WO2014156601A1 - Igzo sputtering target and igzo film - Google Patents

Igzo sputtering target and igzo film Download PDF

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Publication number
WO2014156601A1
WO2014156601A1 PCT/JP2014/056250 JP2014056250W WO2014156601A1 WO 2014156601 A1 WO2014156601 A1 WO 2014156601A1 JP 2014056250 W JP2014056250 W JP 2014056250W WO 2014156601 A1 WO2014156601 A1 WO 2014156601A1
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Prior art keywords
phase
raw material
powder
sputtering
zno
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PCT/JP2014/056250
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French (fr)
Japanese (ja)
Inventor
幸三 長田
浩二 角田
敏也 栗原
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Jx日鉱日石金属株式会社
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Application filed by Jx日鉱日石金属株式会社 filed Critical Jx日鉱日石金属株式会社
Priority to JP2015508253A priority Critical patent/JP5883990B2/en
Priority to KR1020177004745A priority patent/KR101973873B1/en
Priority to CN201480002040.8A priority patent/CN105308208A/en
Priority to KR1020157001570A priority patent/KR20150023832A/en
Publication of WO2014156601A1 publication Critical patent/WO2014156601A1/en

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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Definitions

  • the present invention relates to an IGZO target suitable for use in manufacturing a transparent semiconductor IGZO film used for an active layer of a thin film transistor in a liquid crystal display device or an organic EL display device by a sputtering method, and sputtering the target.
  • the IGZO film obtained by doing this.
  • Thin film transistors using an active layer made of a silicon-based material for driving each pixel are used in display elements such as active matrix liquid crystal display devices.
  • the aperture ratio is increased due to the increase in the area occupied by transistors as pixels become smaller.
  • a thin film transistor using a transparent oxide semiconductor has been developed due to a decrease in the number of films and a need for high-temperature film formation.
  • Transparent oxide semiconductors are attracting attention from the viewpoint of being able to form a uniform film over a large area by a sputtering method, and having high mobility.
  • In—Ga—Zn—O containing indium, gallium, zinc, and oxygen as constituent elements.
  • the mobility of an amorphous IGZO film made of a base material (hereinafter referred to as “IGZO”) is higher than that of amorphous silicon, and a field effect transistor using the amorphous IGZO film as an active layer is turned on / off. Since it has characteristics such as a large ratio and a low off-state current value, it is considered promising (see Non-Patent Document 1 and Patent Document 1).
  • a sputtering method that is excellent in mass productivity is the most appropriate.
  • the IGZO target needs to have a high density.
  • Patent Document 2 describes a method for producing an indium oxide-based sputtering target using indium oxide powder having a chlorine concentration of 50 mass ppm or less. However, only the effect of the chlorine concentration contained in the indium oxide powder is disclosed in the specification. Patent Document 3 has a description relating to an indium oxide powder having a low halogen element content. However, in the examples, only indium nitrate is used as a raw material.
  • Patent Document 4 discloses that "an oxide including an indium element (In), a gallium element (Ga, and a zinc element (Zn), and an oxide crystal phase represented by (Ga, In) 2 O 3" .
  • the oxide (the oxide crystal phase represented by Ga, In 2 O 3 is 50% by mass or more with respect to the entire crystal phase contained in the oxide.
  • Indium element (In), gallium element ( The oxide is described in which the atomic ratio of each element with respect to the sum of Ga) and zinc element (Zn) (In + Ga + Zn) satisfies the relationships of the following formulas (1) to (3).
  • 0.05 ⁇ Zn / (In + Ga + Zn) ⁇ 0.9 (3) 0.05 ⁇ Zn / (In + Ga + Zn) ⁇ 0.9 (3)
  • Patent Document 5 discloses that “a sputtering target containing oxide A shown below and indium oxide (In 2 O 3 ) having a Bix (registered trademark) byte type crystal structure.
  • Oxide A Indium It contains an element (In), a gallium element (Ga), and a zinc element (Zn).
  • the incident angle (2 ⁇ ) is 7.0 ° to 8.4 °, 30.6 by X-ray diffraction measurement (Cuk ⁇ ray).
  • the component composition of a wide range of target is described, there is a problem that the effect of suppressing abnormal discharge is small because the crystal structure (phase) of the target is not sufficiently adjusted.
  • the present invention has been made by paying attention to such a situation, and an object thereof is to provide a high-density IGZO target as a sputtering target necessary for forming a transparent semiconductor IGZO film by sputtering. Further, it is an object to provide an IGZO target technology capable of reducing the bulk resistance of a sputtering target, keeping the carrier concentration and mobility of the sputtered film within a certain range, minimizing arcing, and performing DC sputtering. And
  • An IGZO sintered sputtering target composed of indium (In), gallium (Ga), zinc (Zn), and oxygen (O), and In, Ga, and Zn are 0.575 ⁇ In / (In + Ga) ⁇ 0 500, and a composition range of Zn / (In + Ga + Zn) ⁇ 0.333, and a single phase structure composed of (In x Ga (1-x) ) 2 ZnO 4 (1>x> 0) phase.
  • a sputtering target comprising: 2) An IGZO sintered sputtering target composed of indium (In), gallium (Ga), zinc (Zn), and oxygen (O), and In, Ga, and Zn are 0.575 ⁇ In / (In + Ga) ⁇ 0 .500 and a composition range of Zn / (In + Ga + Zn) ⁇ 0.333, and is composed of an (In x Ga (1-x) ) 2 ZnO 4 (1>x> 0) phase and an In 2 O 3 phase.
  • a sputtering target having a structure of a two-phase structure and having a maximum diameter of the In 2 O 3 phase of 10 ⁇ m or less.
  • a high-density IGZO oxide sintered body used as a sputtering target for producing a transparent semiconductor IGZO film can provide a high-density IGZO target, and a sputtering target.
  • IGZO target technology capable of DC sputtering by reducing the bulk resistance of the substrate, keeping the carrier concentration and mobility of the sputtered film within a certain range, minimizing the occurrence of arcing, and active matrix driving.
  • the transparent semiconductor IGZO film which becomes an active layer portion of the thin film transistor in the liquid crystal display element or the organic EL display element, has an effect that it can be produced with high quality and efficiency.
  • the oxide sintered body used in the present invention contains indium (In), gallium (Ga), zinc (Zn), and oxygen (O) as constituent elements.
  • the oxygen partial pressure during film formation is reduced to obtain predetermined film characteristics (carrier concentration, mobility).
  • the carrier concentration in the film decreases as the oxygen partial pressure during film formation increases.
  • a carrier concentration of the order of 10 15 (cm ⁇ 3 ) or less is necessary, and in order to obtain this, it is necessary to introduce oxygen during film formation.
  • As the oxygen partial pressure increases negative factors such as a decrease in sputtering rate and plasma instability occur, so a lower oxygen partial pressure is preferable.
  • the IGZO sputtering target composed of indium (In), gallium (Ga), zinc (Zn), and oxygen (O) has an In, Ga, and Zn content excluding oxygen of 0.575 ⁇ In / (In + Ga) ⁇ 0. 500 and a composition range of Zn / (In + Ga + Zn) ⁇ 0.333.
  • DC sputtering can be performed while keeping the carrier concentration and mobility in a certain range, minimizing the occurrence of arcing.
  • the In 2 O 3 phase grows remarkably, and a large different phase having different electrical characteristics exists in the IGZO phase, leading to abnormal discharge.
  • the carrier concentration in the film tends to increase, and in order to obtain a film with a low carrier concentration, it is necessary to introduce a large amount of oxygen at the time of film formation, which makes the plasma during sputtering uneasy, and this also causes abnormal discharge. Become.
  • the amount of In is too small, the mobility of the film will be insufficient, so a certain amount or more is necessary. In order to ensure a predetermined mobility while avoiding abnormalities during sputtering, it is necessary to control the In composition in the present specification.
  • the IGZO target of the present invention has only the (In x Ga (1-x) ) 2 ZnO 4 (1>x> 0) phase, or (In x Ga (1-x) ) 2 ZnO 4 (1> x It is one of the major features that part of the In 2 O 3 phase is contained in addition to the> 0) phase and the bulk resistance is 15 m ⁇ ⁇ cm or less.
  • the sputtering target is characterized by having a structure in which the maximum diameter of the In 2 O 3 phase is 10 ⁇ m or less and having a relative density of 95% or more.
  • an IGZO film having film characteristics with a carrier concentration of 5 ⁇ 10 15 (cm ⁇ 3 ) or less and a mobility of 5 (cm 2 / Vs) or more can be obtained. These conditions can be set as necessary according to the purpose of improving the characteristics.
  • the relative density of the oxide sintered body of the present invention can be 95% or more, can be 98% or more, and can be 99% or more.
  • the relative density of the oxide sintered body is less than 95%, the variation in the carrier concentration of the film becomes large.
  • the oxide sintered body is used as a sputtering target and sputtered, The advantage of the present invention is clear because there is a disadvantage that the occurrence of arcing increases with the passage of time and the obtained film characteristics deteriorate.
  • the measurement method of the relative density of the oxide sintered body can first determine the value of the density at which the relative density of the oxide sintered body is 100% from each constituent element and form for each composition.
  • the density of the actually produced oxide sintered body can be obtained by the Archimedes method or the like, and the relative density can be obtained by dividing by the density value of 100%.
  • the measurement of the particle size of In 2 O 3 contained in the oxide sintered body becomes the maximum of each In 2 O 3 phase by image analysis from a structural photograph containing In 2 O 3 by a reflected electron image of SEM or the like. The diameter was measured and the maximum diameter in one field of view was determined. Five fields of view were measured at random, and the maximum value among them was taken as the maximum length.
  • the sputtering voltage during film formation can be lowered by reducing the bulk resistance of the target of the present invention.
  • the sputtering voltage is high, the film formed by the secondary ions and high energy scattering particles generated by sputtering is impacted and damaged, resulting in many oxygen vacancies.
  • the amount of oxygen vacancies in the film is reduced, and the partial pressure of oxygen during sputtering necessary for obtaining a predetermined carrier concentration can be reduced.
  • the size of the In 2 O 3 phase can be controlled by the component composition and the sintering temperature. That is, the higher the In concentration, the larger the In 2 O 3 phase grows, and the larger the size when sintered at a high temperature. Thus, the size of the In 2 O 3 phase can be controlled.
  • the sintering temperature is preferably 1420 ° C. or higher and 1480 ° C. or lower. If the sintering temperature is raised too much, the In 2 O 3 phase becomes coarse and the number of arcing increases, which is not preferable.
  • a representative example of the production process of the oxide sintered body according to the present invention is as follows.
  • a raw material indium oxide (In 2 O 3 ), gallium oxide (Ga 2 O 3 ), and zinc oxide (ZnO) can be used.
  • In 2 O 3 indium oxide
  • gallium oxide Ga 2 O 3
  • zinc oxide ZnO
  • Each raw material powder is weighed so as to have a desired composition ratio. As described above, impurities inevitably contained in these are included.
  • the target is prepared by calcining the raw material as necessary. After mixing each raw material with a super mixer, if necessary, they are packed in an alumina sagger and calcined at a temperature in the range of 950 to 1350 ° C. The holding time for the calcination is 2 to 10 hours in an oxygen atmosphere or an air atmosphere.
  • the mixed raw material is finely pulverized in units of 1 to 20 kg per batch, for example, with an attritor ( ⁇ 3 mm zirconia beads, agitator rotation speed 300 rpm) or LMZ (Star Mill: manufactured by Ashizawa Finetech) for about 2 to 5 hours.
  • an attritor ⁇ 3 mm zirconia beads, agitator rotation speed 300 rpm
  • LMZ Star Mill: manufactured by Ashizawa Finetech
  • the raw material is batched in units of 20 to 1000 kg and finely pulverized by LMZ (Star Mill: manufactured by Ashizawa Finetech) for about 2 to 8 hours ( ⁇ 0.5 mm zirconia beads, input power 2.0 to 20.0 kW ⁇ Hr )
  • the finely pulverized slurry is added with a binder, dried with a granulator at 100 to 250 ° C., and sieved with a sieve having an opening of 250 ⁇ m to collect powder.
  • the specific surface area of each powder is measured before and after pulverization. 50 to 200 cc of an aqueous PVA solution (6% PVA solid content) is mixed with 1000 g of IGZO powder.
  • a mold of ⁇ 210 mm is filled with 1000 g of powder and pressed at a surface pressure of 400 to 1000 kgf ⁇ cm 2 to obtain a molded body.
  • This molded body is double vacuum packed with vinyl and CIPed at 1500 to 4000 kgf / cm 2 .
  • sintering is performed at a predetermined temperature (retention time 5 to 24 hours, in an oxygen atmosphere) to obtain a sintered body.
  • the oxide sintered body obtained as described above is processed into a target of, for example, 152.4 ⁇ ⁇ 5 tmm by performing cylindrical grinding on the outer periphery and surface grinding on the surface side.
  • an indium alloy or the like is bonded to a copper backing plate as a bonding metal to obtain a sputtering target.
  • the raw material powder used in the examples is as shown in Table 1.
  • IGZO raw materials prepare In, Ga, Zn excluding oxygen in the metal ratio, In / (In + Ga) ⁇ 0.575, Zn / (In + Ga + Zn) ⁇ 0.333, and balance with Ga composition. Then, these raw material combinations and production conditions (fine pulverization, calcination temperature, sintering temperature) were changed to produce targets, and various tests were performed. Details thereof are shown in Examples 1 to 7 in Table 1.
  • the bulk resistance value was measured by a four-probe method using a resistivity measuring instrument ( ⁇ -5 +, manufactured by NP Corporation).
  • sputtering conditions As the sputtering apparatus, a DC magnetron sputtering apparatus was used. The film formation conditions were room temperature, DC 500 W, oxygen concentration 6%, and the annealing conditions were 300 ° C. ⁇ 1 hr in an air atmosphere.
  • the carrier concentration and mobility of the film were measured using a Toyo Technica (ResiTest8400 Hall effect measuring device).
  • the target was a carrier concentration of 5 ⁇ 10 15 (cm ⁇ 3 ) or less and a mobility of 5 (cm 2 / Vs) or more.
  • Example 1 In 2 O 3 as raw materials, using In 2 O 3 powder having a particle size of 1.3 .mu.m, specific surface area (BET) 4.4m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area 9.
