CN103849842B - Sputtering target and conductive metal oxide film - Google Patents
Sputtering target and conductive metal oxide film Download PDFInfo
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- CN103849842B CN103849842B CN201310092782.1A CN201310092782A CN103849842B CN 103849842 B CN103849842 B CN 103849842B CN 201310092782 A CN201310092782 A CN 201310092782A CN 103849842 B CN103849842 B CN 103849842B
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- oxide film
- sputtering target
- target material
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- indium
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 65
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 64
- 238000005477 sputtering target Methods 0.000 title claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 58
- 239000002184 metal Substances 0.000 claims abstract description 57
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000004544 sputter deposition Methods 0.000 claims abstract description 39
- 229910052738 indium Inorganic materials 0.000 claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 26
- 239000011701 zinc Substances 0.000 claims abstract description 26
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052718 tin Inorganic materials 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000013077 target material Substances 0.000 claims description 46
- 239000004411 aluminium Substances 0.000 claims description 28
- 239000004615 ingredient Substances 0.000 claims description 17
- 238000002834 transmittance Methods 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 7
- 238000002441 X-ray diffraction Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 239000010936 titanium Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 76
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000843 powder Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 16
- 238000005259 measurement Methods 0.000 description 12
- 239000010409 thin film Substances 0.000 description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- HRHKULZDDYWVBE-UHFFFAOYSA-N indium;oxozinc;tin Chemical compound [In].[Sn].[Zn]=O HRHKULZDDYWVBE-UHFFFAOYSA-N 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910003437 indium oxide Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C14/54—Controlling or regulating the coating process
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Non-Insulated Conductors (AREA)
Abstract
A sputter target comprising indium, a first metal, a second metal, and oxygen, the atomic content of indium being in the range of 10 to 20at.%, the atomic content of the first metal being in the range of 60 to 80at.%, and the atomic content of the second metal being in the range of 10 to 20at.%, based on the total atomic content of indium, first metal, and second metal taken as 100at.%, wherein the first metal is selected from the group consisting of zinc, tin, and combinations thereof, and the second metal is selected from the group consisting of aluminum, titanium, and combinations thereof. The invention also provides a conductive metal oxide film formed by sputtering the sputtering target, the resistivity of the conductive metal oxide film is high, the preset thickness of the conductive metal oxide film is further maintained not to be reduced and not to be damaged easily, and the yield of the conductive metal oxide film applied to a photoelectric element is effectively improved.
Description
Technical field
The present invention relates to a kind of sputtering target material and conductive metal oxide film, is formed more particularly to one kind through sputtering
The sputtering target material and high resisitivity conductive metal-oxide film of the high conductive metal oxide film of resistivity.
Background technology
One conductive metal oxide film is typically to be deposited and obtained using sputtering process, can utilize metal or metal alloy target
Material is made in a manner of reaction equation sputters, and also can form this through sputtering the identical metal oxide sputtering target material of a component and lead
Metal oxide film.
Wherein, since an indium and tin oxide film (calling ito thin film in the following text) possesses excellent conductive characteristic (namely resistivity
It is low), and transparency is also high under the irradiation of visible ray, so being to develop conductive metal oxide film the most ripe, is also
Most widely used conductive metal oxide film in opto-electronics, particularly electrode layer or electric current of the application as photoelectric cell
Diffusion layer.
Afterwards, there is scholar's discovery, when also containing zinc in the indium and tin oxide film, and form an indium zinc tin oxide film
When, in addition to maintaining the characteristic of high conductivity, also possess the light transmittance of higher under the irradiation of the light of short wavelength range.Cause
This, indium zinc tin oxide film is also that one kind can be applied as transparent conductive film (transparent conducting
Oxide conductive metal oxide film).
With product day different diversification required on the market, for conductive metal oxide film characteristic demand not yet
As required lifting conductivity simply in the past, for example, when being applied to contact panel, the of a relatively high conduction of resistance value is needed on the contrary
Metal-oxide film.And general main way is thinning ito thin film, to lift the resistance value of film；However, subtract simply
The way of low ito thin film thickness, easily produces following shortcoming (side effect), for example, film is excessively thin to cause breakage, or it is thin
Film it is in uneven thickness, it will cause the yield rate of electrically unstable and obtained photoelectric cell low.
