパッタリング
　　磁界強度：１０００Ｇａｕｓｓ（ターゲット直上、水平成分）
　　基板温度：２５０℃
　　到達真空度：５×１０-5Ｐａ
　　スパッタリングガス：Ａｒ
　　スパッタリングガス圧：０．５Ｐａ
　　ＤＣパワー：３００Ｗ Next, the obtained sintered body was processed into a shape of 4 inches φ and 6 mm thick, and bonded to an oxygen-free copper backing plate using indium solder to prepare a target. And using this target, the film-forming by sputtering method was performed on the following conditions, the transparent conductive film with a film thickness of 500 nm was formed on the transparent base material (quartz glass substrate), and the transparent conductive substrate was obtained. The Al content in the formed film was 2.3% by weight.
Sputtering equipment: Canon Anelva “E-200S”
Sputtering method: DC magnetron sputtering Magnetic field strength: 1000 Gauss (directly above the target, horizontal component)
Substrate temperature: 250 ° C
Ultimate vacuum: 5 × 10 −5 Pa
Sputtering gas: Ar
Sputtering gas pressure: 0.5 Pa
DC power: 300W
　得られた透明導電性基板上の透明導電膜の比抵抗は４．２×１０-4Ω・ｃｍであり、表面抵抗は８．４Ω／□であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５０％であった。
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の２．１倍であり、耐湿性に劣ることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の２．０倍であり、耐熱性に劣ることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬後には膜は完全に溶解し、消失していた。また、得られた透明導電性基板の耐酸性を評価したところ、膜は完全に溶解し、消失していた。 The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 × 10 −4 Ω · cm, and the surface resistance was 8.4 Ω / □.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 50% in the infrared region (780 nm to 2700 nm).
When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 2.1 times the surface resistance before the moisture resistance test, and the moisture resistance was poor. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 2.0 times the surface resistance before the heat test, and the heat resistance was poor.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared after immersion. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, the film was completely dissolved and disappeared.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗ではあるが、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）には劣る透明導電膜であることが明らかである。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film which is transparent and low in resistance but inferior in chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear.
　（実施例３８）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化ガリウム（Ｇａ2Ｏ3、住友化学（株）製）、および酸化チタン（Ｔｉ2Ｏ3、（株）高純度化学研究所製）を、亜鉛元素とガリウム元素とチタン元素の元素数比が９６．５：０．５：３．０となるように秤量し、ポリプロピレン製の容器に入れ、更に２ｍｍφジルコニア製ボールと混合溶媒としてエタノールを入れた。これをボールミルにより混合し、混合粉末を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を金型に入れ、４０ＭＰａの圧力で加圧し、円盤型の成形体を得た。これを電気炉に入れ、Ａｒ雰囲気中、１３００℃で加熱処理を行い、焼結体を得た。この焼結体の相対密度を焼結体のサイズから算出したところ９６．８％であった。なお、相対密度は、実施例３６と同様にして求めている。得られた焼結体に研削、表面研磨を施し、５０．８ｍｍφ、厚さ３ｍｍの焼結体を得た。 (Example 38)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, gallium element, and titanium element is 96.5: 0.5: 3.0, put in a polypropylene container, and then add 2mmφ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put in an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 96.8% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 36. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
　得られた焼結体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍφ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） The obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target size: 50.8mmφ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、４．１×１０-4Ω・ｃｍであった。表面抵抗は８．２Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５９％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 1 × 10 −4 Ω · cm. The surface resistance was 8.2Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。また、耐アルカリ性、耐酸性に優れていることから、パターニングの際には適当なエッチングレートを有することが推測される。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
　（実施例３９）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化ガリウム（Ｇａ2Ｏ3、住友化学（株）製）、および酸化チタン（Ｔｉ2Ｏ3、（株）高純度化学研究所製）を、亜鉛元素とガリウム元素とチタン元素の元素数比が９４．５：０．５：５．０となるように秤量し、ポリプロピレン製の容器に入れ、更に２ｍｍφジルコニア製ボールと混合溶媒としてエタノールを入れた。これをボールミルにより混合し、混合粉末を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を金型に入れ、４０ＭＰａの圧力で加圧し、円盤型の成形体を得た。これを電気炉に入れ、Ａｒ雰囲気で１３００℃で加熱処理を行い、焼結体を得た。この焼結体の相対密度を焼結体のサイズから算出したところ９４．６％であった。なお、相対密度は、実施例３６と同様にして求めている。得られた焼結体に研削、表面研磨を施し、５０．８ｍｍφ、厚さ３ｍｍの焼結体を得た。 (Example 39)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, gallium element and titanium element is 94.5: 0.5: 5.0, put in a polypropylene container, and then add 2mmφ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. When the relative density of the sintered body was calculated from the size of the sintered body, it was 94.6%. The relative density is obtained in the same manner as in Example 36. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
　得られた焼結体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍφ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） The obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target size: 50.8mmφ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、４．６×１０-4Ω・ｃｍであった。表面抵抗は９．２Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５９％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. 0.6 × 10 −4 Ω · cm. The surface resistance was 9.2Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。また、耐アルカリ性、耐酸性に優れていることから、パターニングの際には適当なエッチングレートを有することが推測される。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
　（実施例４０）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化ガリウム（Ｇａ2Ｏ3、住友化学（株）製）、および酸化チタン（Ｔｉ2Ｏ3、（株）高純度化学研究所製）を、亜鉛元素とガリウム元素とチタン元素の元素数比が９２．５：０．５：７．０となるように秤量し、ポリプロピレン製の容器に入れ、更に２ｍｍφジルコニア製ボールと混合溶媒としてエタノールを入れた。これをボールミルにより混合し、混合粉末を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を金型に入れ、４０ＭＰａの圧力で加圧し、円盤型の成形体を得た。これを電気炉に入れ、Ａｒ雰囲気で１３００℃で加熱処理を行い、焼結体を得た。この焼結体の相対密度を焼結体のサイズから算出したところ９３．９％であった。なお、相対密度は、実施例３６と同様にして求めている。得られた焼結体に研削、表面研磨を施し、５０．８ｍｍφ、厚さ３ｍｍの焼結体を得た。 (Example 40)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, gallium element and titanium element is 92.5: 0.5: 7.0, put in a polypropylene container, and then add 2mmφ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 93.9% when the relative density of this sintered compact was computed from the size of a sintered compact. The relative density is obtained in the same manner as in Example 36. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
　得られた焼結体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍφ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） The obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target size: 50.8mmφ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、５．５×１０-4Ω・ｃｍであった。表面抵抗は１１．０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５９％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 5 × 10 −4 Ω · cm. The surface resistance was 11.0Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。また、耐アルカリ性、耐酸性に優れていることから、パターニングの際には適当なエッチングレートを有することが推測される。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
　（実施例４１）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化ガリウム（Ｇａ2Ｏ3、住友化学（株）製）、および酸化チタン（ＴｉＯ（II）、（株）高純度化学研究所製）を、亜鉛元素とガリウム元素とチタン元素の元素数比が９６．５：０．５：３．０となるように秤量し、ポリプロピレン製の容器に入れ、更に２ｍｍφジルコニア製ボールと混合溶媒としてエタノールを入れた。これをボールミルにより混合し、混合粉末を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を金型に入れ、４０ＭＰａの圧力で加圧し、円盤型の成形体を得た。これを電気炉に入れ、Ａｒ雰囲気で１３００℃で加熱処理を行い、焼結体を得た。この焼結体の相対密度を焼結体のサイズから算出したところ９６．７％であった。なお、相対密度は、実施例３６と同様にして求めている。得られた焼結体に研削、表面研磨を施し、５０．８ｍｍφ、厚さ３ｍｍの焼結体を得た。 (Example 41)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, gallium element and titanium element is 96.5: 0.5: 3.0, put in a polypropylene container, and then add 2mmφ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 96.7% when the relative density of this sintered compact was computed from the size of a sintered compact. The relative density is obtained in the same manner as in Example 36. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
　得られた焼結体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍφ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） The obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target size: 50.8mmφ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、３．９×１０-4Ω・ｃｍであった。表面抵抗は７．８Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５９％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 9 × 10 −4 Ω · cm. The surface resistance was 7.8Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。また、耐アルカリ性、耐酸性に優れていることから、パターニングの際には適当なエッチングレートを有することが推測される。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
　（実施例４２）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化ガリウム（Ｇａ2Ｏ3、住友化学（株）製）、および酸化チタン（ＴｉＯ（II）、（株）高純度化学研究所製）を、亜鉛元素とガリウム元素とチタン元素の元素数比が９４．５：０．５：５．０となるように秤量し、ポリプロピレン製の容器に入れ、更に２ｍｍφジルコニア製ボールと混合溶媒としてエタノールを入れた。これをボールミルにより混合し、混合粉末を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を金型に入れ、４０ＭＰａの圧力で加圧し、円盤型の成形体を得た。これを電気炉に入れ、Ａｒ雰囲気で１３００℃で加熱処理を行い、焼結体を得た。この焼結体の相対密度を焼結体のサイズから算出したところ９４．５％であった。なお、相対密度は、実施例３６と同様にして求めている。得られた焼結体に研削、表面研磨を施し、５０．８ｍｍφ、厚さ３ｍｍの焼結体を得た。 (Example 42)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, gallium element and titanium element is 94.5: 0.5: 5.0, put in a polypropylene container, and then add 2mmφ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 94.5% when the relative density of this sintered compact was computed from the size of a sintered compact. The relative density is obtained in the same manner as in Example 36. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
　得られた焼結体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍφ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） The obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target size: 50.8mmφ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、４．４×１０-4Ω・ｃｍであった。表面抵抗は８．８Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５９％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor. 4 × 10 −4 Ω · cm. The surface resistance was 8.8Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。また、耐アルカリ性、耐酸性に優れていることから、パターニングの際には適当なエッチングレートを有することが推測される。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