  • BET specific surface area
  • a 1 m 2 / g Ga 2 O 3 powder was used, and a ZnO powder having a particle size of 1.1 ⁇ m and a specific surface area of 3.8 m 2 / g was used as a ZnO raw material.
  • the In 2 O 3 raw material is 46.6 wt%
  • the Ga 2 O 3 raw material is 28.6 wt%
  • the ZnO raw material is 24.8 wt%
  • the total is 100 wt%
  • the metal ratio of In, Ga, and Zn is 0.524 in In / (In + Ga), Zn / (In + Ga + Zn) is 0.323, and the balance is Ga.
  • the specific surface area before pulverization was 6.0 m 2 / g.
  • the specific surface area after pulverization was 17.8 m 2 / g. This difference was 11.8 m 2 / g.
  • the sintering temperature of the powder was 1430 ° C., and the sintering atmosphere was sintered in an oxygen atmosphere.
  • the density is 6.32 g / cm 3
  • the relative density is 96.8%
  • the bulk resistance value is 3.8 m ⁇ ⁇ cm, and it has a low bulk resistance value that allows DC sputtering sufficiently. It was.
  • the maximum size (major axis) of the In 2 O 3 phase was 4.9 ⁇ m, and the phase state was two phases of In x Ga (1-x ) 2 ZnO 4 phase and In 2 O 3 phase.
  • the carrier concentration was 2.21 ⁇ 10 15 (cm ⁇ 3 ) and the mobility was 9.14 (cm 2 / Vs).
  • the occurrence of arcing during sputtering was as small as 121 times. All satisfied the conditions of the present invention.
  • Example 2 In 2 O 3 powder, particle size 1.3 .mu.m, using In 2 O 3 powder having a specific surface area of 4.4 m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area of 9.1 m 2 / g using Ga 2 O 3 powder, ZnO as a raw material, with particle size 1.1 .mu.m, ZnO powder having a specific surface area of 3.8 m 2 / g.
  • the In 2 O 3 raw material is 44.7 wt%
  • the Ga 2 O 3 raw material is 29.6 wt%
  • the ZnO raw material is 25.7 wt%
  • the total is 100 wt%
  • In, Ga, and Zn have a metal ratio of In / (In + Ga) of 0.505, Zn / (In + Ga + Zn) of 0.331, and the balance of Ga.
  • the specific surface area before pulverization was 6.0 m 2 / g.
  • the specific surface area after pulverization was 18.0 m 2 / g. This difference was 12.0 m 2 / g.
  • the sintering temperature of the powder was 1430 ° C., and the sintering atmosphere was sintered in an oxygen atmosphere.
  • the density is 6.33 g / cm 3
  • the relative density is high as 97.3%
  • the bulk resistance value is 5.8 m ⁇ ⁇ cm, and it has a low bulk resistance value that allows DC sputtering sufficiently.
  • the phase state was a single phase of In x Ga (1-x) ) 2 ZnO 4 phase.
  • the carrier concentration was 1.34 ⁇ 10 15 (cm ⁇ 3 ) and the mobility was 6.46 (cm 2 / Vs).
  • the occurrence of arcing during sputtering was as small as 86 times. All satisfied the conditions of the present invention.
  • Example 3 In 2 O 3 powder, particle size 1.3 .mu.m, using In 2 O 3 powder having a specific surface area of 4.4 m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area of 9.1 m 2 / g of Ga 2 O 3 powder was used, and ZnO powder having a particle size of 1.1 ⁇ m and a specific surface area of 3.8 m 2 / g was used as a ZnO raw material.
  • the density is 6.33 g / cm 3
  • the relative density is 97.1%
  • the bulk resistance value is 4.3 m ⁇ ⁇ cm, and it has a low bulk resistance value that enables DC sputtering sufficiently. It was.
  • the maximum size (major axis) of the In 2 O 3 phase was 5.2 ⁇ m, and the phase state was two phases of In x Ga (1-x ) 2 ZnO 4 phase and In 2 O 3 phase.
  • the carrier concentration was 1.56 ⁇ 10 15 (cm ⁇ 3 ) and the mobility was 7.23 (cm 2 / Vs).
  • the occurrence of arcing during sputtering was as small as 130 times. All satisfied the conditions of the present invention.
  • Example 4 In 2 O 3 powder, particle size 1.3 .mu.m, using In 2 O 3 powder having a specific surface area of 4.4 m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area of 9.1 m 2 / g using Ga 2 O 3 powder, ZnO as a raw material, with particle size 1.1 .mu.m, ZnO powder having a specific surface area of 3.8 m 2 / g.
  • the In 2 O 3 raw material is 46.6 wt%
  • the Ga 2 O 3 raw material is 28.6 wt%
  • the ZnO raw material is 24.8 wt%
  • the total is 100 wt%
  • the metal ratio of In, Ga, and Zn is 0.524 in In / (In + Ga), Zn / (In + Ga + Zn) is 0.323, and the balance is Ga.
  • the density is 6.32 g / cm 3
  • the relative density is as high as 96.8%
  • the bulk resistance value is 2.9 m ⁇ ⁇ cm, and it has a low bulk resistance value that allows DC sputtering sufficiently. It was.
  • the maximum size (major axis) of the In 2 O 3 phase was 4.3 ⁇ m, and the phase state was two phases of In x Ga (1-x ) 2 ZnO 4 phase and In 2 O 3 phase.
  • the carrier concentration was 1.72 ⁇ 10 15 (cm ⁇ 3 ) and the mobility was 8.62 (cm 2 / Vs).
  • the occurrence of arcing during sputtering was as small as 128 times. All satisfied the conditions of the present invention.
  • Example 5 In 2 O 3 powder, particle size 1.3 .mu.m, using In 2 O 3 powder having a specific surface area of 4.4 m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area of 9.1 m 2 / g of Ga 2 O 3 powder was used, and ZnO powder having a particle size of 1.1 ⁇ m and a specific surface area of 3.8 m 2 / g was used as a ZnO raw material.
  • the In 2 O 3 raw material is 46.6 wt%
  • the Ga 2 O 3 raw material is 28.6 wt%
  • the ZnO raw material is 24.8 wt%
  • the total is 100 wt%
  • the metal ratio of In, Ga, and Zn is 0.524 in In / (In + Ga), Zn / (In + Ga + Zn) is 0.323, and the balance is Ga.
  • the specific surface area before pulverization was 5.9 m 2 / g.
  • the specific surface area after pulverization was 17.5 m 2 / g. This difference was 11.6 m 2 / g.
  • the sintering temperature of the powder was 1370 ° C., and the sintering atmosphere was sintered in an oxygen atmosphere.
  • the density is 6.32 g / cm 3
  • the relative density is 96.8%
  • the bulk resistance value is 8.0 m ⁇ ⁇ cm, and it has a low bulk resistance value that allows DC sputtering sufficiently. It was.
  • the maximum size (major axis) of the In 2 O 3 phase was 3.5 ⁇ m, and the phase state was two phases of In x Ga (1-x ) 2 ZnO 4 phase and In 2 O 3 phase.
  • the carrier concentration was 2.61 ⁇ 10 15 (cm ⁇ 3 ) and the mobility was 8.89 (cm 2 / Vs). Moreover, the occurrence of arcing during sputtering was as small as 142 times. All satisfied the conditions of the present invention.
  • Example 6 In 2 O 3 powder, particle size 1.3 .mu.m, using In 2 O 3 powder having a specific surface area of 4.4 m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area of 9.1 m 2 / g of Ga 2 O 3 powder was used, and ZnO powder having a particle size of 1.1 ⁇ m and a specific surface area of 3.8 m 2 / g was used as a ZnO raw material.
  • the In 2 O 3 raw material is 49.9 wt%
  • the Ga 2 O 3 raw material is 24.9 wt%
  • the ZnO raw material is 25.3 wt%
  • the total is 100 wt%
  • the metal ratio of In, Ga, and Zn is 0.575 in In / (In + Ga), Zn / (In + Ga + Zn) is 0.332, and the balance is Ga.
  • the density is 6.38 g / cm 3
  • the relative density is as high as 97.5%
  • the bulk resistance value is 9.8 m ⁇ ⁇ cm, and it has a low bulk resistance value that allows DC sputtering sufficiently.
  • the phase state was a single phase of In x Ga (1-x) ) 2 ZnO 4 phase.
  • the carrier concentration was 3.53 ⁇ 10 15 (cm ⁇ 3 ) and the mobility was 9.53 (cm 2 / Vs).
  • the occurrence of arcing during sputtering was as small as 134 times. All satisfied the conditions of the present invention.
  • Example 7 In 2 O 3 powder, particle size 1.3 .mu.m, using In 2 O 3 powder having a specific surface area of 4.4 m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area of 9.1 m 2 / g of Ga 2 O 3 powder was used, and ZnO powder having a particle size of 1.1 ⁇ m and a specific surface area of 3.8 m 2 / g was used as a ZnO raw material.
  • the In 2 O 3 raw material is 52.4 wt%
  • the Ga 2 O 3 raw material is 26.2 wt%
  • the ZnO raw material is 21.4 wt%
  • the total is 100 wt%
  • In, Ga, and Zn are metal ratios
  • In / (In + Ga) is 0.575
  • Zn / (In + Ga + Zn) is 0.286
  • the balance is Ga.
  • the specific surface area before pulverization was 6.2 m 2 / g.
  • the specific surface area after pulverization was 15.5 m 2 / g. This difference was 9.3 m 2 / g.
  • the sintering temperature of the powder was 1430 ° C., and the sintering atmosphere was sintered in an oxygen atmosphere.
  • the density is 6.42 g / cm 3
  • the relative density is 97.2%
  • the bulk resistance value is 2.1 m ⁇ ⁇ cm
  • the maximum size (major axis) of the In 2 O 3 phase was 8.8 ⁇ m
  • the phase state was two phases of In x Ga (1-x ) 2 ZnO 4 phase and In 2 O 3 phase.
  • the carrier concentration was 4.55 ⁇ 10 15 (cm ⁇ 3 ) and the mobility was 7.34 (cm 2 / Vs).
  • the occurrence of arcing during sputtering was as small as 173 times. All satisfied the conditions of the present invention.
  • the density was 6.33 g / cm 3
  • the relative density was as high as 97.3%
  • the bulk resistance value was as high as 32 m ⁇ ⁇ cm
  • DC sputtering was not sufficient.
  • the phase state was a single phase of In x Ga (1-x) ) 2 ZnO 4 phase.
  • the carrier concentration increased to 5.87 ⁇ 10 15 (cm ⁇ 3 ).
  • the mobility was 8.92 (cm 2 / Vs).
  • the occurrence of arcing during sputtering was as small as 92 times. The conditions of the present invention were not satisfied.
  • the In 2 O 3 raw material is 46.6 wt%
  • the Ga 2 O 3 raw material is 28.6 wt%
  • the ZnO raw material is 24.8 wt%
  • the total is 100 wt%
  • the metal ratio of In, Ga, and Zn is 0.500 in In / (In + Ga), Zn / (In + Ga + Zn) is 0.333, and the balance is Ga.
  • the density was 6.32 g / cm 3
  • the relative density was 97.2%
  • the bulk resistance was as high as 80 m ⁇ ⁇ cm
  • DC sputtering was not sufficient.
  • the phase state was a single phase of In x Ga (1-x) ) 2 ZnO 4 phase.
  • the carrier concentration increased to 10.8 ⁇ 10 15 (cm ⁇ 3 ).
  • the mobility was 10.5 (cm 2 / Vs).
  • the occurrence of arcing during sputtering was as small as 76 times. The conditions of the present invention were not satisfied.
  • the In 2 O 3 raw material is 61.7 wt%
  • the Ga 2 O 3 raw material is 16.7 wt%
  • the ZnO raw material is 21.7 wt%
  • the total is 100 wt%
  • the metal ratio of In, Ga, and Zn is 0.714 in In / (In + Ga), Zn / (In + Ga + Zn) is 0.333, and the balance is Ga.
  • the specific surface area before pulverization was 5.1 m 2 / g.
  • the specific surface area after pulverization was 16.0 m 2 / g. This difference was 10.9 m 2 / g.
  • the sintering temperature of the powder was 1430 ° C., and the sintering atmosphere was sintered in an oxygen atmosphere.
  • the density is 6.55 g / cm 3
  • the relative density is 98.3%
  • the bulk resistance value is 2.7 m ⁇ ⁇ cm, and it has a low bulk resistance value that allows DC sputtering sufficiently. It was.
  • the maximum size (major axis) of the In 2 O 3 phase was increased to 11.1 ⁇ m, and the phase state was two phases of In x Ga (1-x ) 2 ZnO 4 phase and In 2 O 3 phase.
  • the carrier concentration increased to 1.15 ⁇ 10 19 (cm ⁇ 3 ).
  • the mobility was 29.0 (cm 2 / Vs).
  • arcing occurred during sputtering as many times as 366 times. This is a result of an increase in the In 2 O 3 phase and did not satisfy the conditions of the present invention.
  • the In 2 O 3 raw material is 52.4 wt%
  • the Ga 2 O 3 raw material is 26.2 wt%
  • the ZnO raw material is 21.4 wt%
  • the total is 100 wt%
  • In, Ga, and Zn are metal ratios
  • In / (In + Ga) is 0.575
  • Zn / (In + Ga + Zn) is 0.286
  • the balance is Ga.
  • the specific surface area before pulverization was 6.2 m 2 / g.
  • the specific surface area after pulverization was 15.5 m 2 / g. This difference was 9.3 m 2 / g.
  • the sintering temperature of the powder was 1490 ° C., and the sintering atmosphere was sintered in an oxygen atmosphere.
  • the density is 6.43 g / cm 3
  • the relative density is 97.4%
  • the bulk resistance value is 1.2 m ⁇ ⁇ cm
  • the maximum size (major axis) of the In 2 O 3 phase increased to 13.5 ⁇ m, and the phase state was two phases of In x Ga (1-x ) 2 ZnO 4 phase and In 2 O 3 phase.
  • the carrier concentration was 4.55 ⁇ 10 15 (cm ⁇ 3 ) and the mobility was 7.34 (cm 2 / Vs).
  • the occurrence of arcing during sputtering was as high as 514 times.
  • Example 7 the component composition is the same as in Example 7, in Comparative Example 4, coarsening of the In 2 O 3 phase was observed. This is probably because the sintering of the In 2 O 3 phase was coarsened because the sintering temperature was higher at 1490 ° C. in Comparative Example 4 than at 1430 ° C. in Example 7.