Therefore, research and propose：To change the way of metallic element or proportion of composing, with different conducting metal oxide
The traditional ito thin film of film substitution, and the way need to consider many subjects under discussion, except the compatibility between the film and other elements whether
Outside similar to the compatibility between ito thin film and other elements, also need to consider that processing apparatus, working procedure parameter and waste recovery flow become
More the problems such as, so, this also becomes the target of industry research.
The content of the invention
According to foregoing, inventor make great efforts research how the sputtering process for making ito thin film at present using being similar to, splashed with one
Material of shooting at the target is high, best in quality through sputtering one operation yield rate of formation, the high conductive metal oxide film of resistivity, and is not required to become
More current processing apparatus and flow.
It is an object of the invention to provide a kind of sputtering target material that high resistivity metal oxide is formed through sputtering.
In addition, another object of the present invention, that is, providing a kind of metal-oxide film of high resistivity.
Sputtering target material of the present invention, includes indium, one first metal, one second metal, and oxygen.
Based on indium, first metal and the bimetallic atom total content in terms of 100at.%, the atom content model of indium
Enclose for 10 to 20at.%, the atom content scope of first metal is 60 to 80at.%, the bimetallic atom content model
Enclose for 10 to 20at.%, wherein, which is selected from zinc, tin, and foregoing combination, which is selected from aluminium, titanium, and
Foregoing combination.
It is preferred that the atom content scope of the indium of foregoing sputtering target material is 12 to 18at.%, the atom of first metal contains
It is 64 to 76at.% to measure scope, which is 12 to 18at.%.
It is preferred that first metal of foregoing sputtering target material is tin and zinc, which is aluminium.
It is preferred that the atom content scope of tin is 10 to 20at.% in first metal of foregoing sputtering target material.
It is preferred that the atom content scope of zinc is 10 to 20at.% in first metal of foregoing sputtering target material.
It is preferred that foregoing sputtering target material includes the principal component of one one-tenth more crystal phase structure, and a crystal phase structure different from this it is main into
The accessory ingredient divided, and the principal component all has indium, first metal, and second metal with the accessory ingredient.
It is preferred that the atom content percentage of aluminium is more than the original of aluminium in the principal component in the accessory ingredient of foregoing sputtering target material
Sub- percentage composition.
It is preferred that foregoing sputtering target material has by X-ray diffraction measure in the position that the angle of diffraction is 33.0 °~35.0 °
Diffraction wave crest.
It is preferred that the resistivity of foregoing sputtering target material is more than 5 × 10-3Ω cm, and less than 10-1Ω·cm。
It is preferred that the absolute density of foregoing sputtering target material is more than 6g/cm-3。
Conductive metal oxide film of the present invention, is formed by above-mentioned sputtering target material through sputtering.
It is preferred that the conductive metal oxide film of aforesaid conductive metal-oxide film is when thickness is 100nm
Resistance value is more than 106Ω。
It is preferred that the resistivity of aforesaid conductive metal-oxide film between 0.1 Ω cm between 1 Ω cm.
It is preferred that the light transmittance of aforesaid conductive metal-oxide film is more than 85%.
The beneficial effects of the present invention are：The sputtering target material the electricity through sputtering formed conductive metal oxide film
Resistance rate is high, and then maintains the predetermined thickness of the conductive metal oxide film not to be contracted by and not cracky, effectively improves this and leads
Metal oxide film is applied to the yield rate of photoelectric cell..
Brief description of the drawings
Illustrate presently preferred embodiments of the present invention.
Fig. 1 is the table that 1 sputtering target material of concrete example carries out the electron beam scanning preferred embodiment with sweep electron microscope
Simultaneously analyze signal graph caused by backscattering electronics in face；
Fig. 2 is the partial enlarged view of Fig. 1；
Fig. 3 is Energy Dispersive Spectroscopy (Energy Dispersive Spectrometer, the below letter of a concrete example 1
Claim EDS) analysis chart；
Fig. 4 is the EDS analysis charts of a concrete example 2；
Fig. 5 is X-ray diffractometer (X-ray diffraction, hereinafter referred to as XRD) the measurement figure of a concrete example 1；
Fig. 6 is the XRD measurement figures of a concrete example 2.