　（実施例４３）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化ガリウム（Ｇａ2Ｏ3、住友化学（株）製）、および酸化チタン（ＴｉＯ（II）、（株）高純度化学研究所製）を、亜鉛元素とガリウム元素とチタン元素の元素数比が９２．５：０．５：７．０となるように秤量し、ポリプロピレン製の容器に入れ、更に２ｍｍφジルコニア製ボールと混合溶媒としてエタノールを入れた。これをボールミルにより混合し、混合粉末を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を金型に入れ、４０ＭＰａの圧力で加圧し、円盤型の成形体を得た。これを電気炉に入れ、Ａｒ雰囲気で１３００℃で加熱処理を行い、焼結体を得た。この焼結体の相対密度を焼結体のサイズから算出したところ９４．０％であった。なお、相対密度は、実施例３６と同様にして求めている。得られた焼結体に研削、表面研磨を施し、５０．８ｍｍΦ、厚さ３ｍｍの焼結体を得た。 (Example 43)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, gallium element and titanium element is 92.5: 0.5: 7.0, put in a polypropylene container, and then add 2mmφ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. When the relative density of the sintered body was calculated from the size of the sintered body, it was 94.0%. The relative density is obtained in the same manner as in Example 36. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
　得られた焼結体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍφ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） The obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target size: 50.8mmφ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、５．３×１０-4Ω・ｃｍであった。表面抵抗は１０．６Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５９％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 3 × 10 −4 Ω · cm. The surface resistance was 10.6Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．１倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。また、耐アルカリ性、耐酸性に優れていることから、パターニングの際には適当なエッチングレートを有することが推測される。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
　（実施例４４）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化ガリウム（Ｇａ2Ｏ3、住友化学（株）製）、および酸化チタン（ＴｉＯ（II）、（株）高純度化学研究所製）を、亜鉛元素とガリウム元素とチタン元素の元素数比が９６．５：０．５：３．０となるように秤量し、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の焼結体を得た。（ホットプレス焼結）
　この焼結体の相対密度を焼結体のサイズから算出したところ９６．３％であった。なお、相対密度は、実施例３６と同様にして求めている。得られた焼結体に研削、表面研磨を施し、５０．８ｍｍφ、厚さ３ｍｍの焼結体を得た。 (Example 44)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) A mixture of raw material powders was obtained by weighing so that the element number ratio of zinc element, gallium element and titanium element was 96.5: 0.5: 3.0. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped sintered body. (Hot press sintering)
It was 96.3% when the relative density of this sintered compact was computed from the size of a sintered compact. The relative density is obtained in the same manner as in Example 36. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
　得られた焼結体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍφ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） The obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target size: 50.8mmφ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、３．９×１０-4Ω・ｃｍであった。表面抵抗は７．８Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５９％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 9 × 10 −4 Ω · cm. The surface resistance was 7.8Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。また、耐アルカリ性、耐酸性に優れていることから、パターニングの際には適当なエッチングレートを有することが推測される。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
　（実施例４５）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化ガリウム（Ｇａ2Ｏ3、住友化学（株）製）、および酸化チタン（ＴｉＯ（II）、（株）高純度化学研究所製）を、亜鉛元素とガリウム元素とチタン元素の元素数比が９４．５：０．５：５．０となるように秤量し、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の焼結体を得た。（ホットプレス焼結）
　この焼結体の相対密度を焼結体のサイズから算出したところ９５．６％であった。なお、相対密度は、実施例３６と同様にして求めている。得られた焼結体に研削、表面研磨を施し、５０．８ｍｍφ、厚さ３ｍｍの焼結体を得た。 (Example 45)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), gallium oxide (Ga 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) A mixture of raw material powders was obtained by weighing so that the element number ratio of zinc element, gallium element and titanium element was 94.5: 0.5: 5.0. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped sintered body. (Hot press sintering)
The relative density of the sintered body was calculated from the size of the sintered body and found to be 95.6%. The relative density is obtained in the same manner as in Example 36. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
　得られた焼結体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍφ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） The obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target size: 50.8mmφ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、４．４×１０-4Ω・ｃｍであった。表面抵抗は８．８Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５９％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor. 4 × 10 −4 Ω · cm. The surface resistance was 8.8Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。また、耐アルカリ性、耐酸性に優れていることから、パターニングの際には適当なエッチングレートを有することが推測される。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
　（実施例４６）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化アルミニウム（Ａｌ2Ｏ3、住友化学（株）製）、および酸化チタン（Ｔｉ2Ｏ3、（株）高純度化学研究所製）を、亜鉛元素とアルミニウム元素とチタン元素の元素数比が９６．５：０．５：３．０となるように秤量し、ポリプロピレン製の容器に入れ、更に２ｍｍφジルコニア製ボールと混合溶媒としてエタノールを入れた。これをボールミルにより混合し、混合粉末を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を金型に入れ、４０ＭＰａの圧力で加圧し、円盤型の成形体を得た。これを電気炉に入れ、Ａｒ雰囲気で１３００℃で加熱処理を行い、焼結体を得た。この焼結体の相対密度を焼結体のサイズから算出したところ９６．９％であった。なお、相対密度は、下記の式から求めている。得られた焼結体に研削、表面研磨を施し、５０．８ｍｍφ、厚さ３ｍｍの焼結体を得た。
　　相対密度＝１００×[（焼結体の密度）／（理論密度）]
　但し、理論密度＝（酸化亜鉛の単体密度×混合重量比＋酸化アルミニウムの単体密度×混合重量比＋酸化チタンの単体密度×混合重量比） (Example 46)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the element number ratio of zinc element, aluminum element and titanium element is 96.5: 0.5: 3.0, put it in a polypropylene container, and then add ethanol as a 2mmφ zirconia ball and mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 96.9% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained from the following formula. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
Relative density = 100 × [(density of sintered body) / (theoretical density)]
However, theoretical density = (Zinc oxide simple substance density × mixing weight ratio + Aluminum oxide simple substance density × mixing weight ratio + titanium oxide simple substance density × mixing weight ratio)
　得られた焼結体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍφ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） The obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target size: 50.8mmφ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、４．１×１０-4Ω・ｃｍであった。表面抵抗は８．２Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５９％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 1 × 10 −4 Ω · cm. The surface resistance was 8.2Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。また、耐アルカリ性、耐酸性に優れていることから、パターニングの際には適当なエッチングレートを有することが推測される。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
　（実施例４７）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化アルミニウム（Ａｌ2Ｏ3、住友化学（株）製）、および酸化チタン（Ｔｉ2Ｏ3、（株）高純度化学研究所製）を、亜鉛元素とアルミニウム元素とチタン元素の元素数比が９４．５：０．５：５．０となるように秤量し、ポリプロピレン製の容器に入れ、更に２ｍｍΦジルコニア製ボールと混合溶媒としてエタノールを入れた。これをボールミルにより混合し、混合粉末を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を金型に入れ、４０ＭＰａの圧力で加圧し、円盤型の成形体を得た。これを電気炉に入れ、Ａｒ雰囲気で１３００℃で加熱処理を行い、焼結体を得た。この焼結体の相対密度を焼結体のサイズから算出したところ９４．８％であった。なお、相対密度は、実施例４６と同様にして求めている。得られた焼結体に研削、表面研磨を施し、５０．８ｍｍφ、厚さ３ｍｍの焼結体を得た。 (Example 47)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, aluminum element and titanium element is 94.5: 0.5: 5.0, put it in a polypropylene container, and then add ethanol as a 2mmΦ zirconia ball and mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 94.8% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
　得られた焼結体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍφ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） The obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target size: 50.8mmφ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、４．６×１０-4Ω・ｃｍであった。表面抵抗は９．２Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５９％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) using the “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. 0.6 × 10 −4 Ω · cm. The surface resistance was 9.2Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。また、耐アルカリ性、耐酸性に優れていることから、パターニングの際には適当なエッチングレートを有することが推測される。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
　（実施例４８）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化アルミニウム（Ａｌ2Ｏ3、住友化学（株）製）、および酸化チタン（Ｔｉ2Ｏ3、（株）高純度化学研究所製）を、亜鉛元素とアルミニウム元素とチタン元素の元素数比が９２．５：０．５：７．０となるように秤量し、ポリプロピレン製の容器に入れ、更に２ｍｍφジルコニア製ボールと混合溶媒としてエタノールを入れた。これをボールミルにより混合し、混合粉末を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を金型に入れ、４０ＭＰａの圧力で加圧し、円盤型の成形体を得た。これを電気炉に入れ、Ａｒ雰囲気で１３００℃で加熱処理を行い、焼結体を得た。この焼結体の相対密度を焼結体のサイズから算出したところ９４．２％であった。なお、相対密度は、実施例４６と同様にして求めている。得られた焼結体に研削、表面研磨を施し、５０．８ｍｍφ、厚さ３ｍｍの焼結体を得た。 (Example 48)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, aluminum element and titanium element is 92.5: 0.5: 7.0, put in a polypropylene container, and then add 2mmφ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 94.2% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
　得られた焼結体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍφ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） The obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target size: 50.8mmφ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、５．５×１０-4Ω・ｃｍであった。表面抵抗は１１．０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５９％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 5 × 10 −4 Ω · cm. The surface resistance was 11.0Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。また、耐アルカリ性、耐酸性に優れていることから、パターニングの際には適当なエッチングレートを有することが推測される。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
　（実施例４９）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化アルミニウム（Ａｌ2Ｏ3、住友化学（株）製）、および酸化チタン（ＴｉＯ（II）、（株）高純度化学研究所製）を、亜鉛元素とアルミニウム元素とチタン元素の元素数比が９６．５：０．５：３．０となるように秤量し、ポリプロピレン製の容器に入れ、更に２ｍｍφジルコニア製ボールと混合溶媒としてエタノールを入れた。これをボールミルにより混合し、混合粉末を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を金型に入れ、４０ＭＰａの圧力で加圧し、円盤型の成形体を得た。これを電気炉に入れ、Ａｒ雰囲気で１３００℃で加熱処理を行い、焼結体を得た。この焼結体の相対密度を焼結体のサイズから算出したところ９６．８％であった。なお、相対密度は、実施例４６と同様にして求めている。得られた焼結体に研削、表面研磨を施し、５０．８ｍｍφ、厚さ３ｍｍの焼結体を得た。 (Example 49)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the element number ratio of zinc element, aluminum element and titanium element is 96.5: 0.5: 3.0, put it in a polypropylene container, and then add ethanol as a 2mmφ zirconia ball and mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 96.8% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
　得られた焼結体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍφ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） The obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target size: 50.8mmφ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、３．９×１０-4Ω・ｃｍであった。表面抵抗は７．８Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５９％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 9 × 10 −4 Ω · cm. The surface resistance was 7.8Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。また、耐アルカリ性、耐酸性に優れていることから、パターニングの際には適当なエッチングレートを有することが推測される。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