  • the In 2 O 3 raw material is 42.9 wt%
  • the Ga 2 O 3 raw material is 31.9 wt%
  • the ZnO raw material is 25.2 wt%
  • the total is 100 wt%
  • In, Ga, and Zn have a metal ratio of In / (In + Ga) of 0.476, Zn / (In + Ga + Zn) of 0.323, and the balance of Ga.
  • the density was 5.60 g / cm 3 and the relative density was as low as 86.5%, and there was no conductivity and DC sputtering could not be performed.
  • the phase state was a single phase of In x Ga (1-x) ) 2 ZnO 4 phase. Since sputtering was not performed, thin film characteristics could not be evaluated.
  • the high-density IGZO oxide sintered body used as the sputtering target for producing the transparent semiconductor IGZO film of the present invention can provide a high-density IGZO target, and can reduce the bulk resistance of the sputtering target and the sputtered film.
  • the IGZO target technology that allows DC sputtering to be performed while keeping the carrier concentration and mobility in a certain range, minimizing the occurrence of arcing, and providing an excellent effect that stable DC sputtering is possible. Have As a result, the target life can be lengthened, and there is little variation in quality, so that mass productivity can be improved.
  • This In—Ga—Zn—O-based (IGZO) material is useful for a field effect transistor because an amorphous oxide having an electron carrier concentration of less than 10 18 / cm 3 can be obtained. Moreover, since it can be used as an IGZO target without hindrance for a wide range of applications, its industrial utility value is high.

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Abstract

Provided is an IGZO sintered body sputtering target that comprises indium (In), gallium (Ga), zinc (Zn), and oxygen (O) and that is characterized by: the In, Ga, and Zn satisfying 0.575 ≥ In/(In+Ga) ≥ 0.500 and being within a composition range that is represented by Zn/(In+Ga+Zn) < 0.333; having a single-phase structure comprising an (InxGa(1-x))2ZnO4(1 > X > 0) phase or a two-phase structure comprising an (InxGa(1-x))2ZnO4(1 > X > 0) phase and an In2O3 phase; and by the In2O3 phase having a maximum diameter of 10 µm or less. Also provided is IGZO target technology that makes DC sputtering possible, that achieves low bulk resistance in a sputtering target, a carrier concentration that is equal to or less than a fixed range, and a target having high density, and that keeps the occurrence of arcing to a minimum.

Description

ＩＧＺＯスパッタリングターゲット及びＩＧＺＯ膜IGZO sputtering target and IGZO film
　本発明は、液晶表示装置や有機EL表示装置中の薄膜トランジスタの活性層等に使用される透明半導体ＩＧＺＯ膜を、スパッタリング法で製造する際に使用するのに適した、ＩＧＺＯターゲット及び該ターゲットをスパッタリングすることにより得られたＩＧＺＯ膜に関する。 The present invention relates to an IGZO target suitable for use in manufacturing a transparent semiconductor IGZO film used for an active layer of a thin film transistor in a liquid crystal display device or an organic EL display device by a sputtering method, and sputtering the target. The IGZO film obtained by doing this.
アクティブマトリックス型液晶表示装置等の表示素子には、各画素駆動用のシリコン系材料を活性層とする薄膜トランジスタが使用されているが、画素の微細化に伴いトランジスタの占有領域が増えることによる開口率の減少、高温成膜が必要等の欠点から、近年、透明酸化物半導体を用いた薄膜トランジスタの開発が行われている。 Thin film transistors using an active layer made of a silicon-based material for driving each pixel are used in display elements such as active matrix liquid crystal display devices. However, the aperture ratio is increased due to the increase in the area occupied by transistors as pixels become smaller. In recent years, a thin film transistor using a transparent oxide semiconductor has been developed due to a decrease in the number of films and a need for high-temperature film formation.
透明酸化物半導体は、スパッタリング法で大面積へ均一成膜可能、高移動度等の観点から注目されており、中でも、インジウム、ガリウム、亜鉛、酸素を構成元素とするＩｎ－Ｇａ－Ｚｎ－Ｏ系材料（以下、「ＩＧＺＯ」と記載する。）からなる非晶質ＩＧＺＯ膜の移動度は、アモルファスシリコンの移動度より高く、非晶質ＩＧＺＯ膜を活性層に用いた電界効果型トランジスタはオンオフ比が大きく、オフ電流値が低い等の特性を有するため、有望視されている（非特許文献１、特許文献１参照）。 Transparent oxide semiconductors are attracting attention from the viewpoint of being able to form a uniform film over a large area by a sputtering method, and having high mobility. In particular, In—Ga—Zn—O containing indium, gallium, zinc, and oxygen as constituent elements. The mobility of an amorphous IGZO film made of a base material (hereinafter referred to as “IGZO”) is higher than that of amorphous silicon, and a field effect transistor using the amorphous IGZO film as an active layer is turned on / off. Since it has characteristics such as a large ratio and a low off-state current value, it is considered promising (see Non-Patent Document 1 and Patent Document 1).
非晶質ＩＧＺＯ膜の作製方法としては、量産性に優れているスパッタリング法が、最も適切であり、そのためには、ＩＧＺＯターゲットは高密度である必要がある。 As a method for producing an amorphous IGZO film, a sputtering method that is excellent in mass productivity is the most appropriate. For this purpose, the IGZO target needs to have a high density.
　しかしながら、これまでに高密度ＩＧＺＯターゲットを製造できる場合もあったが、生産継続中に焼結体の密度が低下し、更に生産を継続していくと、また、高密度ターゲットができるようになるといったことがあり、その原因として、焼結条件等のターゲット製造プロセス条件の不適切が予想されたが、結局、原因は不明ということがあった。 However, there have been cases where high-density IGZO targets can be manufactured so far, but the density of the sintered body decreases during production continuation, and if production continues further, high-density targets can be produced. As the cause, it was predicted that the target manufacturing process conditions such as sintering conditions were inappropriate, but the cause was unknown in the end.
　特許文献２には、塩素濃度が５０質量ｐｐｍ以下の酸化インジウム粉を用いた酸化インジウム系スパッタリングターゲットの製造方法について記載されている。しかしながら該明細書で開示されているのは酸化インジウム粉に含まれる塩素濃度の効果のみである。特許文献３には、ハロゲン元素の含有量が少ない酸化インジウム粉当に関する記載がある。しかしながら、実施例では、原料としては、硝酸インジウムが用いられているのみである。 Patent Document 2 describes a method for producing an indium oxide-based sputtering target using indium oxide powder having a chlorine concentration of 50 mass ppm or less. However, only the effect of the chlorine concentration contained in the indium oxide powder is disclosed in the specification. Patent Document 3 has a description relating to an indium oxide powder having a low halogen element content. However, in the examples, only indium nitrate is used as a raw material.
　この他、特許文献４には、「インジウム元素（Ｉｎ）、ガリウム元素（Ｇａ 、及び亜鉛元素（Ｚｎ）を含み、（Ｇａ,Ｉｎ）２Ｏ３で表される酸化物結晶相を含む酸化物。前記酸化物に含まれる結晶相全体に対し、前記（Ｇａ，Ｉｎ２Ｏ３で表される酸化物結晶相が、５０質量％以上である前記酸化物。インジウム元素（Ｉｎ）、ガリウム元素（Ｇａ）、及び亜鉛元素（Ｚｎ）の合計（Ｉｎ＋Ｇａ＋Ｚｎ）に対する、各元素の原子比が下記式（１）～（３）の関係を満たす、前記酸化物が記載されている。
０．０５≦Ｉｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）≦０．９（１）
０．０５≦Ｇａ／（Ｉｎ＋Ｇａ＋Ｚｎ）≦０．９（２）
０．０５≦Ｚｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）≦０．９（３）」 In addition, Patent Document 4 discloses that "an oxide including an indium element (In), a gallium element (Ga, and a zinc element (Zn), and an oxide crystal phase represented by (Ga, In) 2 O 3" . The oxide (the oxide crystal phase represented by Ga, In 2 O 3 is 50% by mass or more with respect to the entire crystal phase contained in the oxide. Indium element (In), gallium element ( The oxide is described in which the atomic ratio of each element with respect to the sum of Ga) and zinc element (Zn) (In + Ga + Zn) satisfies the relationships of the following formulas (1) to (3).
0.05 ≦ In / (In + Ga + Zn) ≦ 0.9 (1)
0.05 ≦ Ga / (In + Ga + Zn) ≦ 0.9 (2)
0.05 ≦ Zn / (In + Ga + Zn) ≦ 0.9 (3) ”
また、特許文献５には、「下記に示す酸化物Ａ と、ビックス（登録商標）バイト型の結晶構造を有する酸化インジウム（Ｉｎ２Ｏ３） と、を含有するスパッタリングターゲット。酸化物Ａ：インジウム元素（Ｉｎ）、ガリウム元素（Ｇａ）、及び亜鉛元素（Ｚｎ） を含み、Ｘ線回折測定（Ｃｕｋα線）により、入射角（２θ）が、７．０°～８．４ °、３０．６°～３２．０°、３３．８°～３５．８°、５３．５°～５６．５°及び５６．５°～５９．５°の各位置に回折ピークが観測される酸化物。インジウム元素（Ｉｎ）、ガリウム元素（Ｇａ）及び亜鉛元素（Ｚｎ）の原子比が、下記式（１）及び（２）を満たす、スパッタリングターゲット。
０．１０≦Ｚｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）≦０．４５（１）
０．０５＜Ｇａ／（Ｉｎ＋Ｇａ＋Ｚｎ）＜０．１８（２）
さらに、インジウム元素（Ｉｎ） 及びガリウム元素（Ｇａ） の原子比が、下記式（３） を満たす前記スパッタリングターゲット。
０．１４≦Ｇａ／（Ｉｎ＋Ｇａ）（３）」が記載されている。
　しかし、これらは広範囲なターゲットの成分組成が記載されているが、ターゲットの結晶組織（相）の調整が十分行われていないので、異常放電の抑制効果が小さいという問題がある。 Patent Document 5 discloses that “a sputtering target containing oxide A shown below and indium oxide (In 2 O 3 ) having a Bix (registered trademark) byte type crystal structure. Oxide A: Indium It contains an element (In), a gallium element (Ga), and a zinc element (Zn). The incident angle (2θ) is 7.0 ° to 8.4 °, 30.6 by X-ray diffraction measurement (Cukα ray). An oxide in which a diffraction peak is observed at each of positions of 3 ° to 32.0 °, 33.8 ° to 35.8 °, 53.5 ° to 56.5 °, and 56.5 ° to 59.5 °. A sputtering target in which an atomic ratio of an element (In), a gallium element (Ga), and a zinc element (Zn) satisfies the following formulas (1) and (2).
0.10 ≦ Zn / (In + Ga + Zn) ≦ 0.45 (1)
0.05 <Ga / (In + Ga + Zn) <0.18 (2)
Furthermore, the said sputtering target with which atomic ratio of an indium element (In) and a gallium element (Ga) satisfy | fills following formula (3).
0.14 ≦ Ga / (In + Ga) (3) ”.
However, although the component composition of a wide range of target is described, there is a problem that the effect of suppressing abnormal discharge is small because the crystal structure (phase) of the target is not sufficiently adjusted.
特開２００６－１７３５８０号公報JP 2006-173580 A 特開２００８－３０８３８５号公報JP 2008-308385 A 特開平１０－１８２１５０号公報Japanese Patent Laid-Open No. 10-182150 特開２００９－２７５２７２号公報JP 2009-275272 A 特開２０１１－１０６００２号公報JP 2011-106002 A
本発明はこのような事情に着目してなされたものであって、その目的は、透明半導体ＩＧＺＯ膜のスパッタ法での成膜に必要なスパッタリングターゲットとして高密度のＩＧＺＯターゲットを提供するものであり、かつスパッタリング用ターゲットの低バルク抵抗化及びスパッタ膜のキャリア濃度及び移動度を一定の範囲とし、かつアーキングの発生を最小限に押さえ、ＤＣスパッタリングが可能であるＩＧＺＯターゲット技術を提供することを課題とする。 The present invention has been made by paying attention to such a situation, and an object thereof is to provide a high-density IGZO target as a sputtering target necessary for forming a transparent semiconductor IGZO film by sputtering. Further, it is an object to provide an IGZO target technology capable of reducing the bulk resistance of a sputtering target, keeping the carrier concentration and mobility of the sputtered film within a certain range, minimizing arcing, and performing DC sputtering. And
かかる知見を基礎として、本発明は以下の発明を提供する。
１）インジウム（Ｉｎ）、ガリウム（Ｇａ）、亜鉛（Ｚｎ）及び酸素（Ｏ）からなるＩＧＺＯ焼結体スパッタリングターゲットであって、Ｉｎ、Ｇａ、Ｚｎが０．５７５≧Ｉｎ／（Ｉｎ＋Ｇａ）≧０．５００であり、かつＺｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）＜０．３３３の組成範囲であり、(ＩｎｘＧａ（１－ｘ）)２ ＺｎＯ４(１＞ｘ＞０)相からなる単一相の組織を有することを特徴とするスパッタリングターゲット。
２）インジウム（Ｉｎ）、ガリウム（Ｇａ）、亜鉛（Ｚｎ）及び酸素（Ｏ）からなるＩＧＺＯ焼結体スパッタリングターゲットであって、Ｉｎ、Ｇａ、Ｚｎが０．５７５≧Ｉｎ／（Ｉｎ＋Ｇａ）≧０．５００であり、かつＺｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）＜０．３３３の組成範囲であり、(ＩｎｘＧａ（１－ｘ）)２ ＺｎＯ４(１＞ｘ＞０)相とＩｎ２Ｏ３相からなる二相構造の組織を有し、当該Ｉｎ２Ｏ３相の最大径が１０μｍ以下であることを特徴とするスパッタリングターゲット。 Based on this knowledge, the present invention provides the following inventions.
1) An IGZO sintered sputtering target composed of indium (In), gallium (Ga), zinc (Zn), and oxygen (O), and In, Ga, and Zn are 0.575 ≧ In / (In + Ga) ≧ 0 500, and a composition range of Zn / (In + Ga + Zn) <0.333, and a single phase structure composed of (In x Ga (1-x) ) 2 ZnO 4 (1>x> 0) phase. A sputtering target comprising:
2) An IGZO sintered sputtering target composed of indium (In), gallium (Ga), zinc (Zn), and oxygen (O), and In, Ga, and Zn are 0.575 ≧ In / (In + Ga) ≧ 0 .500 and a composition range of Zn / (In + Ga + Zn) <0.333, and is composed of an (In x Ga (1-x) ) 2 ZnO 4 (1>x> 0) phase and an In 2 O 3 phase. A sputtering target having a structure of a two-phase structure and having a maximum diameter of the In 2 O 3 phase of 10 μm or less.