Embodiment
The preferred embodiment of sputtering target material of the present invention includes indium, one first metal, one second metal, and oxygen, based on indium, is somebody's turn to do
In terms of 100at.%, the atom content scope of indium is 10 to 20at.%, should for first metal and the bimetallic atom total content
The atom content scope of first metal is 60 to 80at.%, which is 10 to 20at.%, its
In, which is selected from zinc, tin, and foregoing combination, which is selected from aluminium, titanium, and foregoing combination, and this second
Resistivity of the resistivity of the oxide of metal higher than the oxide of first metal.
When the preferred embodiment is formed a conductive metal oxide film through sputtering in the cavity of a sputtering machine table,
Due to sputtering be based on physical deposition principle in a manner of form film, then containing indium, first metal, second metal,
And the conductive metal oxide film that the sputtering target material of oxygen is formed also contains indium, first metal, second metal, and
Oxygen.
Herein it should be noted that, although the characteristic of conductive metal oxide film is except the shadow formed by target material composition
Outside ringing, it can also be influenced by sputtering environment and parameter value setting.Oxygen is also passed through during sputtering to the sputtering for example, working as
When in the cavity of board, oxygen also can regard environment (such as oxygen content in the temperature of cavity or the pressure of cavity or cavity) and
Reacted with the metal ingredient of the sputtering target material, and then influence the characteristic of conductive metal oxide film.But sputter environment and parameter
Influence of the value setting to conductive metal oxide film resistivity is typically limited in the range of one, and method is not splashed in appropriate
Stable high resistance ito thin film or indium zinc tin oxide film are obtained under the conditions of penetrating.It is therefore advantageous to mode be still necessary to adopt
With the metal oxide target of proper composition and proportion of composing to obtain the conductive metal oxide film of high resistivity.
The bimetallic atom content of the preferred embodiment is 10 to 20at.%, then is formed after sputtering process
The component of conductive metal oxide film also contain second metal, and the resistance value of the conductive metal oxide film is more than
The sheet resistance of the ito thin film of same thickness, also greater than the sheet resistance of the indium zinc tin oxide film of same thickness；Furthermore its is saturating
Light rate is still suitable with the light transmittance of current indium zinc tin oxide film.Specifically, when the conductive metal oxide film is in film
When thickness is 100nm, its resistance value is more than 106Ω, and average transmittance is more than 85%.
And also need to put forward explanation, the resistivity for the conductive metal oxide film which is formed is big
It is in one of reason of the resistivity of indium zinc tin oxide film：Add the aluminium atom or titanium atom and indium zinc of predetermined concentration
Tin forms the higher compound of resistivity, thus reduces electron mobility, and lifts resistivity.
Specifically, if the bimetallic atom content of the preferred embodiment is less than 10at.%, through sputtering process
The too low conductive metal oxide film of bimetallic atom content is easily formed afterwards；Illustrated and made using aluminium as second metal
Illustrate, when the aluminium content in a conductive metal oxide film is too low, aluminium atom occupies the lattice position of former zinc or indium and produces
Raw substituting effect, thus increase the carrier concentration in oxide, cause the conductivity of conductive metal oxide film to rise.
In addition, if the bimetallic atom content of the preferred embodiment is more than 20at.%, insulate in its material
Property high aluminium oxide or titanium oxide content it is excessive, the resistance value mistake through sputtering formed conductive metal oxide film will be caused
It is high and conductive capability is insufficient.
More accurately, the content range of the indium of the preferred embodiment is 12 to 18at.%, the atom content of first metal
Scope is 64 to 76at.%, which is 12 to 18at.%.
And it is preferred that first metal is tin and zinc, which is aluminium, and the atom content scope of zinc for 10 to
20at.%, or the atom content scope of tin is 10 to 20at.%, all and then makes the conducting metal oxide formed through sputtering
Resistance value of the film when thickness is 100nm is more than 5 × 106Ω, and in the light irradiation that wave-length coverage is 300 to 1300nm
Light transmittance be more than 87%.
More preferably, which contains a principal component, and a lattice structure different from the accessory ingredient of the principal component, the master
Component is with the accessory ingredient all containing indium, first metal, and second metal.The bimetallic atom content in the accessory ingredient
Percentage is more than the bimetallic atom content percentage in the principal component, thus it is speculated that higher containing resistivity in the accessory ingredient
Compound；Atom content percentage referred to herein is also based respectively on indium, first metal in principal component or accessory ingredient, and should
Bimetallic atom total content is in terms of 100at.%.