　（実施例５０）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化アルミニウム（Ａｌ2Ｏ3、住友化学（株）製）、および酸化チタン（ＴｉＯ（II）、（株）高純度化学研究所製）を、亜鉛元素とアルミニウム元素とチタン元素の元素数比が９４．５：０．５：５．０となるように秤量し、ポリプロピレン製の容器に入れ、更に２ｍｍφジルコニア製ボールと混合溶媒としてエタノールを入れた。これをボールミルにより混合し、混合粉末を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を金型に入れ、４０ＭＰａの圧力で加圧し、円盤型の成形体を得た。これを電気炉に入れ、Ａｒ雰囲気で１３００℃で加熱処理を行い、焼結体を得た。この焼結体の相対密度を焼結体のサイズから算出したところ９４．７％であった。なお、相対密度は、実施例４６と同様にして求めている。得られた焼結体に研削、表面研磨を施し、５０．８ｍｍφ、厚さ３ｍｍの焼結体を得た。 (Example 50)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, aluminum element and titanium element is 94.5: 0.5: 5.0, put it in a polypropylene container, and then add ethanol as a 2mmφ zirconia ball and mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 94.7% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
　得られた焼結体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍΦ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） The obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target dimensions: 50.8mmΦ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、４．４×１０-4Ω・ｃｍであった。表面抵抗は８．８Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５９％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor. 4 × 10 −4 Ω · cm. The surface resistance was 8.8Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。また、耐アルカリ性、耐酸性に優れていることから、パターニングの際には適当なエッチングレートを有することが推測される。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
　（実施例５１）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化アルミニウム（Ａｌ2Ｏ3、住友化学（株）製）、および酸化チタン（ＴｉＯ（II）、（株）高純度化学研究所製）を、亜鉛元素とアルミニウム元素とチタン元素の元素数比が９２．５：０．５：７．０となるように秤量し、ポリプロピレン製の容器に入れ、更に２ｍｍφジルコニア製ボールと混合溶媒としてエタノールを入れた。これをボールミルにより混合し、混合粉末を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を金型に入れ、４０ＭＰａの圧力で加圧し、円盤型の成形体を得た。これを電気炉に入れ、Ａｒ雰囲気で１３００℃で加熱処理を行い、焼結体を得た。この焼結体の相対密度を焼結体のサイズから算出したところ９４．２％であった。なお、相対密度は、実施例４６と同様にして求めている。得られた焼結体に研削、表面研磨を施し、５０．８ｍｍφ、厚さ３ｍｍの焼結体を得た。 (Example 51)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the number ratio of zinc element, aluminum element and titanium element is 92.5: 0.5: 7.0, put in a polypropylene container, and then add 2mmφ zirconia balls and ethanol as a mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. It was 94.2% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
　得られた焼結体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍφ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） The obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target size: 50.8mmφ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、５．５×１０-4Ω・ｃｍであった。表面抵抗は１１．０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５９％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 5 × 10 −4 Ω · cm. The surface resistance was 11.0Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．１倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the heat test was 1.1 times the surface resistance before the heat test, and the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。また、耐アルカリ性、耐酸性に優れていることから、パターニングの際には適当なエッチングレートを有することが推測される。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
　（実施例５２）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化アルミニウム（Ａｌ2Ｏ3、住友化学（株）製）、および酸化チタン（ＴｉＯ（II）、（株）高純度化学研究所製）を、亜鉛元素とアルミニウム元素とチタン元素の元素数比が９６．５：０．５：３．０となるように秤量し、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の焼結体を得た。（ホットプレス焼結）
　この焼結体の相対密度を焼結体のサイズから算出したところ９６．６％であった。なお、相対密度は、実施例４６と同様にして求めている。得られた焼結体に研削、表面研磨を施し、５０．８ｍｍφ、厚さ３ｍｍの焼結体を得た。 (Example 52)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) A mixture of raw material powders was obtained by weighing so that the element number ratio of zinc element, aluminum element and titanium element was 96.5: 0.5: 3.0. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped sintered body. (Hot press sintering)
It was 96.6% when the relative density of this sintered compact was computed from the size of the sintered compact. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
　得られた焼結体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍφ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） The obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target size: 50.8mmφ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、３．９×１０-4Ω・ｃｍであった。表面抵抗は７．８Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５９％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 9 × 10 −4 Ω · cm. The surface resistance was 7.8Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。また、耐アルカリ性、耐酸性に優れていることから、パターニングの際には適当なエッチングレートを有することが推測される。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
　（実施例５３）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化アルミニウム（Ａｌ2Ｏ3、住友化学（株）製）、および酸化チタン（ＴｉＯ（II）、（株）高純度化学研究所製）を、亜鉛元素とアルミニウム元素とチタン元素の元素数比が９４．５：０．５：５．０となるように秤量し、原料粉末の混合物を得た。混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の焼結体を得た。（ホットプレス焼結）
　この焼結体の相対密度を焼結体のサイズから算出したところ９５．８％であった。なお、相対密度は、実施例４６と同様にして求めている。得られた焼結体に研削、表面研磨を施し、５０．８ｍｍφ、厚さ３ｍｍの焼結体を得た。 (Example 53)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) A mixture of raw material powders was obtained by weighing so that the element number ratio of zinc element, aluminum element and titanium element was 94.5: 0.5: 5.0. After the mixing operation, the mixed powder obtained by removing the balls and ethanol is put into a mold (die) made of graphite, and vacuum-pressed at a pressure of 40 MPa with a punch made of graphite, followed by heat treatment at 1000 ° C. for 4 hours. To obtain a disk-shaped sintered body. (Hot press sintering)
The relative density of the sintered body was calculated from the size of the sintered body and found to be 95.8%. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
　得られた焼結体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍφ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） The obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target size: 50.8mmφ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、４．４×１０-4Ω・ｃｍであった。表面抵抗は８．８Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５９％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor. 4 × 10 −4 Ω · cm. The surface resistance was 8.8Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the obtained transparent conductive substrate was an average of 89% in the visible region (380 nm to 780 nm) and an average of 59% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．２倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．２倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and the moisture resistance was excellent. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.2 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、透明かつ低抵抗であるとともに、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）をも兼ね備えた透明導電膜であることが明らかである。また、耐アルカリ性、耐酸性に優れていることから、パターニングの際には適当なエッチングレートを有することが推測される。 From the above, the film on the obtained transparent conductive substrate is a transparent conductive film that is transparent and has low resistance, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). It is clear that there is. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning.
　（比較例１５）
　酸化亜鉛（ＺｎＯ、キシダ化学（株）製）、酸化アルミニウム（Ａｌ2Ｏ3、住友化学（株）製）、および酸化チタン（ＴｉＯ（II）、（株）高純度化学研究所製）を、亜鉛元素とアルミニウム元素とチタン元素の元素数比が９０．０：７．０：３．０となるように秤量し、ポリプロピレン製の容器に入れ、更に２ｍｍΦジルコニア製ボールと混合溶媒としてエタノールを入れた。これをボールミルにより混合し、混合粉末を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を金型に入れ、４０ＭＰａの圧力で加圧し、円盤型の成形体を得た。これを電気炉に入れ、Ａｒ雰囲気で１３００℃で加熱処理を行い、焼結体を得た。この焼結体の相対密度を焼結体のサイズから算出したところ９３．０％であった。なお、相対密度は、実施例４６と同様にして求めている。得られた焼結体に研削、表面研磨を施し、５０．８ｍｍφ、厚さ３ｍｍの焼結体を得た。 (Comparative Example 15)
Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), aluminum oxide (Al 2 O 3 , manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by Kojundo Chemical Laboratory Co., Ltd.) Weigh so that the element number ratio of zinc element, aluminum element, and titanium element is 90.0: 7.0: 3.0, put in a polypropylene container, and then add ethanol as a 2mmΦ zirconia ball and mixed solvent. It was. This was mixed by a ball mill to obtain a mixed powder.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol was placed in a mold and pressurized with a pressure of 40 MPa to obtain a disk-shaped molded body. This was put into an electric furnace and heat-treated at 1300 ° C. in an Ar atmosphere to obtain a sintered body. When the relative density of the sintered body was calculated from the size of the sintered body, it was 93.0%. The relative density is obtained in the same manner as in Example 46. The obtained sintered body was ground and polished to obtain a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
　得られた焼結体を、銅板をバッキングプレートとして用い、インジウム半田を用いてボンディングし、スパッタリングターゲットを得た。
　得られたスパッタリングターゲットを用い、スパッタリングにより成膜を行った。スパッタ条件は以下のとおりであり、厚さ約５００ｎｍの薄膜を得た。
　　ターゲット寸法　：５０．８ｍｍΦ　３ｍｍ厚
　　スパッタリング装置　：キャノンアネルバ製　「Ｅ-２００Ｓ」
　　スパッタ方式　：ＤＣマグネトロンスパッタリング
　　到達真空度　：２．０×１０-4Ｐａ
　　Ａｒ圧力　：０．５Ｐａ
　　基板温度　：２５０℃
　　スパッタ電力　：３０Ｗ
　　使用基板　：ソーダライムガラス（５０．８ｍｍ×５０．８ｍｍ×０．５ｍｍ） The obtained sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target.
Using the obtained sputtering target, a film was formed by sputtering. The sputtering conditions were as follows, and a thin film having a thickness of about 500 nm was obtained.
Target dimensions: 50.8mmΦ 3mm thickness Sputtering device: "E-200S" manufactured by Canon Anelva
Sputtering method: DC magnetron sputtering Ultimate vacuum: 2.0 × 10 −4 Pa
Ar pressure: 0.5 Pa
Substrate temperature: 250 ° C
Sputtering power: 30W
Substrate used: Soda lime glass (50.8 mm x 50.8 mm x 0.5 mm)
　得られた薄膜を２倍希釈した塩酸に溶解させ、ＩＣＰ－ＡＥＳ（サーモサイエンティフィック社製「Ｔｈｅｒｍｏ－６５００」）により薄膜組成を測定したところ、ターゲット組成とほぼ等しい組成の薄膜が得られていた。
　また、この透明導電膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた薄膜のシート抵抗を四探針法（三菱化学（株）製、ロレスタ）で、膜厚をＴｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」を用いて測定し、抵抗率を算出したところ、８．２×１０-3Ω・ｃｍであった。表面抵抗は１６４Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均５０％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 The obtained thin film was dissolved in 2-fold diluted hydrochloric acid, and the thin film composition was measured by ICP-AES (Thermo Scientific “Thermo-6500”). As a result, a thin film having a composition almost equal to the target composition was obtained. It was.
The transparent conductive film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM-). EDX) was used to investigate the doping state of titanium into zinc, and further, the crystal structure was examined using a field emission electron microscope (FE-SEM). Was found to be substituted and dissolved in zinc.