３）バルク抵抗が１５ｍΩ・ｃｍ以下であることを特徴とする上記１）又は２）に記載のスパッタリングターゲット。
４）相対密度が９５％以上であることを特徴とする上記１）～３）のいずれか一項に記載のスパッタリングターゲット。
５）上記１）～４）のいずれか一項に記載のスパッタリングターゲットを用いてスパッタリングすることにより得られる膜であって、キャリア濃度５×１０１５(ｃｍ－３)以下、移動度５(ｃｍ２／Ｖｓ)以上の膜特性を有することを特徴とする膜。 3) The sputtering target according to 1) or 2) above, wherein the bulk resistance is 15 mΩ · cm or less.
4) The sputtering target according to any one of 1) to 3) above, wherein the relative density is 95% or more.
5) A film obtained by sputtering using the sputtering target according to any one of 1) to 4) above, wherein the carrier concentration is 5 × 10 15 (cm −3 ) or less, and the mobility is 5 (cm 2 / Vs) or more.
以上の様に、本発明によれば、透明半導体ＩＧＺＯ膜作製用のスパッタリングターゲットとして使用される高密度ＩＧＺＯ酸化物焼結体は、高密度のＩＧＺＯターゲットを提供することができ、かつスパッタリング用ターゲットの低バルク抵抗化及びスパッタ膜のキャリア濃度及び移動度を一定の範囲とし、かつアーキングの発生を最小限に押さえ、ＤＣスパッタリングが可能であるＩＧＺＯターゲット技術を提供することができるので、アクティブマトリックス駆動の液晶表示素子や有機ＥＬ表示素子中の薄膜トランジスタの活性層部分となる良好な透明半導体ＩＧＺＯ膜を、高品位かつ効率的に作製することができる効果を有する。 As described above, according to the present invention, a high-density IGZO oxide sintered body used as a sputtering target for producing a transparent semiconductor IGZO film can provide a high-density IGZO target, and a sputtering target. IGZO target technology capable of DC sputtering by reducing the bulk resistance of the substrate, keeping the carrier concentration and mobility of the sputtered film within a certain range, minimizing the occurrence of arcing, and active matrix driving. The transparent semiconductor IGZO film, which becomes an active layer portion of the thin film transistor in the liquid crystal display element or the organic EL display element, has an effect that it can be produced with high quality and efficiency.
本発明に使用する酸化物焼結体は、インジウム（Ｉｎ）、ガリウム（Ｇａ）、亜鉛（Ｚｎ）及び酸素（Ｏ）を構成元素とする。ターゲットの組成、バルク抵抗、組織を制御することで、成膜時の酸素分圧を減らして所定の膜特性(キャリア濃度、移動度)を得る。ＩＧＺＯ膜は成膜時の酸素分圧が増加するほど、膜中のキャリア濃度は低くなる。
半導体特性を得るには１０１５(ｃｍ－３)オーダー以下のキャリア濃度が必要であり、これを得るために成膜時に酸素の導入が必要となる。酸素分圧が増えるとスパッタレートの低下、プラズマの不安定化などのマイナス要因が生じるため、酸素分圧は低い方が好ましい。 The oxide sintered body used in the present invention contains indium (In), gallium (Ga), zinc (Zn), and oxygen (O) as constituent elements. By controlling the composition, bulk resistance, and structure of the target, the oxygen partial pressure during film formation is reduced to obtain predetermined film characteristics (carrier concentration, mobility). In the IGZO film, the carrier concentration in the film decreases as the oxygen partial pressure during film formation increases.
In order to obtain semiconductor characteristics, a carrier concentration of the order of 10 15 (cm −3 ) or less is necessary, and in order to obtain this, it is necessary to introduce oxygen during film formation. As the oxygen partial pressure increases, negative factors such as a decrease in sputtering rate and plasma instability occur, so a lower oxygen partial pressure is preferable.
本発明のインジウム（Ｉｎ）、ガリウム（Ｇａ）、亜鉛（Ｚｎ）及び酸素（Ｏ）からなるＩＧＺＯスパッタリングターゲットは、酸素を除くＩｎ、Ｇａ、Ｚｎが０．５７５≧Ｉｎ／（Ｉｎ＋Ｇａ）≧０．５００であり、かつＺｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）＜０．３３３の組成範囲である。
　本願は、Ｉｎ：Ｇａ：Ｚｎ＝１：１：１の組成のＩＧＺＯターゲットを改良する発明であり、高密度のＩＧＺＯターゲットを提供することができ、かつスパッタリング用ターゲットの低バルク抵抗化及びスパッタ膜のキャリア濃度及び移動度を一定の範囲とし、かつアーキングの発生を最小限に押さえ、ＤＣスパッタリングが可能である。 The IGZO sputtering target composed of indium (In), gallium (Ga), zinc (Zn), and oxygen (O) according to the present invention has an In, Ga, and Zn content excluding oxygen of 0.575 ≧ In / (In + Ga) ≧ 0. 500 and a composition range of Zn / (In + Ga + Zn) <0.333.
The present application is an invention that improves an IGZO target having a composition of In: Ga: Zn = 1: 1: 1, can provide a high-density IGZO target, has a low bulk resistance of a sputtering target, and a sputtered film. DC sputtering can be performed while keeping the carrier concentration and mobility in a certain range, minimizing the occurrence of arcing.
ここで、Ｉｎ量が多くなるとＩｎ２Ｏ３相が著しく成長し、ＩＧＺＯ相中に電気特性の異なる大きな異相が存在することとなり、異常放電に繋がる。またＩｎが多いと膜中のキャリア濃度が増えやすく、低キャリア濃度の膜を得るために、成膜時に多量の酸素導入が必要となり、スパッタ中のプラズマが不安となり、これまた異常放電の要因となる。反対にＩｎが少なすぎると膜の移動度が不足してしまうため、一定量以上必要である。
スパッタ時の異常を避けつつ所定の移動度を確保するには本明細中のＩｎ組成にコントロールする必要がある。 Here, when the amount of In increases, the In 2 O 3 phase grows remarkably, and a large different phase having different electrical characteristics exists in the IGZO phase, leading to abnormal discharge. Also, if there is a lot of In, the carrier concentration in the film tends to increase, and in order to obtain a film with a low carrier concentration, it is necessary to introduce a large amount of oxygen at the time of film formation, which makes the plasma during sputtering uneasy, and this also causes abnormal discharge. Become. On the other hand, if the amount of In is too small, the mobility of the film will be insufficient, so a certain amount or more is necessary.
In order to ensure a predetermined mobility while avoiding abnormalities during sputtering, it is necessary to control the In composition in the present specification.
また、Ｇａが増えるとターゲット密度が上がらず、導電性も損なわれる。さらに、Ｇａ、Ｚｎが増えすぎると、得られる膜の移動度が著しく低下するので、ＧａとＺｎの組成もコントロールする必要がある。上記の組成範囲は、これらの問題を解決できる範囲に調整したものであり、これは本願発明の必須の要件である。
また、本願発明のＩＧＺＯターゲットは、(ＩｎｘＧａ（１－ｘ）)２ ＺｎＯ４(１＞ｘ＞０)相のみ、又は(ＩｎｘＧａ（１－ｘ）)２ ＺｎＯ４(１＞ｘ＞０)相以外にＩｎ２Ｏ３相を一部含有し、バルク抵抗が１５ｍΩ・ｃｍ以下であることも、大きな特徴の一つである。 Further, when Ga increases, the target density does not increase and the conductivity is also impaired. Furthermore, since the mobility of the obtained film | membrane will fall remarkably when Ga and Zn increase too much, it is necessary to control the composition of Ga and Zn. The above composition range is adjusted to a range that can solve these problems, and this is an essential requirement of the present invention.
In addition, the IGZO target of the present invention has only the (In x Ga (1-x) ) 2 ZnO 4 (1>x> 0) phase, or (In x Ga (1-x) ) 2 ZnO 4 (1> x It is one of the major features that part of the In 2 O 3 phase is contained in addition to the> 0) phase and the bulk resistance is 15 mΩ · cm or less.
さらに、上記スパッタリングターゲットにおいて、Ｉｎ２Ｏ３相の最大径が１０μｍ以下の組織を有すること、相対密度が９５％以上であることも特徴の一つである。
このＩＧＺＯスパッタリングターゲットを用いてスパッタリングすることにより、キャリア濃度５×１０１５(ｃｍ－３)以下、移動度５(ｃｍ２／Ｖｓ)以上の膜特性を有するＩＧＺＯ膜を得ることができる。これらの条件は、特性を向上させる目的に応じて、必要により設定可能である。 Further, the sputtering target is characterized by having a structure in which the maximum diameter of the In 2 O 3 phase is 10 μm or less and having a relative density of 95% or more.
By sputtering using this IGZO sputtering target, an IGZO film having film characteristics with a carrier concentration of 5 × 10 15 (cm −3 ) or less and a mobility of 5 (cm 2 / Vs) or more can be obtained. These conditions can be set as necessary according to the purpose of improving the characteristics.
上記の通り、本発明の酸化物焼結体の相対密度は９５％以上とすることが可能であり、また９８％以上に、さらには９９％以上を達成することができる。酸化物焼結体の相対密度が９５％未満であると、膜のキャリア濃度のばらつきが大きくなることに加えて、その酸化物焼結体をスパッタリングターゲットとして用いて、スパッタ成膜した場合、スパッタ時間の経過に伴って、アーキングの発生が多くなり、得られる膜特性が劣化するという不利があるので、本願発明の優位性は明らかである。 As described above, the relative density of the oxide sintered body of the present invention can be 95% or more, can be 98% or more, and can be 99% or more. When the relative density of the oxide sintered body is less than 95%, the variation in the carrier concentration of the film becomes large. In addition, when the oxide sintered body is used as a sputtering target and sputtered, The advantage of the present invention is clear because there is a disadvantage that the occurrence of arcing increases with the passage of time and the obtained film characteristics deteriorate.
　酸化物焼結体の相対密度の測定方法は、まず、各組成に対して、各構成元素と形態から酸化物焼結体の相対密度が１００％となる密度の値が決定でき、次に、実際に作製した酸化物焼結体の密度をアルキメデス法等で求めて、相対密度が１００％の密度の値で除したものとして求めることができる。
酸化物焼結体に含まれるＩｎ２Ｏ３の粒径の測定は、ＳＥＭの反射電子像等により、Ｉｎ２Ｏ３を含む組織写真から、画像解析により各Ｉｎ２Ｏ３相の最大となる径を測定し、１視野中の最大径を求めた。これをランダムに５視野測定し、その中で最大となる値を最大経とした。 The measurement method of the relative density of the oxide sintered body can first determine the value of the density at which the relative density of the oxide sintered body is 100% from each constituent element and form for each composition. The density of the actually produced oxide sintered body can be obtained by the Archimedes method or the like, and the relative density can be obtained by dividing by the density value of 100%.
The measurement of the particle size of In 2 O 3 contained in the oxide sintered body becomes the maximum of each In 2 O 3 phase by image analysis from a structural photograph containing In 2 O 3 by a reflected electron image of SEM or the like. The diameter was measured and the maximum diameter in one field of view was determined. Five fields of view were measured at random, and the maximum value among them was taken as the maximum length.
本発明のターゲットの低バルク抵抗化で成膜時のスパッタ電圧を下げることが出来る。スパッタ電圧が高い場合、スパッタにより生成した２次イオンや高エネルギー散乱粒子によって成膜した膜が衝撃されてダメージを受け，多くの酸素欠損を生じる。
酸化物半導体のスパッタ成膜においては、酸素欠損量を低減し所定のキャリア濃度を得るために成膜雰囲気中に多量の酸素を供給する必要があるが、ターゲットの低バルク抵抗化によってスパッタ電圧を低下させることによって膜中の酸素欠損量が減り、所定のキャリア濃度を得るために必要なスパッタ中の酸素分圧を低減出来る。 The sputtering voltage during film formation can be lowered by reducing the bulk resistance of the target of the present invention. When the sputtering voltage is high, the film formed by the secondary ions and high energy scattering particles generated by sputtering is impacted and damaged, resulting in many oxygen vacancies.
In sputter deposition of an oxide semiconductor, it is necessary to supply a large amount of oxygen in the deposition atmosphere in order to reduce the amount of oxygen vacancies and obtain a predetermined carrier concentration. By reducing the amount, the amount of oxygen vacancies in the film is reduced, and the partial pressure of oxygen during sputtering necessary for obtaining a predetermined carrier concentration can be reduced.
Ｉｎ２Ｏ３相のサイズは、成分組成及び焼結温度で制御可能である。すなわち、Ｉｎ濃度が高いほどＩｎ２Ｏ３相は大きく成長し易く、高温で焼結するとサイズも大きくなるので、これによって、Ｉｎ２Ｏ３相の大きさを制御できる。焼結温度は１４２０度以上１４８０度以下とすることが好ましい。焼結温度を上げ過ぎると、Ｉｎ２Ｏ３相の粗大化が起り、アーキング数が増大するので好ましくない。 The size of the In 2 O 3 phase can be controlled by the component composition and the sintering temperature. That is, the higher the In concentration, the larger the In 2 O 3 phase grows, and the larger the size when sintered at a high temperature. Thus, the size of the In 2 O 3 phase can be controlled. The sintering temperature is preferably 1420 ° C. or higher and 1480 ° C. or lower. If the sintering temperature is raised too much, the In 2 O 3 phase becomes coarse and the number of arcing increases, which is not preferable.
（酸化物焼結体の製造方法）
　上記の本発明に係る酸化物焼結体の製造工程の代表例を示すと、次の通りである。
　原料としては、酸化インジウム（Ｉｎ２Ｏ３）、酸化ガリウム（Ｇａ２Ｏ３）、及び酸化亜鉛（ＺｎＯ）を使用することができる。不純物による電気特性への悪影響を避けるために、純度４Ｎ以上の原料を用いることが望ましい。各々の原料粉を所望の組成比となるように秤量する。なお、上記の通り、これらに不可避的に含有される不純物は含まれるものである。 (Method for manufacturing oxide sintered body)
A representative example of the production process of the oxide sintered body according to the present invention is as follows.