It is preferred that the resistivity of the sputtering target material is more than 5 × 10-3Ω cm, and less than 10-1Ω cm, to ensure to sputter
Process can carry out under d.c. sputtering.
Hereinafter, will be using the first metal as tin and zinc, and the second metal is aluminium, the present invention will be described in detail sputtering target material it is preferable
The production method of embodiment.
First, an indium oxide powder of the purity more than 99.9%, a Zinc oxide powder, tin monoxide powder are prepared respectively,
An and alumina powder.
Then, a ball milling step is carried out, first by the indium oxide powder, the Zinc oxide powder, the stannic oxide powder, and the oxygen
Change aluminium powder and mix a mixed-powder, be placed into a ball mill, then more several zirconia balls are added in the ball mill,
Then, more than when making these zirconia balls and the mixed-powder continuous ball milling 8 small, then by the mixed-powder after ball milling and these oxygen
Change the separation of zirconium ball.
Come again, carry out a granulation step, the mixed-powder after ball milling is formed particle size range in a manner of spray drying is
20 to 100 μm of a pelletizing.
Continue, carry out a forming step, prepare a mould for scribbling a remover, be placed into the pelletizing, then in a pressure
Power scope is 200 to 1200kg/cm3, and the environment that temperature range is 30 to 50 DEG C is suppressed, and obtain a relative density scope and be
50 to 65% raw embryo target.
Then, a sintering step is carried out, which is placed in one and is passed through in the high temperature sintering furnace of oxygen, then with model
The temperature enclosed for 1300 to 1600 DEG C sinters the preferred embodiment to form sputtering target material of the present invention.
Finally, also visual demand carries out a shaping step, which is cut, into predetermined size,
And surface grinding is carried out, make surface smooth and smooth.
It is next, thin for the concrete example and comparative example of sputtering target material of the present invention, and its conducting metal oxide formed
The measurement and analysis of the component ratio and characteristic of film.
《Measurement and analysis》
[concrete example 1]
The concrete example 1 is more than 99.9% with obtained by the production method of the above-mentioned preferred embodiment, using 19.2 grams of purity
Indium oxide powder, 11.3 grams of Zinc oxide powders, 62.5 grams of stannic oxide powders, and 7.0 grams of alumina powders.When with indium, zinc,
Tin, the atom content of aluminium are counted for 100at.%, and the atom content of the indium of the concrete example 1 is 16.7at.%, and the atom content of zinc is
16.7at.%, the atom content of tin is 50at.%, and the atom content of aluminium is 16.7at.%.(above-mentioned is respectively to contain atom
Value is rounded to below decimal point the 1st expression)
Continue, the target using the concrete example 1 as sputtering process, is 3W/cm in power density2, temperature control is in room
Temperature, be passed through the oxygen that flow velocity is substantially the argon gas of 70sccm and flow velocity is substantially 4sccm, and the chamber that operating pressure is 3.5mTorr
Body environment, sputtering forms a film on a substrate with the target interval, and is tempered after sputtering again with 200 DEG C, and is made one
The conductive metal oxide film formed by the concrete example 1.
[concrete example 2]
The concrete example 2 is obtained by the production method of the similar concrete example 1,99.9% oxygen is more than using 23.7 grams of purity
Change indium powder about, 41.8 grams of Zinc oxide powders, 25.8 grams of stannic oxide powders, and 8.7 grams of alumina powders.When with indium, zinc, tin,
The atom content of aluminium is counted for 100at.%, and the atom content of the indium of the concrete example 1 is 16.7at.%, and the atom content of zinc is
50at.%, the atom content of tin is 16.7at.%, and the atom content of aluminium is 16.7at.%.(above-mentioned is respectively to contain atom
Value is rounded to below decimal point the 1st expression)
Continue, the target using the concrete example 2 as sputtering process, the sputtering process through being passed through similar to the concrete example 1,
And a film is formed, and be tempered after sputtering again with 280 DEG C, and a conducting metal oxide formed by the concrete example 2 is made
Film.
[comparative example 1]
The comparative example 1 then prepares 73.2 grams respectively with obtained by the production method of the similar concrete example 1, its difference is in
Indium oxide powder of the purity more than 99.9%, 9.8 grams of Zinc oxide powders, and 17.0 grams of stannic oxide powders.