The sheet resistance of the obtained thin film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., Loresta) and the film thickness was measured using “Alpha-Step IQ” manufactured by Tencor, and the resistivity was calculated. It was 2 × 10 −3 Ω · cm. The surface resistance was 164Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 50% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　得られた透明導電性基板の耐湿性を評価したところ、耐湿試験後の表面抵抗は、耐湿試験前の表面抵抗の１．３倍であり、耐湿性に優れることがわかった。また、得られた透明導電性基板の耐熱性を評価したところ、耐熱試験後の表面抵抗は、耐熱試験前の表面抵抗の１．３倍であり、耐熱性に優れることがわかった。
　得られた透明導電性基板の耐アルカリ性を評価したところ、浸漬前後で膜質に変化はなく耐アルカリ性に優れていることがわかった。また、得られた透明導電性基板の耐酸性を評価したところ、浸漬後、膜厚が薄くなっており溶解していたが、浸漬前後で膜質に変化はなく耐酸性に優れていることがわかった。 When the moisture resistance of the obtained transparent conductive substrate was evaluated, it was found that the surface resistance after the moisture resistance test was 1.3 times the surface resistance before the moisture resistance test and was excellent in moisture resistance. Moreover, when the heat resistance of the obtained transparent conductive substrate was evaluated, the surface resistance after the heat test was 1.3 times the surface resistance before the heat test, and it was found that the heat resistance was excellent.
When the alkali resistance of the obtained transparent conductive substrate was evaluated, it was found that there was no change in film quality before and after immersion, and the alkali resistance was excellent. Moreover, when the acid resistance of the obtained transparent conductive substrate was evaluated, it was found that after immersion, the film thickness was thin and dissolved, but the film quality did not change before and after immersion, and the acid resistance was excellent. It was.
　以上のことから、得られた透明導電性基板上の膜は、化学的耐久性（耐熱性、耐湿性、耐アルカリ性、耐酸性）と耐アルカリ性、耐酸性に優れていることも兼ね備えた透明導電膜であるが、近赤外透過性が低く、高抵抗である。 From the above, the obtained film on the transparent conductive substrate is a transparent conductive film that has both chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance), alkali resistance, and acid resistance. Although it is a film, it has low near-infrared transmittance and high resistance.
　（実施例５４）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3；（株）高純度化学品研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９２：８となる割合で混合し、原料粉末の混合物を得た。
　次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（０．１０１３ＭＰａ）のアルゴン雰囲気下、４００℃で３時間アニールして、酸化物混合体（３２）を得た。
　得られた酸化物混合体（３２）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９２：８（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０８）であった。この酸化物混合体（３２）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）と酸化チタン（Ｔｉ2Ｏ3）の結晶相の混合物であった。 (Example 54)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by High Purity Chemicals Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. Were mixed in such a ratio that the atomic ratio of Zn: Ti was 92: 8 to obtain a mixture of raw material powders.
Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was annealed at 400 ° C. for 3 hours under an atmospheric pressure (0.1013 MPa) argon atmosphere to obtain an oxide mixture (32).
When the obtained oxide mixture (32) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 92. : 8 (Ti / (Zn + Ti) = 0.08). When the crystal structure of this oxide mixture (32) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), the crystal phase of zinc oxide (ZnO) and titanium oxide (Ti 2 O 3 ) It was a mixture.
　次に、得られた酸化物混合体（３２）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により酸化亜鉛系薄膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力７５Ｗ、基板温度２５０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの酸化亜鉛系薄膜を形成した。 Next, a target is prepared by processing the obtained oxide mixture (32) into a disk shape of 50 mmφ, and a zinc oxide-based thin film is formed by sputtering using the target to obtain a transparent conductive substrate. It was. That is, the above-mentioned target and a transparent substrate (quartz glass substrate) were respectively installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a zinc oxide thin film having a thickness of 500 nm on the substrate.
　形成した酸化亜鉛系薄膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９２：８（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０８）であった。また、この酸化亜鉛系薄膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の酸化亜鉛系薄膜の比抵抗は８．３×１０-4Ω・ｃｍであり、表面抵抗は１６．６Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６５％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 Quantitative analysis of the composition (Zn: Ti) in the formed zinc oxide thin film using a calibration curve by the fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation) As a result, Zn: Ti (atomic ratio) = 92: 8 (Ti / (Zn + Ti) = 0.08). The zinc oxide thin film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM). -EDX) was used to investigate the doping state of titanium with zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. It was found that titanium was substituted and dissolved in zinc.
The specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 8.3 × 10 −4 Ω · cm, and the surface resistance was 16.6 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　次に、形成された薄膜を３０℃の１質量％クエン酸水溶液に６０秒間浸漬させたときの膜厚の減少速度（ｎｍ／秒）を測定することにより、膜のエッチング速度を調べた。なお、膜厚は、触針式膜厚計（Ｔｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」）を用いて測定した。その結果、形成された薄膜のエッチング速度は０．２７ｎｍ／秒であった。 Next, the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1% by mass citric acid aqueous solution at 30 ° C. for 60 seconds. The film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.27 nm / second.
　一般に、エッチング速度が０．５ｎｍ／秒以下であれば十分に制御可能なレベルであり、この薄膜に対し、前記クエン酸水溶液をエッチング液として所定パターンのマスクを用いてパターニングしたところ、良好なエッチングパターンの形成が可能であった。そして、エッチングレートは容易に制御可能であり、導電性の酸化亜鉛系薄膜パターンが得られた。 In general, if the etching rate is 0.5 nm / second or less, the level is sufficiently controllable. When this thin film is patterned using the citric acid aqueous solution as an etchant using a predetermined pattern mask, good etching is achieved. A pattern could be formed. The etching rate can be easily controlled, and a conductive zinc oxide thin film pattern was obtained.
　（実施例５５）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９７：３となる割合で混合し、原料粉末の混合物を得た。
　次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（１．０１３２５×１０2ｋＰａ）のアルゴン雰囲気下、８００℃で４時間焼結して、酸化物焼結体（３３）を得た。
　得られた酸化物焼結体（３３）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。この酸化物焼結体（３３）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 55)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture.
Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 800 ° C. for 4 hours in an argon atmosphere at normal pressure (1.01325 × 10 2 kPa) to obtain an oxide sintered body (33).
When the obtained oxide sintered body (33) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 97: 3 (Ti / (Zn + Ti) = 0.03). When the crystal structure of this oxide sintered body (33) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
　次に、得られた酸化物焼結体（３３）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により酸化亜鉛系薄膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力７５Ｗ、基板温度２５０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの酸化亜鉛系薄膜を形成した。 Next, by processing the obtained oxide sintered body (33) into a disk shape of 50 mmφ, a target is prepared, and a zinc oxide-based thin film is formed by sputtering using this, and a transparent conductive substrate is formed. Obtained. That is, the above-mentioned target and a transparent substrate (quartz glass substrate) were respectively installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a zinc oxide thin film having a thickness of 500 nm on the substrate.
　形成した酸化亜鉛系薄膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０４）であった。また、この酸化亜鉛系薄膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の酸化亜鉛系薄膜の比抵抗は４．４×１０-4Ω・ｃｍであり、表面抵抗は８．８Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 Quantitative analysis of the composition (Zn: Ti) in the formed zinc oxide-based thin film using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation) As a result, Zn: Ti (atomic ratio) = 97: 3 (Ti / (Zn + Ti) = 0.04). The zinc oxide thin film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM). -EDX) was used to investigate the doping state of titanium with zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. It was found that titanium was substituted and dissolved in zinc.
The specific resistance of the zinc oxide thin film on the obtained transparent conductive substrate was 4.4 × 10 −4 Ω · cm, and the surface resistance was 8.8Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　次に、形成された薄膜を３０℃の１質量％クエン酸水溶液に６０秒間浸漬させたときの膜厚の減少速度（ｎｍ／秒）を測定することにより、膜のエッチング速度を調べた。なお、膜厚は、触針式膜厚計（Ｔｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」）を用いて測定した。その結果、形成された薄膜のエッチング速度は０．４０ｎｍ／秒であった。 Next, the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1% by mass citric acid aqueous solution at 30 ° C. for 60 seconds. The film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.40 nm / second.
　一般に、エッチング速度が０．５ｎｍ／秒以下であれば十分に制御可能なレベルであり、この薄膜に対し、前記クエン酸水溶液をエッチング液として所定パターンのマスクを用いてパターニングしたところ、良好なエッチングパターンの形成が可能であった。そして、エッチングレートは容易に制御可能であり、導電性の酸化亜鉛系薄膜パターンが得られた。 In general, if the etching rate is 0.5 nm / second or less, the level is sufficiently controllable. When this thin film is patterned using the citric acid aqueous solution as an etchant using a predetermined pattern mask, good etching is achieved. A pattern could be formed. The etching rate can be easily controlled, and a conductive zinc oxide thin film pattern was obtained.
　（比較例１６）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（Ｔｉ2Ｏ3；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９９：１となる割合で混合し、原料粉末の混合物を得た。
　次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（０．１０１３ＭＰａ）のアルゴン雰囲気下、４００℃で３時間アニールして、酸化物混合体（Ｃ１４）を得た。
　得られた酸化物混合体（Ｃ１４）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９９：１（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０１）であった。 (Comparative Example 16)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti 2 O 3 ; manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. A mixture of raw material powders was obtained by mixing at a ratio of the Zn: Ti atomic ratio of 99: 1.
Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was annealed at 400 ° C. for 3 hours under an atmospheric pressure (0.1013 MPa) argon atmosphere to obtain an oxide mixture (C14).
When the obtained oxide mixture (C14) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 99. : 1 (Ti / (Zn + Ti) = 0.01).
　次に、得られた酸化物混合体（Ｃ１４）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により酸化亜鉛系薄膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力１００Ｗ、基板温度１３０℃の条件下でスパッタリングを行い、基板上に膜厚２００ｎｍの酸化亜鉛系薄膜を形成した。 Next, the obtained oxide mixture (C14) is processed into a disk shape of 50 mmφ to prepare a target, and a zinc oxide-based thin film is formed by sputtering using this to obtain a transparent conductive substrate. It was. That is, in the sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), the target and the transparent base material (quartz glass substrate) were respectively installed, and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 100 W, and a substrate temperature of 130 ° C. to form a zinc oxide thin film having a thickness of 200 nm on the substrate.
　形成した酸化亜鉛系薄膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９９：１（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０１）であった。また、この酸化亜鉛系薄膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の酸化亜鉛系薄膜の比抵抗は２．２５×１０-3Ω・ｃｍであり、表面抵抗は１１２．５Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均７０％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 Quantitative analysis of the composition (Zn: Ti) in the formed zinc oxide-based thin film using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation) As a result, Zn: Ti (atomic ratio) = 99: 1 (Ti / (Zn + Ti) = 0.01). The zinc oxide thin film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM). -EDX) was used to investigate the doping state of titanium with zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. It was found that titanium was substituted and dissolved in zinc.
The specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 2.25 × 10 −3 Ω · cm, and the surface resistance was 112.5 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 70% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　次に、実施例５４と同様に、形成された薄膜のエッチング速度を調べたところ、１．２ｎｍ／秒であった。 Next, as in Example 54, the etching rate of the formed thin film was examined and found to be 1.2 nm / second.
　この膜の場合、エッチング速度が１．０ｎｍ／秒以上であるので制御が難しく、この薄膜に対し、実施例１と同様のクエン酸水溶液をエッチング液として所定パターンのマスクを用いてパターニングしたところ、良好なエッチングパターンの形成は困難であった。 In the case of this film, it is difficult to control because the etching rate is 1.0 nm / second or more, and when this thin film is patterned using a citric acid aqueous solution similar to Example 1 as an etching solution using a mask of a predetermined pattern, It was difficult to form a good etching pattern.
　（比較例１７）
　酸化アルミニウムを２質量％含有した酸化亜鉛スパッタリング用ターゲットを用い、直流マグネトロンスパッタリング法により、アルミニウム原子をドープした酸化亜鉛薄膜を、ソーダライムガラス（厚さ０．７ｍｍ）上に形成した。なお、スパッタリングは、成膜時の電力を７５Ｗ、成膜圧力を０．５Ｐａ、酸素分圧を０Ｐａ、基板温度を室温、成膜時間を３０分間として行った。 (Comparative Example 17)
A zinc oxide thin film doped with aluminum atoms was formed on soda lime glass (thickness 0.7 mm) by a direct current magnetron sputtering method using a zinc oxide sputtering target containing 2% by mass of aluminum oxide. Sputtering was performed at a power of 75 W during film formation, a film formation pressure of 0.5 Pa, an oxygen partial pressure of 0 Pa, a substrate temperature of room temperature, and a film formation time of 30 minutes.
　次に、実施例５４と同様に、形成された薄膜のエッチング速度を調べたところ、１．５ｎｍ／秒であった。 Next, as in Example 54, the etching rate of the formed thin film was examined and found to be 1.5 nm / second.
　この膜の場合、エッチング速度が１．０ｎｍ／秒以上であるので制御が難しく、この薄膜に対し、実施例１と同様のクエン酸水溶液をエッチング液として所定パターンのマスクを用いてパターニングしたところ、良好なエッチングパターンの形成は困難であった。 In the case of this film, it is difficult to control because the etching rate is 1.0 nm / second or more, and when this thin film is patterned using a citric acid aqueous solution similar to Example 1 as an etching solution using a mask of a predetermined pattern, It was difficult to form a good etching pattern.
　（実施例５６）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（ＴｉＯ（II）；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９２：８となる割合で混合し、原料粉末の混合物を得た。
　次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（０．１０１３ＭＰａ）のアルゴン雰囲気下、４００℃で３時間アニールして、酸化物混合体（３４）を得た。
　得られた酸化物混合体（３４）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９２：８（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０８）であった。この酸化物混合体（３４）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）と酸化チタン（Ｔｉ2Ｏ3）の結晶相の混合物であった。 (Example 56)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. A mixture of raw material powders was obtained by mixing at a ratio where the atomic ratio of Zn: Ti was 92: 8.
Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This compact was annealed at 400 ° C. for 3 hours in an argon atmosphere at normal pressure (0.1013 MPa) to obtain an oxide mixture (34).
When the obtained oxide mixture (34) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 92. : 8 (Ti / (Zn + Ti) = 0.08). When the crystal structure of this oxide mixture (34) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), the crystal phase of zinc oxide (ZnO) and titanium oxide (Ti 2 O 3 ) It was a mixture.
　次に、得られた酸化物混合体（３４）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により酸化亜鉛系薄膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力７５Ｗ、基板温度２５０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの酸化亜鉛系薄膜を形成した。 Next, a target is prepared by processing the obtained oxide mixture (34) into a disk shape of 50 mmφ, and a zinc oxide-based thin film is formed by sputtering using this to obtain a transparent conductive substrate. It was. That is, the above-mentioned target and a transparent substrate (quartz glass substrate) were respectively installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a zinc oxide thin film having a thickness of 500 nm on the substrate.
　形成した酸化亜鉛系薄膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９２：８（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０８）であった。また、この酸化亜鉛系薄膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の酸化亜鉛系薄膜の比抵抗は７．６×１０-4Ω・ｃｍであり、表面抵抗は１５．２Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均９０％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６５％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 Quantitative analysis of the composition (Zn: Ti) in the formed zinc oxide thin film using a calibration curve by the fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation) As a result, Zn: Ti (atomic ratio) = 92: 8 (Ti / (Zn + Ti) = 0.08). The zinc oxide thin film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM). -EDX) was used to investigate the doping state of titanium with zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. It was found that titanium was substituted and dissolved in zinc.
The specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 7.6 × 10 −4 Ω · cm, and the surface resistance was 15.2 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was 90% on average in the visible region (380 nm to 780 nm) and 65% on average in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　次に、形成された薄膜を３０℃の１質量％クエン酸水溶液に６０秒間浸漬させたときの膜厚の減少速度（ｎｍ／秒）を測定することにより、膜のエッチング速度を調べた。なお、膜厚は、触針式膜厚計（Ｔｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」）を用いて測定した。その結果、形成された薄膜のエッチング速度は０．２７ｎｍ／秒であった。 Next, the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1% by mass citric acid aqueous solution at 30 ° C. for 60 seconds. The film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.27 nm / second.
　一般に、エッチング速度が０．５ｎｍ／秒以下であれば十分に制御可能なレベルであり、この薄膜に対し、前記クエン酸水溶液をエッチング液として所定パターンのマスクを用いてパターニングしたところ、良好なエッチングパターンの形成が可能であった。そして、エッチングレートは容易に制御可能であり、導電性の酸化亜鉛系薄膜パターンが得られた。 In general, if the etching rate is 0.5 nm / second or less, the level is sufficiently controllable. When this thin film is patterned using the citric acid aqueous solution as an etchant using a predetermined pattern mask, good etching is achieved. A pattern could be formed. The etching rate can be easily controlled, and a conductive zinc oxide thin film pattern was obtained.
　（実施例５７）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（ＴｉＯ（II）；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９７：３となる割合で混合し、原料粉末の混合物を得た。
　次いで、得られた混合物を金型に入れ、一軸プレスにより成形圧５００ｋｇ／ｃｍ2にて成形し、直径３０ｍｍ、厚さ５ｍｍの円盤状の成形体を得た。この成形体を常圧（１．０１３２５×１０2ｋＰａ）のアルゴン雰囲気下、８００℃で４時間焼結して、酸化物焼結体（３５）を得た。
　得られた酸化物焼結体（３５）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３
）であった。この酸化物焼結体（３５）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 57)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture.
Subsequently, the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 800 ° C. for 4 hours under an argon atmosphere at normal pressure (1.01325 × 10 2 kPa) to obtain an oxide sintered body (35).
When the obtained oxide sintered body (35) was analyzed with an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 97: 3 (Ti / (Zn + Ti) = 0.03)
)Met. When the crystal structure of this oxide sintered body (35) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a mixture of phases and no titanium oxide was present.
　次に、得られた酸化物焼結体（３５）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により酸化亜鉛系薄膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力７５Ｗ、基板温度２５０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの酸化亜鉛系薄膜を形成した。 Next, by processing the obtained oxide sintered body (35) into a disk shape of 50 mmφ, a target is prepared, and a zinc oxide thin film is formed by sputtering using the target, and a transparent conductive substrate is formed. Obtained. That is, the above-mentioned target and a transparent substrate (quartz glass substrate) were respectively installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a zinc oxide thin film having a thickness of 500 nm on the substrate.
　形成した酸化亜鉛系薄膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。また、この酸化亜鉛系薄膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の酸化亜鉛系薄膜の比抵抗は４．２×１０-4Ω・ｃｍであり、表面抵抗は８．４Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 Quantitative analysis of the composition (Zn: Ti) in the formed zinc oxide thin film using a calibration curve by the fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation) As a result, Zn: Ti (atomic ratio) = 97: 3 (Ti / (Zn + Ti) = 0.03). The zinc oxide thin film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM). -EDX) was used to investigate the doping state of titanium with zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. It was found that titanium was substituted and dissolved in zinc.
The specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 4.2 × 10 −4 Ω · cm, and the surface resistance was 8.4 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　次に、形成された薄膜を３０℃の１質量％クエン酸水溶液に６０秒間浸漬させたときの膜厚の減少速度（ｎｍ／秒）を測定することにより、膜のエッチング速度を調べた。なお、膜厚は、触針式膜厚計（Ｔｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」）を用いて測定した。その結果、形成された薄膜のエッチング速度は０．４０ｎｍ／秒であった。 Next, the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1% by mass citric acid aqueous solution at 30 ° C. for 60 seconds. The film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.40 nm / second.
　一般に、エッチング速度が０．５ｎｍ／秒以下であれば十分に制御可能なレベルであり、この薄膜に対し、前記クエン酸水溶液をエッチング液として所定パターンのマスクを用いてパターニングしたところ、良好なエッチングパターンの形成が可能であった。そして、エッチングレートは容易に制御可能であり、導電性の酸化亜鉛系薄膜パターンが得られた。 In general, if the etching rate is 0.5 nm / second or less, the level is sufficiently controllable. When this thin film is patterned using the citric acid aqueous solution as an etchant using a predetermined pattern mask, good etching is achieved. A pattern could be formed. The etching rate can be easily controlled, and a conductive zinc oxide thin film pattern was obtained.
　（実施例５８）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（ＴｉＯ（II）；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９７：３となる割合で混合し、原料粉末の混合物を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（３６）を得た。得られた酸化物焼結体（３６）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。
　この酸化物焼結体（３６）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 58)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (36). When the obtained oxide sintered body (36) was analyzed with an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 97: 3 (Ti / (Zn + Ti) = 0.03).
When the crystal structure of this oxide sintered body (36) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
　次に、得られた酸化物焼結体（３６）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により酸化亜鉛系薄膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力７５Ｗ、基板温度２５０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの酸化亜鉛系薄膜を形成した。 Next, by processing the obtained oxide sintered body (36) into a disk shape of 50 mmφ, a target is prepared, and a zinc oxide thin film is formed by sputtering using this, and a transparent conductive substrate is formed. Obtained. That is, the above-mentioned target and a transparent substrate (quartz glass substrate) were respectively installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a zinc oxide thin film having a thickness of 500 nm on the substrate.