As a raw material, indium oxide (In 2 O 3 ), gallium oxide (Ga 2 O 3 ), and zinc oxide (ZnO) can be used. In order to avoid an adverse effect on electrical characteristics due to impurities, it is desirable to use a raw material having a purity of 4N or higher. Each raw material powder is weighed so as to have a desired composition ratio. As described above, impurities inevitably contained in these are included.
　次に、混合と粉砕を行う。粉砕が不充分であると、製造したターゲット中に各成分が偏析して、高抵抗率領域と低抵抗率領域が存在することになり、スパッタ成膜時に高抵抗率領域での帯電等によるアーキングなどの異常放電の原因となってしまうので、充分な混合と粉砕が必要である。
ターゲットの作製は必要に応じて原料の仮焼を行う。スーパーミキサーにて各原料を混合した後、必要に応じて、これらをアルミナ製匣鉢に詰め、温度９５０～１３５０°Ｃの範囲で仮焼する。仮焼の保持時間は、２～１０ｈｒ、酸素雰囲気または大気雰囲気で行う。 Next, mixing and grinding are performed. If the pulverization is insufficient, each component will segregate in the manufactured target and there will be a high resistivity region and a low resistivity region, and arcing due to charging etc. in the high resistivity region during sputter deposition. Therefore, sufficient mixing and pulverization are necessary.
The target is prepared by calcining the raw material as necessary. After mixing each raw material with a super mixer, if necessary, they are packed in an alumina sagger and calcined at a temperature in the range of 950 to 1350 ° C. The holding time for the calcination is 2 to 10 hours in an oxygen atmosphere or an air atmosphere.
混合原料は、少量の場合は、例えば１バッチ１～20ｋｇ単位でアトライター(φ３ｍｍジルコニアビーズ、アジテータ回転数３００ｒｐｍ)又はＬＭＺ（スターミル：アシザワファインテック製）にて２～５ｈｒ程度、微粉砕する。
大量の場合は、原料を１バッチ２０～１０００ｋｇ単位で、ＬＭＺ（スターミル：アシザワファインテック製）にて２～8ｈｒ程度微粉砕（φ０．５ｍｍジルコニアビーズ、投入電力２．０～２０．０ｋＷ・Ｈｒ）する。
　次に、微粉砕後のスラリーはバインダーを加え造粒機で、１００～２５０°Ｃで乾燥して、目開き２５０μｍ篩で篩別して粉を回収する。なお、微粉砕の前後で、それぞれの粉末の比表面積を測定する。１０００ｇのＩＧＺＯ粉にＰＶＡ水溶液(ＰＶＡ固形分６％)を５０～２００ｃｃ混合する。 In the case of a small amount, the mixed raw material is finely pulverized in units of 1 to 20 kg per batch, for example, with an attritor (φ3 mm zirconia beads, agitator rotation speed 300 rpm) or LMZ (Star Mill: manufactured by Ashizawa Finetech) for about 2 to 5 hours.
In the case of a large amount, the raw material is batched in units of 20 to 1000 kg and finely pulverized by LMZ (Star Mill: manufactured by Ashizawa Finetech) for about 2 to 8 hours (φ0.5 mm zirconia beads, input power 2.0 to 20.0 kW · Hr )
Next, the finely pulverized slurry is added with a binder, dried with a granulator at 100 to 250 ° C., and sieved with a sieve having an opening of 250 μm to collect powder. The specific surface area of each powder is measured before and after pulverization. 50 to 200 cc of an aqueous PVA solution (6% PVA solid content) is mixed with 1000 g of IGZO powder.
次に、φ２１０ｍｍの金型に、粉末１０００ｇを充填し、面圧４００～１０００ｋｇｆ・ｃｍ２でプレスして成型体を得る。この成型体をビニールで２重に真空パックし、１５００～４０００ｋｇｆ/ｃｍ２でＣＩＰする。そして、所定の温度で焼結を行ない(保持時間５～２４ｈｒ、酸素雰囲気中)、焼結体を得る。
　ターゲットの製作に際しては、上記によって得られた酸化物焼結体の外周の円筒研削、面側の平面研削をすることによって、例えば１５２．４φ×５ｔｍｍのターゲットに加工する。これをさらに、例えば銅製のバッキングプレートに、インジウム系合金などをボンディングメタルとして、貼り合わせることでスパッタリングターゲットとする。 Next, a mold of φ210 mm is filled with 1000 g of powder and pressed at a surface pressure of 400 to 1000 kgf · cm 2 to obtain a molded body. This molded body is double vacuum packed with vinyl and CIPed at 1500 to 4000 kgf / cm 2 . Then, sintering is performed at a predetermined temperature (retention time 5 to 24 hours, in an oxygen atmosphere) to obtain a sintered body.
When the target is manufactured, the oxide sintered body obtained as described above is processed into a target of, for example, 152.4φ × 5 tmm by performing cylindrical grinding on the outer periphery and surface grinding on the surface side. Further, for example, an indium alloy or the like is bonded to a copper backing plate as a bonding metal to obtain a sputtering target.
　以下、実施例および比較例に基づいて説明する。なお、本実施例はあくまで一例であり、この例によって何ら制限されるものではない。すなわち、本発明は特許請求の範囲によってのみ制限されるものであり、本発明に含まれる実施例以外の種々の変形を包含するものである。 Hereinafter, description will be made based on examples and comparative examples. In addition, a present Example is an example to the last, and is not restrict | limited at all by this example. In other words, the present invention is limited only by the scope of the claims, and includes various modifications other than the examples included in the present invention.
実施例に使用した原料粉は、表１に示す通りである。ＩＧＺＯの原料について、酸素を除くＩｎ、Ｇａ、Ｚｎをメタル比で、Ｉｎ／（Ｉｎ＋Ｇａ）≦０．５７５とし、Ｚｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）＜０．３３３、残部をＧａの組成となるよう原料を調合し、これらの原料組合せと製造条件(微粉砕、仮焼温度、焼結温度)を変えて、ターゲットを作製し、各種の試験を行った。これらの詳細を、表１の実施例１～７に示す。 The raw material powder used in the examples is as shown in Table 1. For IGZO raw materials, prepare In, Ga, Zn excluding oxygen in the metal ratio, In / (In + Ga) ≦ 0.575, Zn / (In + Ga + Zn) <0.333, and balance with Ga composition. Then, these raw material combinations and production conditions (fine pulverization, calcination temperature, sintering temperature) were changed to produce targets, and various tests were performed. Details thereof are shown in Examples 1 to 7 in Table 1.
下記に示す実施例及び比較例において、各種の分析測定や評価が必要となるが、その条件・装置名等を以下に示す。
（原料の平均粒径の測定）
粒径の測定は、粒度分布測定装置(日機装株式会社製、Microtrac MT3000)を用いて行った。
(密度の測定)
密度の測定は純水を溶媒として用いたアルキメデス法にて測定を行った。相対密度の算出に用いた理論密度は、各原料の密度(Ｉｎ２Ｏ３：７．１８ｇ／ｃｍ３、Ｇａ２Ｏ３：６．４４ｇ／ｃｍ３、ＺｎＯ：５．６１ｇ／ｃｍ３)を組成に応じた重量比より体積換算して算出した。 In the examples and comparative examples shown below, various analytical measurements and evaluations are required, and the conditions, device names, etc. are shown below.
(Measurement of average particle size of raw material)
The particle size was measured using a particle size distribution measurement device (Microtrac MT3000, manufactured by Nikkiso Co., Ltd.).
(Density measurement)
The density was measured by the Archimedes method using pure water as a solvent. The theoretical density used to calculate the relative density is the density of each raw material (In 2 O 3 : 7.18 g / cm 3 , Ga 2 O 3 : 6.44 g / cm 3 , ZnO: 5.61 g / cm 3 ). The volume was calculated from the weight ratio corresponding to the composition.
(バルク抵抗値の測定)
バルク抵抗値の測定は、抵抗率測定器(エヌピイエス株式会社製、Σ－５＋)を用いて、四探針法で行った。 (Measurement of bulk resistance)
The bulk resistance value was measured by a four-probe method using a resistivity measuring instrument (Σ-5 +, manufactured by NP Corporation).
（スパッタリング条件）
　スパッタリング装置は、ＤＣマグネトロンスパッタ装置を使用し、成膜条件は、室温、ＤＣ５００Ｗ、酸素濃度６％、アニール条件は大気雰囲気で３００℃×１ｈｒで行った。 (Sputtering conditions)
As the sputtering apparatus, a DC magnetron sputtering apparatus was used. The film formation conditions were room temperature, DC 500 W, oxygen concentration 6%, and the annealing conditions were 300 ° C. × 1 hr in an air atmosphere.
　膜のキャリア濃度、移動度の測定は、東陽テクニカ製（ResiTest8400 ホール効果測定装置）を使用して行った。キャリア濃度５×１０１５(ｃｍ－３)以下、移動度５(ｃｍ２／Ｖｓ)以上を目標とした。 The carrier concentration and mobility of the film were measured using a Toyo Technica (ResiTest8400 Hall effect measuring device). The target was a carrier concentration of 5 × 10 15 (cm −3 ) or less and a mobility of 5 (cm 2 / Vs) or more.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（実施例１）
Ｉｎ２Ｏ３原料として、粒径１．３μｍ、比表面積(ＢＥＴ)４．４ｍ２／ｇのＩｎ２Ｏ３粉末を用い、Ｇａ２Ｏ３原料として、粒径５．６μｍ、比表面積９．１ｍ２／ｇのＧａ２Ｏ３粉末を用い、ＺｎＯ原料として、粒径１．１μｍ、比表面積３．８ｍ２／ｇのＺｎＯ粉末を用いた。これらの粉末を、Ｉｎ２Ｏ３原料を４６．６ｗｔ％、Ｇａ２Ｏ３原料を２８．６ｗｔ％、ＺｎＯ原料を２４．８ｗｔ％とし、合計が１００ｗｔ％となるように調整することで、
Ｉｎ、Ｇａ、Ｚｎをメタル比で、Ｉｎ／（Ｉｎ＋Ｇａ）で０．５２４とし、Ｚｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）を０．３２３、残部をＧａの組成となる。 (Example 1)
In 2 O 3 as raw materials, using In 2 O 3 powder having a particle size of 1.3 .mu.m, specific surface area (BET) 4.4m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area 9. A 1 m 2 / g Ga 2 O 3 powder was used, and a ZnO powder having a particle size of 1.1 μm and a specific surface area of 3.8 m 2 / g was used as a ZnO raw material. By adjusting these powders so that the In 2 O 3 raw material is 46.6 wt%, the Ga 2 O 3 raw material is 28.6 wt%, the ZnO raw material is 24.8 wt%, and the total is 100 wt%,
The metal ratio of In, Ga, and Zn is 0.524 in In / (In + Ga), Zn / (In + Ga + Zn) is 0.323, and the balance is Ga.
　次に、これらの粉末を混合した（仮焼せず）。粉砕前の比表面積は６．０ｍ２／ｇであった。また、粉砕後の比表面積は１７．８ｍ２／ｇであった。この差は、１１．８ｍ２／ｇであった。粉末の焼結温度を１４３０℃、焼結雰囲気：酸素雰囲気で焼結した。 Next, these powders were mixed (not calcined). The specific surface area before pulverization was 6.0 m 2 / g. The specific surface area after pulverization was 17.8 m 2 / g. This difference was 11.8 m 2 / g. The sintering temperature of the powder was 1430 ° C., and the sintering atmosphere was sintered in an oxygen atmosphere.
この結果、密度は６．３２ｇ／ｃｍ３、相対密度は９６．８％と高密度であり、バルク抵抗値は３．８ｍΩ・ｃｍで、ＤＣスパッタリングが十分可能である低バルク抵抗値を有していた。Ｉｎ２Ｏ３相の最大サイズ(長径)が４．９μｍ、相状態はＩｎｘＧａ（１－ｘ）)２ ＺｎＯ４相とＩｎ２Ｏ３相の２相であった。
そして、キャリア濃度が２．２１×１０１５(ｃｍ－３)、移動度９．１４(ｃｍ２／Ｖｓ)であった。また、スパッタリング中のアーキングの発生は１２１回と少なかった。いずれも、本願発明の条件を満たしていた。 As a result, the density is 6.32 g / cm 3 , the relative density is 96.8%, the bulk resistance value is 3.8 mΩ · cm, and it has a low bulk resistance value that allows DC sputtering sufficiently. It was. The maximum size (major axis) of the In 2 O 3 phase was 4.9 μm, and the phase state was two phases of In x Ga (1-x ) 2 ZnO 4 phase and In 2 O 3 phase.
The carrier concentration was 2.21 × 10 15 (cm −3 ) and the mobility was 9.14 (cm 2 / Vs). Moreover, the occurrence of arcing during sputtering was as small as 121 times. All satisfied the conditions of the present invention.
（実施例２）
Ｉｎ２Ｏ３原料として、粒径1.3μｍ、比表面積４．４ｍ２／ｇのＩｎ２Ｏ３粉末を用い、Ｇａ２Ｏ３原料として、粒径５．６μｍ、比表面積９．１ｍ２／ｇのＧａ２Ｏ３粉末を用い、ＺｎＯ原料として、粒径１．１μｍ、比表面積３．８ｍ２／ｇのＺｎＯ粉末を用いた。
これらの粉末を、Ｉｎ２Ｏ３原料を４４．７ｗｔ％、Ｇａ２Ｏ３原料を２９．６ｗｔ％、ＺｎＯ原料を２５．７ｗｔ％とし、合計が１００ｗｔ％となるように調整することで、
Ｉｎ、Ｇａ、Ｚｎをメタル比で、Ｉｎ／（Ｉｎ＋Ｇａ）で０．５０５とし、Ｚｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）を０．３３１、残部をＧａの組成となる。 (Example 2)
In 2 O 3 powder, particle size 1.3 .mu.m, using In 2 O 3 powder having a specific surface area of 4.4 m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area of 9.1 m 2 / g using Ga 2 O 3 powder, ZnO as a raw material, with particle size 1.1 .mu.m, ZnO powder having a specific surface area of 3.8 m 2 / g.
By adjusting these powders so that the In 2 O 3 raw material is 44.7 wt%, the Ga 2 O 3 raw material is 29.6 wt%, the ZnO raw material is 25.7 wt%, and the total is 100 wt%,
In, Ga, and Zn have a metal ratio of In / (In + Ga) of 0.505, Zn / (In + Ga + Zn) of 0.331, and the balance of Ga.