Continue, the target using the comparative example 1 as sputtering process, the sputtering process through being passed through similar to the concrete example 1,
And a film is formed, and be tempered after sputtering again with 280 DEG C, and a conducting metal oxide formed by the comparative example 1 is made
Film.
[comparative example 2]
The comparative example 2 with obtained by the production method of the similar concrete example 1, its difference be in then prepare respectively 90 grams it is pure
The 10 grams of stannic oxide powders of indium oxide powder of degree more than 99.9%.
Continue, the target using the comparative example 2 as sputtering process, the sputtering process through being passed through similar to the concrete example 1,
And a film is formed, and be tempered after sputtering again with 280 DEG C, and a conducting metal oxide formed by the comparative example 2 is made
Film (namely ito thin film)
[comparative example 3]
The comparative example 3 with obtained by the production method of the similar concrete example 1, its difference be in then prepare respectively 98 grams it is pure
Zinc oxide powder of the degree more than 99.9%, and 2 grams of alumina powders.
Continue, the target using the comparative example 3 as sputtering process, the sputtering process through being passed through similar to the concrete example 1,
And a film is formed, and be tempered after sputtering again with 170 DEG C, and a conducting metal oxide formed by the comparative example 3 is made
Film (namely AZO films).
Measurement result in relation to component ratio and characteristic, lists such as table 1 respectively.
Table 1
It need to first chat bright, the measuring condition of resistance is that the thickness of fixed concrete example and comparative example is all 100nm in table 1；
Furthermore concrete example 1 and 2 resistance value of concrete example are higher, more than four-point probe resistance measurement mode measurement range, and can not
With the resistance of four-point probe measurement film, therefore megger is used to measure.Further, since the resistance listed by table 1 is in thickness 100nm
Under conditions of measure, resistivity be then by the measured value of resistance be multiplied by film thickness conversion and obtain；Light transmittance is in thickness 100nm
And the result that measurement obtains when being irradiated by the light that wave-length coverage is 300 to 1300nm.
First, the resistance value of the conductive metal oxide film formed by concrete example 1 with concrete example 2 will be seen that, when this
First metal of sputtering target material is zinc and tin, when which is aluminium, the resistance of the conductive metal oxide film formed
Value far above only by indium zinc tin oxide target, indium-tin oxide target material, and Zinc-aluminium target material (be respectively comparative example 1,
2 and the sheet resistance of the conductive metal oxide film 3) formed；This represent when indium atom content scope 12 to
18at.%, the atom content scope of first metal is 64 to 76at.%, and the bimetallic atom content scope is 12
During to 18at.%, especially the resistivity for the conductive metal oxide film that the sputtering target material is formed can be promoted to one and made a reservation for
Scope.And will be seen that by the measurement result of comparative example 3, the atom content of the aluminium in the sputtering target material is less than 10at.%, then its
The atom content of the aluminium of the conductive metal oxide film formed is too low, can not effectively lift resistivity；Again by comparative example 1
It will be seen that with comparative example 2, when which only has indium, zinc and/or tin, even if adjustment indium and the first intermetallic ratio
Relation, can not still form the high conductive metal oxide film of resistivity.
Secondly, will be seen that by table 1, concrete example 1 of the present invention is with concrete example 2 through sputtering formed conducting metal oxide
The light transmittance of film is still greater than 85%, and with comparative example 1,2,3 through sputtering the printing opacity of formed conductive metal oxide film
Rate is suitable.
It is 1 sputtering target material of concrete example with sweep electron microscope (Scanning Electron refering to Fig. 1, Fig. 2
Microscope, hereinafter referred to as SEM) carry out the surface of the electron beam scanning preferred embodiment and analyze backscattering electronics being produced
Raw signal graph (back-scattering electron, hereinafter referred to as BSE), by diagram, it will be seen that, concrete example 1 wraps at the same time
A principal component (at light color), and a crystal phase structure are included different from the accessory ingredient of the principal component (at dark color).