　形成した酸化亜鉛系薄膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。また、この酸化亜鉛系薄膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の酸化亜鉛系薄膜の比抵抗は４．２×１０-4Ω・ｃｍであり、表面抵抗は８．４Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 Quantitative analysis of the composition (Zn: Ti) in the formed zinc oxide thin film using a calibration curve by the fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation) As a result, Zn: Ti (atomic ratio) = 97: 3 (Ti / (Zn + Ti) = 0.03). The zinc oxide thin film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM). -EDX) was used to investigate the doping state of titanium with zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. It was found that titanium was substituted and dissolved in zinc.
The specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 4.2 × 10 −4 Ω · cm, and the surface resistance was 8.4 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　次に、形成された薄膜を３０℃の１質量％クエン酸水溶液に６０秒間浸漬させたときの膜厚の減少速度（ｎｍ／秒）を測定することにより、膜のエッチング速度を調べた。なお、膜厚は、触針式膜厚計（Ｔｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」）を用いて測定した。その結果、形成された薄膜のエッチング速度は０．４０ｎｍ／秒であった。 Next, the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1% by mass citric acid aqueous solution at 30 ° C. for 60 seconds. The film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.40 nm / second.
　一般に、エッチング速度が０．５ｎｍ／秒以下であれば十分に制御可能なレベルであり、この薄膜に対し、前記クエン酸水溶液をエッチング液として所定パターンのマスクを用いてパターニングしたところ、良好なエッチングパターンの形成が可能であった。そして、エッチングレートは容易に制御可能であり、導電性の酸化亜鉛系薄膜パターンが得られた。 In general, if the etching rate is 0.5 nm / second or less, the level is sufficiently controllable. When this thin film is patterned using the citric acid aqueous solution as an etchant using a predetermined pattern mask, good etching is achieved. A pattern could be formed. The etching rate can be easily controlled, and a conductive zinc oxide thin film pattern was obtained.
　（比較例１８）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（ＴｉＯ（II）；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が８８：１２となる割合で混合し、原料粉末の混合物を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（Ｃ１５）を得た。得られた酸化物焼結体（Ｃ１５）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝８８：１２（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．１２）であった。
　この酸化物焼結体（Ｃ１５）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Comparative Example 18)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. A mixture of raw material powders was obtained by mixing the Zn: Ti at an atomic ratio of 88:12.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (C15). When the obtained oxide sintered body (C15) was analyzed by an energy dispersive X-ray fluorescence apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 88:12 (Ti / (Zn + Ti) = 0.12).
When the crystal structure of this oxide sintered body (C15) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
　次に、得られた酸化物焼結体（Ｃ１５）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により酸化亜鉛系薄膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力７５Ｗ、基板温度２５０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの酸化亜鉛系薄膜を形成した。 Next, by processing the obtained oxide sintered body (C15) into a disk shape of 50 mmφ, a target is prepared, and a zinc oxide-based thin film is formed by sputtering using this, and a transparent conductive substrate is formed. Obtained. That is, the above-mentioned target and a transparent substrate (quartz glass substrate) were respectively installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a zinc oxide thin film having a thickness of 500 nm on the substrate.
　形成した酸化亜鉛系薄膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝８８：１２（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．１２）であった。また、この酸化亜鉛系薄膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の酸化亜鉛系薄膜の比抵抗は２．１×１０-2Ω・ｃｍであり、表面抵抗は４２０．０Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 Quantitative analysis of the composition (Zn: Ti) in the formed zinc oxide-based thin film using a calibration curve by a fluorescent X-ray method using a wavelength dispersive X-ray fluorescence apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation) As a result, Zn: Ti (atomic ratio) = 88: 12 (Ti / (Zn + Ti) = 0.12). The zinc oxide thin film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM). -EDX) was used to investigate the doping state of titanium with zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. It was found that titanium was substituted and dissolved in zinc.
The specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 2.1 × 10 −2 Ω · cm, and the surface resistance was 420.0Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　次に、形成された薄膜を３０℃の１質量％クエン酸水溶液に６０秒間浸漬させたときの膜厚の減少速度（ｎｍ／秒）を測定することにより、膜のエッチング速度を調べた。なお、膜厚は、触針式膜厚計（Ｔｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」）を用いて測定した。その結果、形成された薄膜のエッチング速度は０．１６ｎｍ／秒であった。 Next, the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1% by mass citric acid aqueous solution at 30 ° C. for 60 seconds. The film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.16 nm / second.
　一般に、エッチング速度が０．５ｎｍ／秒以下であれば十分に制御可能なレベルであり、この薄膜に対し、前記クエン酸水溶液をエッチング液として所定パターンのマスクを用いてパターニングしたところ、良好なエッチングパターンの形成が可能であった。そして、エッチングレートは容易に制御可能であり、導電性の酸化亜鉛系薄膜パターンが得られた。エッチングレートは十分制御可能であるが、抵抗が高かった。 In general, if the etching rate is 0.5 nm / second or less, the level is sufficiently controllable. When this thin film is patterned using the citric acid aqueous solution as an etchant using a predetermined pattern mask, good etching is achieved. A pattern could be formed. The etching rate can be easily controlled, and a conductive zinc oxide thin film pattern was obtained. Although the etching rate was sufficiently controllable, the resistance was high.
　（実施例５９）
　酸化亜鉛粉末（ＺｎＯ；和光純薬工業（株）製、特級）および酸化チタン粉末（ＴｉＯ（II）；（株）高純度化学研究所製、純度９９．９９％）を原料粉末とし、これらをＺｎ：Ｔｉの原子数比が９７：３となる割合で混合し、原料粉末の混合物を得た。
　混合操作後、ボールとエタノールを除去して得られた混合粉末を黒鉛からなる金型（ダイス）に入れ、黒鉛からなるパンチにて４０ＭＰａの圧力で真空加圧し、１０００℃、４時間、加熱処理を行い円盤型の酸化物焼結体（３７）を得た。得られた酸化物焼結体（３７）をエネルギー分散型蛍光Ｘ線装置（（株）島津製作所製「ＥＤＸ－７００Ｌ」）にて分析したところ、ＺｎとＴｉの原子数比はＺｎ：Ｔｉ＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。
　この酸化物焼結体（３７）の結晶構造をＸ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）により調べたところ、酸化亜鉛（ＺｎＯ）とチタン酸亜鉛（Ｚｎ2ＴｉＯ4）の結晶相の混合物であり、酸化チタンは全く存在していなかった。 (Example 59)
Zinc oxide powder (ZnO; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II); manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) are used as raw material powders. Mixing was performed at a Zn: Ti atomic ratio of 97: 3 to obtain a raw material powder mixture.
After the mixing operation, the mixed powder obtained by removing the balls and ethanol is placed in a graphite mold (die), vacuum-pressed at a pressure of 40 MPa with a graphite punch, and heated at 1000 ° C. for 4 hours. To obtain a disk-shaped oxide sintered body (37). When the obtained oxide sintered body (37) was analyzed with an energy dispersive fluorescent X-ray apparatus (“EDX-700L” manufactured by Shimadzu Corporation), the atomic ratio of Zn and Ti was Zn: Ti = 97: 3 (Ti / (Zn + Ti) = 0.03).
When the crystal structure of this oxide sintered body (37) was examined with an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation), crystals of zinc oxide (ZnO) and zinc titanate (Zn 2 TiO 4 ) were obtained. It was a phase mixture and no titanium oxide was present.
　次に、得られた酸化物焼結体（３７）を５０ｍｍφの円盤状に加工することにより、ターゲットを作製し、これを用いてスパッタリング法により酸化亜鉛系薄膜を成膜し、透明導電基板を得た。すなわち、スパッタリング装置（キャノンアネルバエンジニアリング（株）製「Ｅ－２００」）内に、上記ターゲットと透明基材（石英ガラス基板）とをそれぞれ設置し、Ａｒガス（純度９９．９９９５％以上、Ａｒ純ガス＝５Ｎ）を１２ｓｃｃｍで導入して、圧力０．５Ｐａ、電力７５Ｗ、基板温度２５０℃の条件下でスパッタリングを行い、基板上に膜厚５００ｎｍの酸化亜鉛系薄膜を形成した。 Next, by processing the obtained oxide sintered body (37) into a disk shape of 50 mmφ, a target is prepared, and a zinc oxide-based thin film is formed by sputtering using this, and a transparent conductive substrate is formed. Obtained. That is, the above-mentioned target and a transparent substrate (quartz glass substrate) were respectively installed in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.), and Ar gas (purity 99.9995% or more, Ar pure) Gas = 5N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C. to form a zinc oxide thin film having a thickness of 500 nm on the substrate.
　形成した酸化亜鉛系薄膜中の組成（Ｚｎ：Ｔｉ）について、波長分散型蛍光Ｘ線装置（（株）島津製作所製「ＸＲＦ－１７００ＷＳ」）を用い蛍光Ｘ線法により検量線を用いて定量分析を行ったところ、Ｚｎ：Ｔｉ（原子数比）＝９７：３（Ｔｉ／（Ｚｎ＋Ｔｉ）＝０．０３）であった。また、この酸化亜鉛系薄膜について、Ｘ線回折装置（理学電機（株）製「ＲＩＮＴ２０００」）を用い薄膜測定用のアタッチメントを使用したＸ線回折を行うとともに、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ－ＥＤＸ）を用いて亜鉛へのチタンのドープ状態を調べ、さらに電界放射型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて結晶構造を調べたところ、Ｃ軸配向したウルツ鉱型の単相であり、チタンが亜鉛に置換固溶していることがわかった。
　得られた透明導電性基板上の酸化亜鉛系薄膜の比抵抗は４．２×１０-4Ω・ｃｍであり、表面抵抗は８．４Ω／□であった。なお、透明基板上の比抵抗の分布は面内均一であった。
　得られた透明導電性基板の透過率は、可視領域（３８０ｎｍ～７８０ｎｍ）で平均８９％、赤外領域（７８０ｎｍ～２７００ｎｍ）で平均６０％であった。なお、成膜前の石英ガラス基板の可視領域（３８０ｎｍ～７８０ｎｍ）における透過率は平均９４％であり、赤外領域（７８０ｎｍ～２７００ｎｍ）における透過率は平均９４％であった。 Quantitative analysis of the composition (Zn: Ti) in the formed zinc oxide thin film using a calibration curve by the fluorescent X-ray method using a wavelength dispersion type fluorescent X-ray apparatus (“XRF-1700WS” manufactured by Shimadzu Corporation) As a result, Zn: Ti (atomic ratio) = 97: 3 (Ti / (Zn + Ti) = 0.03). The zinc oxide thin film is subjected to X-ray diffraction using an attachment for thin film measurement using an X-ray diffractometer (“RINT2000” manufactured by Rigaku Corporation) and an energy dispersive X-ray microanalyzer (TEM). -EDX) was used to investigate the doping state of titanium with zinc, and further the field structure electron microscope (FE-SEM) was used to examine the crystal structure. It was found that titanium was substituted and dissolved in zinc.