　次に、これらの粉末を混合した（仮焼せず）。粉砕前の比表面積は６．０ｍ２／ｇであった。また、粉砕後の比表面積は１８．０ｍ２／ｇであった。この差は、１２．０ｍ２／ｇであった。粉末の焼結温度を１４３０℃、焼結雰囲気：酸素雰囲気で焼結した。 Next, these powders were mixed (not calcined). The specific surface area before pulverization was 6.0 m 2 / g. The specific surface area after pulverization was 18.0 m 2 / g. This difference was 12.0 m 2 / g. The sintering temperature of the powder was 1430 ° C., and the sintering atmosphere was sintered in an oxygen atmosphere.
この結果、密度は６．３３ｇ／ｃｍ３、相対密度は９７．３％と高密度であり、バルク抵抗値は５．８ｍΩ・ｃｍで、ＤＣスパッタリングが十分可能である低バルク抵抗値を有していた。相状態はＩｎｘＧａ（１－ｘ）)２ ＺｎＯ４相の単相であった。
そして、キャリア濃度が１．３４×１０１５(ｃｍ－３)、移動度６．４６(ｃｍ２／Ｖｓ)であった。また、スパッタリング中のアーキングの発生は８６回と少なかった。いずれも、本願発明の条件を満たしていた。 As a result, the density is 6.33 g / cm 3 , the relative density is high as 97.3%, the bulk resistance value is 5.8 mΩ · cm, and it has a low bulk resistance value that allows DC sputtering sufficiently. It was. The phase state was a single phase of In x Ga (1-x) ) 2 ZnO 4 phase.
The carrier concentration was 1.34 × 10 15 (cm −3 ) and the mobility was 6.46 (cm 2 / Vs). Moreover, the occurrence of arcing during sputtering was as small as 86 times. All satisfied the conditions of the present invention.
（実施例３）
Ｉｎ２Ｏ３原料として、粒径１．３μｍ、比表面積４．４ｍ２／ｇのＩｎ２Ｏ３粉末を用い、Ｇａ２Ｏ３原料として、粒径５．６μｍ、比表面積９．１ｍ２／ｇのＧａ２Ｏ３粉末を用い、ＺｎＯ原料として、粒径１．１μｍ、比表面積３．８ｍ２／ｇのＺｎＯ粉末を用いた。
これらの粉末を、Ｉｎ２Ｏ３原料を４５．４ｗｔ％、Ｇａ２Ｏ３原料を２９．２ｗｔ％、ＺｎＯ原料を２５．４ｗｔ％とし、合計が１００ｗｔ％となるように調整することで、酸素を除くＩｎ、Ｇａ、Ｚｎをメタル比で、Ｉｎ／（Ｉｎ＋Ｇａ）で０．５１２とし、Ｚｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）を０．３２８、残部をＧａの組成となる。 (Example 3)
In 2 O 3 powder, particle size 1.3 .mu.m, using In 2 O 3 powder having a specific surface area of 4.4 m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area of 9.1 m 2 / g of Ga 2 O 3 powder was used, and ZnO powder having a particle size of 1.1 μm and a specific surface area of 3.8 m 2 / g was used as a ZnO raw material.
These powders were adjusted so that the In 2 O 3 raw material was 45.4 wt%, the Ga 2 O 3 raw material was 29.2 wt%, the ZnO raw material was 25.4 wt%, and the total was 100 wt%. In, Ga, and Zn, excluding, are 0.512 in terms of metal ratio, In / (In + Ga), Zn / (In + Ga + Zn) is 0.328, and the balance is Ga.
　次に、これらの粉末を混合した（仮焼せず）。粉砕前の比表面積は５．８ｍ２／ｇであった。また、粉砕後の比表面積は１６．８ｍ２／ｇであった。この差は、１１．０ｍ２／ｇであった。粉末の焼結温度を１４３０℃、焼結雰囲気：酸素雰囲気で焼結した。 Next, these powders were mixed (not calcined). The specific surface area before pulverization was 5.8 m 2 / g. The specific surface area after pulverization was 16.8 m 2 / g. This difference was 11.0 m 2 / g. The sintering temperature of the powder was 1430 ° C., and the sintering atmosphere was sintered in an oxygen atmosphere.
この結果、密度は６．３３ｇ／ｃｍ３、相対密度は９７．１％と高密度であり、バルク抵抗値は４．３ｍΩ・ｃｍで、ＤＣスパッタリングが十分可能である低バルク抵抗値を有していた。Ｉｎ２Ｏ３相の最大サイズ(長径)が５．２μｍ、相状態はＩｎｘＧａ（１－ｘ）)２ ＺｎＯ４相とＩｎ２Ｏ３相の２相であった。
そして、キャリア濃度が１．５６×１０１５(ｃｍ－３)、移動度７．２３(ｃｍ２／Ｖｓ)であった。また、スパッタリング中のアーキングの発生は１３０回と少なかった。いずれも、本願発明の条件を満たしていた。 As a result, the density is 6.33 g / cm 3 , the relative density is 97.1%, the bulk resistance value is 4.3 mΩ · cm, and it has a low bulk resistance value that enables DC sputtering sufficiently. It was. The maximum size (major axis) of the In 2 O 3 phase was 5.2 μm, and the phase state was two phases of In x Ga (1-x ) 2 ZnO 4 phase and In 2 O 3 phase.
The carrier concentration was 1.56 × 10 15 (cm −3 ) and the mobility was 7.23 (cm 2 / Vs). Moreover, the occurrence of arcing during sputtering was as small as 130 times. All satisfied the conditions of the present invention.
（実施例４）
Ｉｎ２Ｏ３原料として、粒径1.3μｍ、比表面積４．４ｍ２／ｇのＩｎ２Ｏ３粉末を用い、Ｇａ２Ｏ３原料として、粒径５．６μｍ、比表面積９．１ｍ２／ｇのＧａ２Ｏ３粉末を用い、ＺｎＯ原料として、粒径１．１μｍ、比表面積３．８ｍ２／ｇのＺｎＯ粉末を用いた。
これらの粉末を、Ｉｎ２Ｏ３原料を４６．６ｗｔ％、Ｇａ２Ｏ３原料を２８．６ｗｔ％、ＺｎＯ原料を２４．８ｗｔ％とし、合計が１００ｗｔ％となるように調整することで、
Ｉｎ、Ｇａ、Ｚｎをメタル比で、Ｉｎ／（Ｉｎ＋Ｇａ）で０．５２４とし、Ｚｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）を０．３２３、残部をＧａの組成となる。 Example 4
In 2 O 3 powder, particle size 1.3 .mu.m, using In 2 O 3 powder having a specific surface area of 4.4 m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area of 9.1 m 2 / g using Ga 2 O 3 powder, ZnO as a raw material, with particle size 1.1 .mu.m, ZnO powder having a specific surface area of 3.8 m 2 / g.
By adjusting these powders so that the In 2 O 3 raw material is 46.6 wt%, the Ga 2 O 3 raw material is 28.6 wt%, the ZnO raw material is 24.8 wt%, and the total is 100 wt%,
The metal ratio of In, Ga, and Zn is 0.524 in In / (In + Ga), Zn / (In + Ga + Zn) is 0.323, and the balance is Ga.
　次に、これらの粉末を混合した（仮焼せず）。粉砕前の比表面積は５．９ｍ２／ｇであった。また、粉砕後の比表面積は１７．５ｍ２／ｇであった。この差は、１１．６ｍ２／ｇであった。粉末の焼結温度を１４３０℃、焼結雰囲気：大気中で焼結した。 Next, these powders were mixed (not calcined). The specific surface area before pulverization was 5.9 m 2 / g. The specific surface area after pulverization was 17.5 m 2 / g. This difference was 11.6 m 2 / g. The sintering temperature of the powder was 1430 ° C., sintering atmosphere: sintered in the air.
この結果、密度は６．３２ｇ／ｃｍ３、相対密度は９６．８％と高密度であり、バルク抵抗値は２．９ｍΩ・ｃｍで、ＤＣスパッタリングが十分可能である低バルク抵抗値を有していた。Ｉｎ２Ｏ３相の最大サイズ(長径)が４．３μｍ、相状態はＩｎｘＧａ（１－ｘ）)２ ＺｎＯ４相とＩｎ２Ｏ３相の２相であった。
そして、キャリア濃度が１．７２×１０１５(ｃｍ－３)、移動度８．６２(ｃｍ２／Ｖｓ)であった。また、スパッタリング中のアーキングの発生は１２８回と少なかった。いずれも、本願発明の条件を満たしていた。 As a result, the density is 6.32 g / cm 3 , the relative density is as high as 96.8%, the bulk resistance value is 2.9 mΩ · cm, and it has a low bulk resistance value that allows DC sputtering sufficiently. It was. The maximum size (major axis) of the In 2 O 3 phase was 4.3 μm, and the phase state was two phases of In x Ga (1-x ) 2 ZnO 4 phase and In 2 O 3 phase.
The carrier concentration was 1.72 × 10 15 (cm −3 ) and the mobility was 8.62 (cm 2 / Vs). Moreover, the occurrence of arcing during sputtering was as small as 128 times. All satisfied the conditions of the present invention.
（実施例５）
Ｉｎ２Ｏ３原料として、粒径１．３μｍ、比表面積４．４ｍ２／ｇのＩｎ２Ｏ３粉末を用い、Ｇａ２Ｏ３原料として、粒径５．６μｍ、比表面積９．１ｍ２／ｇのＧａ２Ｏ３粉末を用い、ＺｎＯ原料として、粒径１．１μｍ、比表面積３．８ｍ２／ｇのＺｎＯ粉末を用いた。
これらの粉末を、Ｉｎ２Ｏ３原料を４６．６ｗｔ％、Ｇａ２Ｏ３原料を２８．６ｗｔ％、ＺｎＯ原料を２４．８ｗｔ％とし、合計が１００ｗｔ％となるように調整することで、
Ｉｎ、Ｇａ、Ｚｎをメタル比で、Ｉｎ／（Ｉｎ＋Ｇａ）で０．５２４とし、Ｚｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）を０．３２３、残部をＧａの組成となる。 (Example 5)
In 2 O 3 powder, particle size 1.3 .mu.m, using In 2 O 3 powder having a specific surface area of 4.4 m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area of 9.1 m 2 / g of Ga 2 O 3 powder was used, and ZnO powder having a particle size of 1.1 μm and a specific surface area of 3.8 m 2 / g was used as a ZnO raw material.
By adjusting these powders so that the In 2 O 3 raw material is 46.6 wt%, the Ga 2 O 3 raw material is 28.6 wt%, the ZnO raw material is 24.8 wt%, and the total is 100 wt%,
The metal ratio of In, Ga, and Zn is 0.524 in In / (In + Ga), Zn / (In + Ga + Zn) is 0.323, and the balance is Ga.
　次に、これらの粉末を混合した（仮焼せず）。粉砕前の比表面積は５．９ｍ２／ｇであった。また、粉砕後の比表面積は１７．５ｍ２／ｇであった。この差は、１１．６ｍ２／ｇであった。粉末の焼結温度を１３７０℃、焼結雰囲気：酸素雰囲気で焼結した。 Next, these powders were mixed (not calcined). The specific surface area before pulverization was 5.9 m 2 / g. The specific surface area after pulverization was 17.5 m 2 / g. This difference was 11.6 m 2 / g. The sintering temperature of the powder was 1370 ° C., and the sintering atmosphere was sintered in an oxygen atmosphere.
この結果、密度は６．３２ｇ／ｃｍ３、相対密度は９６．８％と高密度であり、バルク抵抗値は８．０ｍΩ・ｃｍで、ＤＣスパッタリングが十分可能である低バルク抵抗値を有していた。Ｉｎ２Ｏ３相の最大サイズ(長径)が３．５μｍ、相状態はＩｎｘＧａ（１－ｘ）)２ ＺｎＯ４相とＩｎ２Ｏ３相の２相であった。 As a result, the density is 6.32 g / cm 3 , the relative density is 96.8%, the bulk resistance value is 8.0 mΩ · cm, and it has a low bulk resistance value that allows DC sputtering sufficiently. It was. The maximum size (major axis) of the In 2 O 3 phase was 3.5 μm, and the phase state was two phases of In x Ga (1-x ) 2 ZnO 4 phase and In 2 O 3 phase.
そして、キャリア濃度が２．６１×１０１５(ｃｍ－３)、移動度８．８９(ｃｍ２／Ｖｓ)であった。また、スパッタリング中のアーキングの発生は１４２回と少なかった。いずれも、本願発明の条件を満たしていた。 The carrier concentration was 2.61 × 10 15 (cm −3 ) and the mobility was 8.89 (cm 2 / Vs). Moreover, the occurrence of arcing during sputtering was as small as 142 times. All satisfied the conditions of the present invention.
（実施例６）
Ｉｎ２Ｏ３原料として、粒径１．３μｍ、比表面積４．４ｍ２／ｇのＩｎ２Ｏ３粉末を用い、Ｇａ２Ｏ３原料として、粒径５．６μｍ、比表面積９．１ｍ２／ｇのＧａ２Ｏ３粉末を用い、ＺｎＯ原料として、粒径１．１μｍ、比表面積３．８ｍ２／ｇのＺｎＯ粉末を用いた。
これらの粉末を、Ｉｎ２Ｏ３原料を４９．９ｗｔ％、Ｇａ２Ｏ３原料を２４．９ｗｔ％、ＺｎＯ原料を２５．３ｗｔ％とし、合計が１００ｗｔ％となるように調整することで、
Ｉｎ、Ｇａ、Ｚｎをメタル比で、Ｉｎ／（Ｉｎ＋Ｇａ）で０．５７５とし、Ｚｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）を０．３３２、残部をＧａの組成となる。 (Example 6)
In 2 O 3 powder, particle size 1.3 .mu.m, using In 2 O 3 powder having a specific surface area of 4.4 m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area of 9.1 m 2 / g of Ga 2 O 3 powder was used, and ZnO powder having a particle size of 1.1 μm and a specific surface area of 3.8 m 2 / g was used as a ZnO raw material.
By adjusting these powders so that the In 2 O 3 raw material is 49.9 wt%, the Ga 2 O 3 raw material is 24.9 wt%, the ZnO raw material is 25.3 wt%, and the total is 100 wt%,
The metal ratio of In, Ga, and Zn is 0.575 in In / (In + Ga), Zn / (In + Ga + Zn) is 0.332, and the balance is Ga.
　次に、これらの粉末を混合した（仮焼せず）。粉砕前の比表面積は５．６ｍ２／ｇであった。また、粉砕後の比表面積は１７．８ｍ２／ｇであった。この差は、１２．２ｍ２／ｇであった。粉末の焼結温度を１４３０℃、焼結雰囲気：酸素雰囲気で焼結した。 Next, these powders were mixed (not calcined). The specific surface area before pulverization was 5.6 m 2 / g. The specific surface area after pulverization was 17.8 m 2 / g. This difference was 12.2 m 2 / g. The sintering temperature of the powder was 1430 ° C., and the sintering atmosphere was sintered in an oxygen atmosphere.
この結果、密度は６．３８ｇ／ｃｍ３、相対密度は９７．５％と高密度であり、バルク抵抗値は９．８ｍΩ・ｃｍで、ＤＣスパッタリングが十分可能である低バルク抵抗値を有していた。相状態はＩｎｘＧａ（１－ｘ）)２ ＺｎＯ４相の単相であった。
そして、キャリア濃度が３．５３×１０１５(ｃｍ－３)、移動度９．５３(ｃｍ２／Ｖｓ)であった。また、スパッタリング中のアーキングの発生は１３４回と少なかった。いずれも、本願発明の条件を満たしていた。 As a result, the density is 6.38 g / cm 3 , the relative density is as high as 97.5%, the bulk resistance value is 9.8 mΩ · cm, and it has a low bulk resistance value that allows DC sputtering sufficiently. It was. The phase state was a single phase of In x Ga (1-x) ) 2 ZnO 4 phase.
The carrier concentration was 3.53 × 10 15 (cm −3 ) and the mobility was 9.53 (cm 2 / Vs). Moreover, the occurrence of arcing during sputtering was as small as 134 times. All satisfied the conditions of the present invention.
（実施例７）
Ｉｎ２Ｏ３原料として、粒径１．３μｍ、比表面積４．４ｍ２／ｇのＩｎ２Ｏ３粉末を用い、Ｇａ２Ｏ３原料として、粒径５．６μｍ、比表面積９．１ｍ２／ｇのＧａ２Ｏ３粉末を用い、ＺｎＯ原料として、粒径１．１μｍ、比表面積３．８ｍ２／ｇのＺｎＯ粉末を用いた。
これらの粉末を、Ｉｎ２Ｏ３原料を５２．４ｗｔ％、Ｇａ２Ｏ３原料を２６．２ｗｔ％、ＺｎＯ原料を２１．４ｗｔ％とし、合計が１００ｗｔ％となるように調整することで、
Ｉｎ、Ｇａ、Ｚｎをメタル比で、Ｉｎ／（Ｉｎ＋Ｇａ）で０．５７５とし、Ｚｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）を０．２８６、残部をＧａの組成となる。 (Example 7)
In 2 O 3 powder, particle size 1.3 .mu.m, using In 2 O 3 powder having a specific surface area of 4.4 m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area of 9.1 m 2 / g of Ga 2 O 3 powder was used, and ZnO powder having a particle size of 1.1 μm and a specific surface area of 3.8 m 2 / g was used as a ZnO raw material.
By adjusting these powders so that the In 2 O 3 raw material is 52.4 wt%, the Ga 2 O 3 raw material is 26.2 wt%, the ZnO raw material is 21.4 wt%, and the total is 100 wt%,
In, Ga, and Zn are metal ratios, and In / (In + Ga) is 0.575, Zn / (In + Ga + Zn) is 0.286, and the balance is Ga.
　次に、これらの粉末を混合した（仮焼せず）。粉砕前の比表面積は６．２ｍ２／ｇであった。また、粉砕後の比表面積は１５．５ｍ２／ｇであった。この差は、９．３ｍ２／ｇであった。粉末の焼結温度を１４３０℃、焼結雰囲気：酸素雰囲気で焼結した。 Next, these powders were mixed (not calcined). The specific surface area before pulverization was 6.2 m 2 / g. The specific surface area after pulverization was 15.5 m 2 / g. This difference was 9.3 m 2 / g. The sintering temperature of the powder was 1430 ° C., and the sintering atmosphere was sintered in an oxygen atmosphere.
この結果、密度は６．４２ｇ／ｃｍ３、相対密度は９７．２％と高密度であり、バルク抵抗値は２．１ｍΩ・ｃｍで、ＤＣスパッタリングが十分可能である低バルク抵抗値を有していた。Ｉｎ２Ｏ３相の最大サイズ(長径)が８．８μｍ、相状態はＩｎｘＧａ（１－ｘ）)２ ＺｎＯ４相とＩｎ２Ｏ３相の２相であった。
そして、キャリア濃度が４．５５×１０１５(ｃｍ－３)、移動度７．３４(ｃｍ２／Ｖｓ)であった。また、スパッタリング中のアーキングの発生は１７３回と少なかった。いずれも、本願発明の条件を満たしていた。 As a result, the density is 6.42 g / cm 3 , the relative density is 97.2%, the bulk resistance value is 2.1 mΩ · cm, and the low bulk resistance value that allows DC sputtering is sufficient. It was. The maximum size (major axis) of the In 2 O 3 phase was 8.8 μm, and the phase state was two phases of In x Ga (1-x ) 2 ZnO 4 phase and In 2 O 3 phase.
The carrier concentration was 4.55 × 10 15 (cm −3 ) and the mobility was 7.34 (cm 2 / Vs). Moreover, the occurrence of arcing during sputtering was as small as 173 times. All satisfied the conditions of the present invention.
（比較例１）
Ｉｎ２Ｏ３原料として、粒径１．３μｍ、比表面積４．４ｍ２／ｇのＩｎ２Ｏ３粉末を用い、Ｇａ２Ｏ３原料として、粒径５．６μｍ、比表面積９．１ｍ２／ｇのＧａ２Ｏ３粉末を用い、ＺｎＯ原料として、粒径１．１μｍ、比表面積３．８ｍ２／ｇのＺｎＯ粉末を用いた。
これらの粉末を、Ｉｎ２Ｏ３原料を４４．２ｗｔ％、Ｇａ２Ｏ３原料を２９．９ｗｔ％、ＺｎＯ原料を２５．９ｗｔ％とし、合計が１００ｗｔ％となるように調整することで、
Ｉｎ、Ｇａ、Ｚｎをメタル比で、Ｉｎ／（Ｉｎ＋Ｇａ）で０．５００とし、Ｚｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）を０．３３３、残部をＧａの組成となる。 (Comparative Example 1)
In 2 O 3 powder, particle size 1.3 .mu.m, using In 2 O 3 powder having a specific surface area of 4.4 m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area of 9.1 m 2 / g of Ga 2 O 3 powder was used, and ZnO powder having a particle size of 1.1 μm and a specific surface area of 3.8 m 2 / g was used as a ZnO raw material.
By adjusting these powders to 44.2 wt% In 2 O 3 raw material, 29.9 wt% Ga 2 O 3 raw material, and 25.9 wt% ZnO raw material, the total is 100 wt%.
The metal ratio of In, Ga, and Zn is 0.500 in In / (In + Ga), Zn / (In + Ga + Zn) is 0.333, and the balance is Ga.
　次に、これらの粉末を混合した（仮焼せず）。粉砕前の比表面積は５．６ｍ２／ｇであった。また、粉砕後の比表面積は１６．６ｍ２／ｇであった。この差は、１１．０ｍ２／ｇであった。粉末の焼結温度を１４３０℃、焼結雰囲気：酸素雰囲気で焼結した。 Next, these powders were mixed (not calcined). The specific surface area before pulverization was 5.6 m 2 / g. The specific surface area after pulverization was 16.6 m 2 / g. This difference was 11.0 m 2 / g. The sintering temperature of the powder was 1430 ° C., and the sintering atmosphere was sintered in an oxygen atmosphere.
この結果、密度は６．３３ｇ／ｃｍ３、相対密度は９７．３％と高密度であり、バルク抵抗値は３２ｍΩ・ｃｍと高く、ＤＣスパッタリングは十分でなかった。相状態はＩｎｘＧａ（１－ｘ）)２ ＺｎＯ４相の単相であった。
そして、キャリア濃度が５．８７×１０１５(ｃｍ－３)と高くなった。移動度８．９２(ｃｍ２／Ｖｓ)であった。また、スパッタリング中のアーキングの発生は９２回と少なかった。本願発明の条件を満たしていなかった。 As a result, the density was 6.33 g / cm 3 , the relative density was as high as 97.3%, the bulk resistance value was as high as 32 mΩ · cm, and DC sputtering was not sufficient. The phase state was a single phase of In x Ga (1-x) ) 2 ZnO 4 phase.
The carrier concentration increased to 5.87 × 10 15 (cm −3 ). The mobility was 8.92 (cm 2 / Vs). Moreover, the occurrence of arcing during sputtering was as small as 92 times. The conditions of the present invention were not satisfied.
（比較例２）
Ｉｎ２Ｏ３原料として、粒径１．３μｍ、比表面積４．４ｍ２／ｇのＩｎ２Ｏ３粉末を用い、Ｇａ２Ｏ３原料として、粒径５．６μｍ、比表面積９．１ｍ２／ｇのＧａ２Ｏ３粉末を用い、ＺｎＯ原料として、粒径１．１μｍ、比表面積３．８ｍ２／ｇのＺｎＯ粉末を用いた。
これらの粉末を、Ｉｎ２Ｏ３原料を４６．６ｗｔ％、Ｇａ２Ｏ３原料を２８．６ｗｔ％、ＺｎＯ原料を２４．８ｗｔ％とし、合計が１００ｗｔ％となるように調整することで、
Ｉｎ、Ｇａ、Ｚｎをメタル比で、Ｉｎ／（Ｉｎ＋Ｇａ）で０．５００とし、Ｚｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）を０．３３３、残部をＧａの組成となる。 (Comparative Example 2)
In 2 O 3 powder, particle size 1.3 .mu.m, using In 2 O 3 powder having a specific surface area of 4.4 m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area of 9.1 m 2 / g of Ga 2 O 3 powder was used, and ZnO powder having a particle size of 1.1 μm and a specific surface area of 3.8 m 2 / g was used as a ZnO raw material.
By adjusting these powders so that the In 2 O 3 raw material is 46.6 wt%, the Ga 2 O 3 raw material is 28.6 wt%, the ZnO raw material is 24.8 wt%, and the total is 100 wt%,
The metal ratio of In, Ga, and Zn is 0.500 in In / (In + Ga), Zn / (In + Ga + Zn) is 0.333, and the balance is Ga.
　次に、これらの粉末を混合した（仮焼せず）。粉砕前の比表面積は５．６ｍ２／ｇであった。また、粉砕後の比表面積は１６．６ｍ２／ｇであった。この差は、１１．０ｍ２／ｇであった。粉末の焼結温度を１３７０℃、焼結雰囲気：酸素雰囲気で焼結した。 Next, these powders were mixed (not calcined). The specific surface area before pulverization was 5.6 m 2 / g. The specific surface area after pulverization was 16.6 m 2 / g. This difference was 11.0 m 2 / g. The sintering temperature of the powder was 1370 ° C., and the sintering atmosphere was sintered in an oxygen atmosphere.
この結果、密度は６．３２ｇ／ｃｍ３、相対密度は９７．２％と高密度であり、バルク抵抗値は８０ｍΩ・ｃｍと高く、ＤＣスパッタリングは十分でなかった。相状態はＩｎｘＧａ（１－ｘ）)２ ＺｎＯ４相の単相であった。
そして、キャリア濃度が１０．８×１０１５(ｃｍ－３)と高くなった。移動度１０．５(ｃｍ２／Ｖｓ)であった。また、スパッタリング中のアーキングの発生は７６回と少なかった。本願発明の条件を満たしていなかった。 As a result, the density was 6.32 g / cm 3 , the relative density was 97.2%, the bulk resistance was as high as 80 mΩ · cm, and DC sputtering was not sufficient. The phase state was a single phase of In x Ga (1-x) ) 2 ZnO 4 phase.
The carrier concentration increased to 10.8 × 10 15 (cm −3 ). The mobility was 10.5 (cm 2 / Vs). Moreover, the occurrence of arcing during sputtering was as small as 76 times. The conditions of the present invention were not satisfied.
（比較例３）
Ｉｎ２Ｏ３原料として、粒径１．３μｍ、比表面積４．４ｍ２／ｇのＩｎ２Ｏ３粉末を用い、Ｇａ２Ｏ３原料として、粒径５．６μｍ、比表面積９．１ｍ２／ｇのＧａ２Ｏ３粉末を用い、ＺｎＯ原料として、粒径１．１μｍ、比表面積３．８ｍ２／ｇのＺｎＯ粉末を用いた。
これらの粉末を、Ｉｎ２Ｏ３原料を６１．７ｗｔ％、Ｇａ２Ｏ３原料を１６．７ｗｔ％、ＺｎＯ原料を２１．７ｗｔ％とし、合計が１００ｗｔ％となるように調整することで、
Ｉｎ、Ｇａ、Ｚｎをメタル比で、Ｉｎ／（Ｉｎ＋Ｇａ）で０．７１４とし、Ｚｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）を０．３３３、残部をＧａの組成となる。 (Comparative Example 3)
In 2 O 3 powder, particle size 1.3 .mu.m, using In 2 O 3 powder having a specific surface area of 4.4 m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area of 9.1 m 2 / g of Ga 2 O 3 powder was used, and ZnO powder having a particle size of 1.1 μm and a specific surface area of 3.8 m 2 / g was used as a ZnO raw material.
By adjusting these powders so that the In 2 O 3 raw material is 61.7 wt%, the Ga 2 O 3 raw material is 16.7 wt%, the ZnO raw material is 21.7 wt%, and the total is 100 wt%,
The metal ratio of In, Ga, and Zn is 0.714 in In / (In + Ga), Zn / (In + Ga + Zn) is 0.333, and the balance is Ga.
　次に、これらの粉末を混合した（仮焼せず）。粉砕前の比表面積は５．１ｍ２／ｇであった。また、粉砕後の比表面積は１６．０ｍ２／ｇであった。この差は、１０．９ｍ２／ｇであった。粉末の焼結温度を１４３０℃、焼結雰囲気：酸素雰囲気で焼結した。 Next, these powders were mixed (not calcined). The specific surface area before pulverization was 5.1 m 2 / g. The specific surface area after pulverization was 16.0 m 2 / g. This difference was 10.9 m 2 / g. The sintering temperature of the powder was 1430 ° C., and the sintering atmosphere was sintered in an oxygen atmosphere.