The specific resistance of the obtained zinc oxide thin film on the transparent conductive substrate was 4.2 × 10 −4 Ω · cm, and the surface resistance was 8.4 Ω / □. The specific resistance distribution on the transparent substrate was uniform in the plane.
The transmittance of the transparent conductive substrate obtained was an average of 89% in the visible region (380 nm to 780 nm) and an average of 60% in the infrared region (780 nm to 2700 nm). Note that the transmittance in the visible region (380 nm to 780 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average.
　次に、形成された薄膜を２０℃の１ｍｏｌ／ｌの酢酸水溶液に１２０秒間浸漬させたときの膜厚の減少速度（ｎｍ／秒）を測定することにより、膜のエッチング速度を調べた。なお、膜厚は、触針式膜厚計（Ｔｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」）を用いて測定した。その結果、形成された薄膜のエッチング速度は０．３３ｎｍ／秒であった。 Next, the etching rate of the film was examined by measuring the rate of decrease in film thickness (nm / second) when the formed thin film was immersed in a 1 mol / l acetic acid aqueous solution at 20 ° C. for 120 seconds. The film thickness was measured using a stylus type film thickness meter (“Alpha-Step IV” manufactured by Tencor). As a result, the etching rate of the formed thin film was 0.33 nm / second.
　一般に、エッチング速度が０．５ｎｍ／秒以下であれば十分に制御可能なレベルであり、この薄膜に対し、前記クエン酸水溶液をエッチング液として所定パターンのマスクを用いてパターニングしたところ、良好なエッチングパターンの形成が可能であった。そして、エッチングレートは容易に制御可能であり、導電性の酸化亜鉛系薄膜パターンが得られた。 In general, if the etching rate is 0.5 nm / second or less, the level is sufficiently controllable. When this thin film is patterned using the citric acid aqueous solution as an etchant using a predetermined pattern mask, good etching is achieved. A pattern could be formed. The etching rate can be easily controlled, and a conductive zinc oxide thin film pattern was obtained.
　（比較例１９）
　酸化アルミニウムを２質量％含有した酸化亜鉛スパッタリング用ターゲットを用い、直流マグネトロンスパッタリング法により、アルミニウム原子をドープした酸化亜鉛薄膜を、ソーダライムガラス（厚さ０．７ｍｍ）上に形成した。なお、スパッタリングは、成膜時の電力を７５Ｗ、成膜圧力を０．５Ｐａ、酸素分圧を０Ｐａ、基板温度を室温、成膜時間を３０分間として行った。 (Comparative Example 19)
A zinc oxide thin film doped with aluminum atoms was formed on soda lime glass (thickness 0.7 mm) by a direct current magnetron sputtering method using a zinc oxide sputtering target containing 2% by mass of aluminum oxide. Sputtering was performed at a power of 75 W during film formation, a film formation pressure of 0.5 Pa, an oxygen partial pressure of 0 Pa, a substrate temperature of room temperature, and a film formation time of 30 minutes.
　次に、実施例１と同様に、形成された薄膜のエッチング速度を調べたところ、１．５ｎｍ／秒であった。
　次に、形成された薄膜を２０℃の１ｍｏｌ／ｌの酢酸水溶液に１２０秒間浸漬させたときの膜厚の減少速度（ｎｍ／秒）を測定することにより、膜のエッチング速度を調べた。なお、膜厚は、触針式膜厚計（Ｔｅｎｃｏｒ社製「Ａｌｐｈａ－Ｓｔｅｐ ＩＱ」）を用いて測定した。その結果、形成された薄膜のエッチング速度は２．４２ｎｍ／秒であった。 Next, when the etching rate of the formed thin film was examined in the same manner as in Example 1, it was 1.5 nm / second.
Next, the etching rate of the film was examined by measuring the rate of film thickness reduction (nm / second) when the formed thin film was immersed in a 1 mol / l acetic acid aqueous solution at 20 ° C. for 120 seconds. The film thickness was measured using a stylus type film thickness meter (“Alpha-Step IQ” manufactured by Tencor). As a result, the etching rate of the formed thin film was 2.42 nm / second.
　この膜の場合、エッチング速度が１．０ｎｍ／秒以上であるので制御が難しく、この薄膜に対し、実施例５９と同様の酢酸水溶液をエッチング液として所定パターンのマスクを用いてパターニングしたところ、良好なエッチングパターンの形成は困難であった。 In the case of this film, it is difficult to control because the etching rate is 1.0 nm / second or more. When this thin film is patterned using an acetic acid aqueous solution similar to that in Example 59 as an etchant using a mask having a predetermined pattern, it is good. It was difficult to form an etching pattern.

Claims (35)

  1. 　実質的に亜鉛、チタンおよび酸素からなり、亜鉛とチタンとの合計に対するチタンの原子数比Ｔｉ／（Ｚｎ＋Ｔｉ）が０．０２を超え０．１以下である酸化物焼結体。 An oxide sintered body substantially consisting of zinc, titanium and oxygen, and having an atomic ratio Ti / (Zn + Ti) of titanium to the total of zinc and titanium of more than 0.02 and 0.1 or less.
  2. 　酸化亜鉛相とチタン酸亜鉛化合物相とから構成される、請求項１に記載の酸化物焼結体。 The oxide sintered body according to claim 1, comprising a zinc oxide phase and a zinc titanate compound phase.
  3. 　チタン酸亜鉛化合物相から構成される、請求項１に記載の酸化物焼結体。 The oxide sintered body according to claim 1, comprising a zinc titanate compound phase.
  4. 　実質的に酸化チタンの結晶相を含有しない、請求項１～３のいずれかに記載の酸化物焼結体。 The oxide sintered body according to any one of claims 1 to 3, which does not substantially contain a crystal phase of titanium oxide.
  5. 　チタンの原子価は４価未満である、請求項１～４のいずれかに記載の酸化物焼結体。 The oxide sintered body according to any one of claims 1 to 4, wherein the valence of titanium is less than 4.
  6. 　ガリウム、アルミニウム、錫、シリコン、ゲルマニウム、ジルコニウムおよびハフニウムからなる群より選ばれる少なくとも１種の元素をも含有する、請求項１～５のいずれかに記載の酸化物焼結体。 The oxide sintered body according to any one of claims 1 to 5, which also contains at least one element selected from the group consisting of gallium, aluminum, tin, silicon, germanium, zirconium and hafnium.
  7. 　請求項１～６のいずれかに記載の酸化物焼結体を製造する方法であって、以下の（Ａ）および／または（Ｂ）を含む原料粉末を成形した後、得られた成形体を不活性雰囲気中、真空中または還元雰囲気あるいは不活性雰囲気中６００℃～１５００℃で焼結する方法。
    （Ａ）酸化チタン粉と酸化亜鉛粉との混合粉もしくは酸化チタン粉と水酸化亜鉛粉との混合粉
    （Ｂ）チタン酸亜鉛化合物粉     A method for producing the oxide sintered body according to any one of claims 1 to 6, wherein after molding a raw material powder containing the following (A) and / or (B): A method of sintering at 600 ° C. to 1500 ° C. in an inert atmosphere, vacuum, reducing atmosphere or inert atmosphere.
    (A) Mixed powder of titanium oxide powder and zinc oxide powder or mixed powder of titanium oxide powder and zinc hydroxide powder (B) Zinc titanate compound powder
  8. 　請求項１～６のいずれかに記載の酸化物焼結体を製造する方法であって、以下の（Ａ）および／または（Ｂ）を含む原料粉末を成形した後、得られた成形体を大気雰囲気中または酸化雰囲気中６００℃～１５００℃で焼結し、その後さらに不活性雰囲気中、真空中または還元雰囲気中でアニール処理を施す方法。
    （Ａ）酸化チタン粉と酸化亜鉛粉との混合粉もしくは酸化チタン粉と水酸化亜鉛粉との混合粉
    （Ｂ）チタン酸亜鉛化合物粉     A method for producing an oxide sintered body according to any one of claims 1 to 6, wherein after molding a raw material powder containing the following (A) and / or (B), A method in which sintering is performed at 600 ° C. to 1500 ° C. in an air atmosphere or an oxidizing atmosphere, and then an annealing treatment is performed in an inert atmosphere, a vacuum, or a reducing atmosphere.
    (A) Mixed powder of titanium oxide powder and zinc oxide powder or mixed powder of titanium oxide powder and zinc hydroxide powder (B) Zinc titanate compound powder
  9. 　前記酸化チタン粉が、式：ＴｉＯ2-X（Ｘ＝０．１～１）で表される低原子価酸化チタンの粉末である、請求項７または８に記載の方法。 The method according to claim 7 or 8, wherein the titanium oxide powder is a low-valent titanium oxide powder represented by the formula: TiO 2 -X (X = 0.1 to 1).
  10. 　前記アニール処理の雰囲気は、窒素、アルゴン、ヘリウム、二酸化炭素、アンモニアおよび水素からなる群より選ばれる少なくとも１種からなる雰囲気または真空である請求項８または９に記載の方法。 The method according to claim 8 or 9, wherein an atmosphere of the annealing treatment is an atmosphere consisting of at least one selected from the group consisting of nitrogen, argon, helium, carbon dioxide, ammonia and hydrogen, or a vacuum.
  11. 　酸化亜鉛および酸化チタンからなり、亜鉛とチタンとの合計に対するチタンの原子数比Ｔｉ／（Ｚｎ＋Ｔｉ）が０．０２を超え０．１以下である酸化物混合体。 An oxide mixture composed of zinc oxide and titanium oxide, wherein the atomic ratio Ti / (Zn + Ti) of titanium to the total of zinc and titanium is more than 0.02 and not more than 0.1.
  12. 　前記酸化チタンにおけるチタンの原子価は、４価未満である、請求項１１に記載の酸化物混合体。 The oxide mixture according to claim 11, wherein the titanium valence in the titanium oxide is less than tetravalent.
  13. 　ガリウム、アルミニウム、錫、シリコン、ゲルマニウム、ジルコニウムおよびハフニウムからなる群より選ばれる少なくとも１種の元素をも含有する、請求項１１または１２に記載の酸化物混合体。 The oxide mixture according to claim 11 or 12, which also contains at least one element selected from the group consisting of gallium, aluminum, tin, silicon, germanium, zirconium and hafnium.