この結果、密度は６．５５ｇ／ｃｍ３、相対密度は９８．３％と高密度であり、バルク抵抗値は２．７ｍΩ・ｃｍで、ＤＣスパッタリングが十分可能である低バルク抵抗値を有していた。Ｉｎ２Ｏ３相の最大サイズ(長径)が１１．１μｍと大きくなり、相状態はＩｎｘＧａ（１－ｘ）)２ ＺｎＯ４相とＩｎ２Ｏ３相の２相であった。
そして、キャリア濃度が１．１５×１０１９(ｃｍ－３)と高くなった。移動度２９．０(ｃｍ２／Ｖｓ)であった。また、スパッタリング中のアーキングの発生は３６６回と多かった。これは、Ｉｎ２Ｏ３相が大きくなった結果であり、本願発明の条件を満たしていなかった。 As a result, the density is 6.55 g / cm 3 , the relative density is 98.3%, the bulk resistance value is 2.7 mΩ · cm, and it has a low bulk resistance value that allows DC sputtering sufficiently. It was. The maximum size (major axis) of the In 2 O 3 phase was increased to 11.1 μm, and the phase state was two phases of In x Ga (1-x ) 2 ZnO 4 phase and In 2 O 3 phase.
The carrier concentration increased to 1.15 × 10 19 (cm −3 ). The mobility was 29.0 (cm 2 / Vs). In addition, arcing occurred during sputtering as many times as 366 times. This is a result of an increase in the In 2 O 3 phase and did not satisfy the conditions of the present invention.
（比較例４）
Ｉｎ２Ｏ３原料として、粒径１．３μｍ、比表面積４．４ｍ２／ｇのＩｎ２Ｏ３粉末を用い、Ｇａ２Ｏ３原料として、粒径５．６μｍ、比表面積９．１ｍ２／ｇのＧａ２Ｏ３粉末を用い、ＺｎＯ原料として、粒径１．１μｍ、比表面積３．８ｍ２／ｇのＺｎＯ粉末を用いた。
これらの粉末を、Ｉｎ２Ｏ３原料を５２．４ｗｔ％、Ｇａ２Ｏ３原料を２６．２ｗｔ％、ＺｎＯ原料を２１．４ｗｔ％とし、合計が１００ｗｔ％となるように調整することで、
Ｉｎ、Ｇａ、Ｚｎをメタル比で、Ｉｎ／（Ｉｎ＋Ｇａ）で０．５７５とし、Ｚｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）を０．２８６、残部をＧａの組成となる。 (Comparative Example 4)
In 2 O 3 powder, particle size 1.3 .mu.m, using In 2 O 3 powder having a specific surface area of 4.4 m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area of 9.1 m 2 / g of Ga 2 O 3 powder was used, and ZnO powder having a particle size of 1.1 μm and a specific surface area of 3.8 m 2 / g was used as a ZnO raw material.
By adjusting these powders so that the In 2 O 3 raw material is 52.4 wt%, the Ga 2 O 3 raw material is 26.2 wt%, the ZnO raw material is 21.4 wt%, and the total is 100 wt%,
In, Ga, and Zn are metal ratios, and In / (In + Ga) is 0.575, Zn / (In + Ga + Zn) is 0.286, and the balance is Ga.
　次に、これらの粉末を混合した（仮焼せず）。粉砕前の比表面積は６．２ｍ２／ｇであった。また、粉砕後の比表面積は１５．５ｍ２／ｇであった。この差は、９．３ｍ２／ｇであった。粉末の焼結温度を１４９０℃、焼結雰囲気：酸素雰囲気で焼結した。 Next, these powders were mixed (not calcined). The specific surface area before pulverization was 6.2 m 2 / g. The specific surface area after pulverization was 15.5 m 2 / g. This difference was 9.3 m 2 / g. The sintering temperature of the powder was 1490 ° C., and the sintering atmosphere was sintered in an oxygen atmosphere.
この結果、密度は６．４３ｇ／ｃｍ３、相対密度は９７．４％と高密度であり、バルク抵抗値は１．２ｍΩ・ｃｍで、ＤＣスパッタリングが十分可能である低バルク抵抗値を有していた。Ｉｎ２Ｏ３相の最大サイズ(長径)が１３．５μｍと大きくなり、相状態はＩｎｘＧａ（１－ｘ）)２ ＺｎＯ４相とＩｎ２Ｏ３相の２相であった。
そして、キャリア濃度が４．５５×１０１５(ｃｍ－３)、移動度７．３４(ｃｍ２／Ｖｓ)であった。また、スパッタリング中のアーキングの発生は５１４回と多かった。これはＩｎ２Ｏ３相が大きくなったことが原因であり、本願発明の条件を満たしていなかった。
実施例７と比較して、成分組成が同一であるが、この比較例４では、Ｉｎ２Ｏ３相の粗大化が観察された。これは、焼結温度が実施例７の１４３０℃に比べて、比較例４では１４９０℃と高いことが原因で、Ｉｎ２Ｏ３相の粗大化が生じたと考えられる。 As a result, the density is 6.43 g / cm 3 , the relative density is 97.4%, the bulk resistance value is 1.2 mΩ · cm, and the low bulk resistance value that allows DC sputtering is sufficient. It was. The maximum size (major axis) of the In 2 O 3 phase increased to 13.5 μm, and the phase state was two phases of In x Ga (1-x ) 2 ZnO 4 phase and In 2 O 3 phase.
The carrier concentration was 4.55 × 10 15 (cm −3 ) and the mobility was 7.34 (cm 2 / Vs). Moreover, the occurrence of arcing during sputtering was as high as 514 times. This is because the In 2 O 3 phase became large and did not satisfy the conditions of the present invention.
Although the component composition is the same as in Example 7, in Comparative Example 4, coarsening of the In 2 O 3 phase was observed. This is probably because the sintering of the In 2 O 3 phase was coarsened because the sintering temperature was higher at 1490 ° C. in Comparative Example 4 than at 1430 ° C. in Example 7.
（比較例５）
Ｉｎ２Ｏ３原料として、粒径１０．７μｍ、比表面積４．４ｍ２／ｇのＩｎ２Ｏ３粉末を用い、Ｇａ２Ｏ３原料として、粒径５．６μｍ、比表面積９．１ｍ２／ｇのＧａ２Ｏ３粉末を用い、ＺｎＯ原料として、粒径１．１μｍ、比表面積３．８ｍ２／ｇのＺｎＯ粉末を用いた。
これらの粉末を、Ｉｎ２Ｏ３原料を４２．９ｗｔ％、Ｇａ２Ｏ３原料を３１．９ｗｔ％、ＺｎＯ原料を２５．２ｗｔ％とし、合計が１００ｗｔ％となるように調整することで、
Ｉｎ、Ｇａ、Ｚｎをメタル比で、Ｉｎ／（Ｉｎ＋Ｇａ）で０．４７６とし、Ｚｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）を０．３２３、残部をＧａの組成となる。 (Comparative Example 5)
In 2 O 3 powder, grain size 10.7, using In 2 O 3 powder having a specific surface area of 4.4 m 2 / g, as Ga 2 O 3 raw material, the particle size 5.6 [mu] m, a specific surface area of 9.1 m 2 / g of Ga 2 O 3 powder was used, and ZnO powder having a particle size of 1.1 μm and a specific surface area of 3.8 m 2 / g was used as a ZnO raw material.
By adjusting these powders so that the In 2 O 3 raw material is 42.9 wt%, the Ga 2 O 3 raw material is 31.9 wt%, the ZnO raw material is 25.2 wt%, and the total is 100 wt%,
In, Ga, and Zn have a metal ratio of In / (In + Ga) of 0.476, Zn / (In + Ga + Zn) of 0.323, and the balance of Ga.
　次に、これらの粉末を混合した（仮焼せず）。粉砕前の比表面積は６．９ｍ２／ｇであった。また、粉砕後の比表面積は１８．７ｍ２／ｇであった。この差は、１１．８ｍ２／ｇであった。粉末の焼結温度を１４３０℃、焼結雰囲気：酸素雰囲気で焼結した。 Next, these powders were mixed (not calcined). The specific surface area before pulverization was 6.9 m 2 / g. The specific surface area after pulverization was 18.7 m 2 / g. This difference was 11.8 m 2 / g. The sintering temperature of the powder was 1430 ° C., and the sintering atmosphere was sintered in an oxygen atmosphere.
この結果、密度は５．６０ｇ／ｃｍ３、相対密度は８６．５％と低密度となり、導電性がなく、ＤＣスパッタリングができなかった。相状態はＩｎｘＧａ（１－ｘ）)２ ＺｎＯ４相の単相であった。スパッタリングを実施していないので、薄膜の特性評価はできなかった。 As a result, the density was 5.60 g / cm 3 and the relative density was as low as 86.5%, and there was no conductivity and DC sputtering could not be performed. The phase state was a single phase of In x Ga (1-x) ) 2 ZnO 4 phase. Since sputtering was not performed, thin film characteristics could not be evaluated.
本発明の透明半導体ＩＧＺＯ膜作製用のスパッタリングターゲットとして使用される高密度ＩＧＺＯ酸化物焼結体は、高密度のＩＧＺＯターゲットを提供することができ、かつスパッタリング用ターゲットの低バルク抵抗化及びスパッタ膜のキャリア濃度及び移動度を一定の範囲とし、かつアーキングの発生を最小限に押さえ、ＤＣスパッタリングが可能であるＩＧＺＯターゲット技術を提供することができ、安定したＤＣスパッタリングが可能であるという優れた効果を有する。これによって、ターゲットライフも長くすることができ、品質のばらつきが少なく量産性を向上させることができる。このＩｎ－Ｇａ－Ｚｎ－Ｏ系（ＩＧＺＯ）材料は、電子キャリア濃度が１０１８／ｃｍ３未満であるアモルファス酸化物が得られるので、電界効果型トランジスタに有用である。また、ＩＧＺＯターゲットとして、広範囲な用途に支障なく使用できるので、産業上の利用価値は高い。 The high-density IGZO oxide sintered body used as the sputtering target for producing the transparent semiconductor IGZO film of the present invention can provide a high-density IGZO target, and can reduce the bulk resistance of the sputtering target and the sputtered film. The IGZO target technology that allows DC sputtering to be performed while keeping the carrier concentration and mobility in a certain range, minimizing the occurrence of arcing, and providing an excellent effect that stable DC sputtering is possible. Have As a result, the target life can be lengthened, and there is little variation in quality, so that mass productivity can be improved. This In—Ga—Zn—O-based (IGZO) material is useful for a field effect transistor because an amorphous oxide having an electron carrier concentration of less than 10 18 / cm 3 can be obtained. Moreover, since it can be used as an IGZO target without hindrance for a wide range of applications, its industrial utility value is high.

Claims (5)

  1. 　インジウム（Ｉｎ）、ガリウム（Ｇａ）、亜鉛（Ｚｎ）及び酸素（Ｏ）からなるＩＧＺＯ焼結体スパッタリングターゲットであって、Ｉｎ、Ｇａ、Ｚｎが０．５７５≧Ｉｎ／（Ｉｎ＋Ｇａ）≧０．５００であり、かつＺｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）＜０．３３３の組成範囲であり、(ＩｎｘＧａ（１－ｘ）)２ ＺｎＯ４(１＞ｘ＞０)相からなる単一相の組織を有することを特徴とするスパッタリングターゲット。 An IGZO sintered sputtering target composed of indium (In), gallium (Ga), zinc (Zn), and oxygen (O), wherein In, Ga, and Zn are 0.575 ≧ In / (In + Ga) ≧ 0.500. And a composition range of Zn / (In + Ga + Zn) <0.333 and having a single-phase structure composed of (In x Ga (1-x) ) 2 ZnO 4 (1>x> 0) phase. Sputtering target characterized by the above.
  2. 　インジウム（Ｉｎ）、ガリウム（Ｇａ）、亜鉛（Ｚｎ）及び酸素（Ｏ）からなるＩＧＺＯ焼結体スパッタリングターゲットであって、Ｉｎ、Ｇａ、Ｚｎが０．５７５≧Ｉｎ／（Ｉｎ＋Ｇａ）≧０．５００であり、かつＺｎ／（Ｉｎ＋Ｇａ＋Ｚｎ）＜０．３３３の組成範囲であり、(ＩｎｘＧａ（１－ｘ）)２ ＺｎＯ４(１＞ｘ＞０)相とＩｎ２Ｏ３相からなる二相構造の組織を有し、当該Ｉｎ２Ｏ３相の最大径が１０μｍ以下であることを特徴とするスパッタリングターゲット。 An IGZO sintered sputtering target composed of indium (In), gallium (Ga), zinc (Zn), and oxygen (O), wherein In, Ga, and Zn are 0.575 ≧ In / (In + Ga) ≧ 0.500. And a composition range of Zn / (In + Ga + Zn) <0.333, and a two-phase composed of an (In x Ga (1-x) ) 2 ZnO 4 (1>x> 0) phase and an In 2 O 3 phase A sputtering target having a structure of structure and having a maximum diameter of the In 2 O 3 phase of 10 μm or less.
  3. バルク抵抗が１５ｍΩ・ｃｍ以下であることを特徴とする請求項１又は２に記載のスパッタリングターゲット。 Bulk resistance is 15 mohm * cm or less, The sputtering target of Claim 1 or 2 characterized by the above-mentioned.
  4. 相対密度が９５％以上であることを特徴とする請求項１～３のいずれか一項に記載のスパッタリングターゲット。 The sputtering target according to any one of claims 1 to 3, wherein the relative density is 95% or more.
  5. 前記請求項１～４のいずれか一項に記載のスパッタリングターゲットを用いてスパッタリングすることにより得られる膜であって、キャリア濃度５×１０１５(ｃｍ－３)以下、移動度５(ｃｍ２／Ｖｓ)以上の膜特性を有することを特徴とする膜。 A film obtained by sputtering using the sputtering target according to any one of claims 1 to 4, wherein the carrier concentration is 5 × 10 15 (cm -3 ) or less, and the mobility is 5 (cm 2 / A film characterized by having a film characteristic equal to or higher than Vs).
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