  14. 　請求項１１～１３のいずれかに記載の酸化物混合体を製造する方法であって、酸化チタン粉と酸化亜鉛粉との混合粉もしくは酸化チタン粉と水酸化亜鉛粉との混合粉を含む原料粉末を成形した後、得られた成形体に大気雰囲気中、酸化雰囲気中、不活性雰囲気中、真空中または還元雰囲気中５０℃以上６００℃未満でアニール処理を施す方法。 A method for producing the oxide mixture according to any one of claims 11 to 13, wherein the raw material contains a mixed powder of titanium oxide powder and zinc oxide powder or a mixed powder of titanium oxide powder and zinc hydroxide powder. A method of performing an annealing treatment at 50 ° C. or higher and lower than 600 ° C. in an air atmosphere, an oxidizing atmosphere, an inert atmosphere, a vacuum, or a reducing atmosphere after forming the powder.
  15. 　前記酸化チタン粉が、式：ＴｉＯ2-X（Ｘ＝０．１～１）で表される低原子価酸化チタンの粉末である、請求項１４に記載の方法。 The method according to claim 14, wherein the titanium oxide powder is a low-valent titanium oxide powder represented by the formula: TiO 2 -X (X = 0.1 to 1).
  16. 　前記アニール処理の雰囲気は、窒素、アルゴン、ヘリウム、二酸化炭素および水素からなる群より選ばれる少なくとも１種からなる雰囲気または真空である、請求項１４または１５に記載の方法。 The method according to claim 14 or 15, wherein an atmosphere of the annealing treatment is an atmosphere made of at least one selected from the group consisting of nitrogen, argon, helium, carbon dioxide and hydrogen, or a vacuum.
  17. 　スパッタリング法、イオンプレーティング法、パルスレーザ堆積法（ＰＬＤ法）またはエレクトロンビーム（ＥＢ）蒸着法による成膜に用いられるターゲットであって、請求項１～６のいずれかに記載の酸化物焼結体または請求項１１～１３のいずれかに記載の酸化物混合体を加工して得られるターゲット。 The oxide sintering according to any one of claims 1 to 6, which is a target used for film formation by sputtering, ion plating, pulsed laser deposition (PLD) or electron beam (EB) vapor deposition. Or a target obtained by processing the oxide mixture according to any one of claims 11 to 13.
  18. 　パルスレーザ堆積法（ＰＬＤ法）、スパッタリング法、イオンプレーティング法およびエレクトロンビーム（ＥＢ）蒸着法からなる群より選ばれる１種により酸化亜鉛系透明導電膜を形成する方法であって、実質的に亜鉛、チタンおよび酸素からなり、亜鉛とチタンとの合計に対するチタンの原子数比Ｔｉ／（Ｚｎ＋Ｔｉ）が０．０２を超え０．１以下である酸化物焼結体または酸化物混合体を加工して得られるターゲットを用いる方法。 A method of forming a zinc oxide-based transparent conductive film by one selected from the group consisting of a pulse laser deposition method (PLD method), a sputtering method, an ion plating method, and an electron beam (EB) vapor deposition method, An oxide sintered body or oxide mixture comprising zinc, titanium, and oxygen, and having an atomic ratio Ti / (Zn + Ti) of titanium to the total of zinc and titanium of more than 0.02 and less than 0.1 is processed. The method using the target obtained in this way.
  19. 　前記チタンは、式ＴｉＯ2-X（Ｘ＝０．１～１）で表される低原子価酸化チタン由来のチタンである、請求項１８に記載の方法。 The method according to claim 18, wherein the titanium is titanium derived from a low valence titanium oxide represented by a formula TiO 2 -X (X = 0.1 to 1).
  20. 　前記低原子価酸化チタンは、２価のチタンからなる酸化チタン（ＴｉＯ）あるいは３価のチタンからなる酸化チタン（Ｔｉ2Ｏ3）である、請求項１９に記載の方法。 The method according to claim 19, wherein the low-valence titanium oxide is titanium oxide (TiO) made of divalent titanium or titanium oxide (Ti 2 O 3 ) made of trivalent titanium.
  21. 　請求項１８～２０のいずれかに記載の方法により形成された、酸化亜鉛系透明導電膜。 A zinc oxide-based transparent conductive film formed by the method according to any one of claims 18 to 20.
  22. 　透明基材上に、請求項２１に記載の酸化亜鉛系透明導電膜を備える透明導電性基板。 A transparent conductive substrate comprising the zinc oxide-based transparent conductive film according to claim 21 on a transparent substrate.
  23. 　前記透明基材が、ガラス板、樹脂フィルムまたは樹脂シートである、請求項２２に記載の透明導電性基板。 The transparent conductive substrate according to claim 22, wherein the transparent substrate is a glass plate, a resin film or a resin sheet.
  24. 　亜鉛とチタンの合計に対するチタンの原子数比Ｔｉ／（Ｚｎ＋Ｔｉ）が０．０２を越え０．１以下であり、酸化亜鉛を主成分とし、ガリウムおよびアルミニウムのうち少なくとも一方の酸化物と、酸化チタンとを含み、ガリウムまたはアルミニウムの原子数の割合が全金属原子数に対して０．５％以上６％以下であり、かつ前記酸化チタンが、式ＴｉＯ2-X（Ｘ＝０．１～１）で表される低原子価酸化チタンである酸化物混合体または酸化物焼結体からなる酸化亜鉛系透明導電膜形成材料。 The atomic ratio Ti / (Zn + Ti) of titanium to the total of zinc and titanium is more than 0.02 and not more than 0.1, zinc oxide as a main component, at least one oxide of gallium and aluminum, and titanium oxide The ratio of the number of atoms of gallium or aluminum is 0.5% or more and 6% or less with respect to the total number of metal atoms, and the titanium oxide has the formula TiO 2-X (X = 0.1 to 1). Zinc oxide-based transparent conductive film-forming material comprising an oxide mixture or oxide sintered body that is a low-valence titanium oxide represented by:
  25. 　前記低原子価酸化チタンにおけるチタンの原子価は、２価または３価である、請求項２４に記載の酸化亜鉛系透明導電膜形成材料。 The zinc oxide-based transparent conductive film-forming material according to claim 24, wherein the valence of titanium in the low-valence titanium oxide is divalent or trivalent.
  26. 　前記酸化物焼結体の相対密度が９３％以上である、請求項２４または２５に記載の酸化亜鉛系透明導電膜形成材料。 The zinc oxide-based transparent conductive film forming material according to claim 24 or 25, wherein a relative density of the oxide sintered body is 93% or more.
  27. 　スパッタリング法、イオンプレーティング法、パルスレーザ堆積法（ＰＬＤ法）またはエレクトロンビーム（ＥＢ）蒸着法による成膜に用いられるターゲットであって、請求項２４～２６のいずれかに記載の酸化亜鉛系透明導電膜形成材料を加工して得られるターゲット。 27. A target used for film formation by sputtering, ion plating, pulsed laser deposition (PLD), or electron beam (EB) vapor deposition, wherein the zinc oxide-based transparent material according to claim 24 is used. A target obtained by processing a conductive film forming material.
  28. 　請求項２７に記載のターゲットを用いて、スパッタリング法、イオンプレーティング法、パルスレーザ堆積法（ＰＬＤ法）またはエレクトロンビーム（ＥＢ）蒸着法により酸化亜鉛系透明導電膜を形成する方法。 A method for forming a zinc oxide-based transparent conductive film by sputtering, ion plating, pulsed laser deposition (PLD) or electron beam (EB) evaporation using the target according to claim 27.
  29. 　透明基材上に、請求項２８に記載の透明導電膜の形成方法により形成された酸化亜鉛系透明導電膜を備える透明導電性基板。 A transparent conductive substrate comprising a zinc oxide-based transparent conductive film formed by the method of forming a transparent conductive film according to claim 28 on a transparent substrate.
  30. 　酸化亜鉛系薄膜を酸によりエッチングしてパターニングする方法であって、前記酸化亜鉛系薄膜が、酸化亜鉛を主成分とし、亜鉛とチタンの合計に対するチタンの原子数比Ｔｉ／（Ｚｎ＋Ｔｉ）が０．０２を超え０．１以下の薄膜であるパターニング方法。 In this method, the zinc oxide thin film is patterned by etching with an acid. The zinc oxide thin film contains zinc oxide as a main component, and the atomic ratio Ti / (Zn + Ti) of titanium to the total of zinc and titanium is 0. A patterning method which is a thin film of more than 02 and 0.1 or less.
  31. 　前記酸化亜鉛系薄膜が、実質的に亜鉛、チタンおよび酸素からなる酸化物焼結体または酸化物混合体を加工して得られたターゲットを膜形成材料として成膜されたものである、請求項３０に記載のパターニング方法。 The zinc oxide-based thin film is formed by using a target obtained by processing an oxide sintered body or an oxide mixture substantially composed of zinc, titanium, and oxygen as a film forming material. 30. The patterning method according to 30.
  32. 　前記チタンは、一般式ＴｉＯ2-X（Ｘ＝０．１～１）で表される低原子価酸化チタン由来のチタンである、請求項３０または３１に記載のパターニング方法。 32. The patterning method according to claim 30, wherein the titanium is titanium derived from low-valent titanium oxide represented by a general formula TiO 2−X (X = 0.1 to 1).
  33. 　前記低原子価酸化チタンは、２価のチタンからなる酸化チタン（ＴｉＯ）または３価のチタンからなる酸化チタン（Ｔｉ2Ｏ3）である、請求項３２に記載のパターニング方法。 The patterning method according to claim 32, wherein the low-valence titanium oxide is titanium oxide (TiO) made of divalent titanium or titanium oxide (Ti 2 O 3 ) made of trivalent titanium.
  34. 　前記酸化亜鉛系薄膜が真空成膜法により成膜された膜である、請求項３０～３３のいずれかに記載のパターニング方法。 The patterning method according to any one of claims 30 to 33, wherein the zinc oxide-based thin film is a film formed by a vacuum film forming method.
  35. 　前記真空成膜法がスパッタリング法、イオンプレーティング法、パルスレーザーデポジション法（ＰＬＤ法）またはエレクトロンビーム（ＥＢ）蒸着法である、請求項３４に記載のパターニング方法。 The patterning method according to claim 34, wherein the vacuum film forming method is a sputtering method, an ion plating method, a pulse laser deposition method (PLD method), or an electron beam (EB) vapor deposition method.
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