Refering to Fig. 3, by Energy Dispersive Spectroscopy (Energy Dispersive Spectrometer, hereinafter referred to as EDS)
Analysis chart will be seen that, the indium of the principal component based on concrete example 1, zinc, the atom content of tin and aluminium are in terms of 100at.%, the original of indium
Sub- content is 18.58at.%, and the atom content of zinc is 14.82at.%, and the atom content of tin is 61.6at.%, and the original of aluminium
Sub- content is 5.00at.%, that is, the atom content of the first metal of the principal component is 76.42at.%, and second metal
Atom content be 5.00at.%；The indium of accessory ingredient based on concrete example 1, zinc, the atom content of tin and aluminium are with 100at.%
Meter, the atom content of indium is 3.4at.%, and the atom content of zinc is 31.12at.%, and the atom content of tin is 6.03at.%, and
The atom content of aluminium is 59.45at.%, that is, the atom content of the first metal of the accessory ingredient is 37.15at.%, and should
Bimetallic atom content is 59.45at.%.
Refering to Fig. 4, it will be seen that by EDS analysis charts, the indium of the principal component based on concrete example 2, zinc, the atom of tin and aluminium contain
For amount in terms of 100at.%, the atom content of indium is 18.42at.%, and the atom content of zinc is 57.89at.%, the atom content of tin
For 19.01at.%, and the atom content of aluminium is 4.68at.%, that is, the atom content of the first metal of the principal component is
76.9at.%, and the bimetallic atom content is 4.68at.%；Indium, zinc, tin and the aluminium of accessory ingredient based on concrete example 2
Atom content in terms of 100at.%, the atom content of indium is 9.02at.%, and the atom content of zinc is 42.82at.%, tin
Atom content is 9.03at.%, and the atom content of aluminium is 38.86at.%, that is, the atom of the first metal of the accessory ingredient
Content is 52.12at.%, and the bimetallic atom content is 38.86at.%.
Refering to Fig. 5, it will be seen that, had by X-ray diffractometer (X-ray diffraction, hereinafter referred to as XRD) measurement figure
Body example 1 is more crystal phase structures, and is respectively 25.5 ° to 26.5 °, 30.5 ° to 31.5 °, 33.0 ° to 34.0 ° in the angle of diffraction, and
Diffraction wave crest can be observed at 51.0 ° to 52.0 °.
Refering to Fig. 6, by XRD measurements figure, it will be seen that, concrete example 2 be more crystal phase structures, and respectively the angle of diffraction be 16 ° extremely
At 18 °, 28.5 ° to 29.5 °, 33.5 ° to 34.5 °, 35.5 ° to 36.5 °, 41 ° to 42 °, 54.5 ° to 55.5 °, and 60 ° to 61 °
It can observe diffraction wave crest.
In conclusion sputtering target material of the present invention contains indium, first metal, second metal, and oxygen, and second metal
Atom content be 10 to 20at.%, and supply to be equal to through sputtering formed conductive metal oxide film in thickness existing
Ito thin film or indium zinc tin oxide film thickness, resistance of its resistivity higher than ito thin film or indium zinc tin oxide film
Rate, and light transmittance remains above 85%, photoelectric cell, such as contact panel and touch control sensor is suitably applied, so really can
Reach the purpose of the present invention.
Only just the specific configuration embodiment of the present invention adds and gives explanation above, without disobey the construction of the present invention with it is spiritual under, it is all
It is skillful in those skilled in the art scholar, still does a variety of change and modification, this all change is still considered as with modification is covered under this case
In row claim.
Claims (12)
1. a kind of sputtering target material, it is characterised in that include：Indium, one first metal, one second metal, and oxygen, based on indium, this
In terms of 100at.%, the atom content scope of indium is 10 to 20at.% for one metal and the bimetallic atom total content, this
The atom content scope of one metal is 60 to 80at.%, which is 10 to 20at.%, wherein,
First metal is the combination of zinc and tin, which is aluminium.
2. sputtering target material as claimed in claim 1, it is characterised in that：The atom content scope of indium is 12 to 18at.%, this
The atom content scope of one metal is 64 to 76at.%, which is 12 to 18at.%.
3. sputtering target material as claimed in claim 1, it is characterised in that：The atom content scope of tin is 10 to 20at.%.
4. sputtering target material as claimed in claim 1, it is characterised in that：The atom content scope of zinc is 10 to 20at.%.
5. sputtering target material as claimed in claim 1, it is characterised in that：The sputtering target material include one one-tenth more crystal phase structure it is main into
Point, and a crystal phase structure is different from the accessory ingredient of the principal component, and the principal component all has indium, first metal with the accessory ingredient,
And second metal.
6. sputtering target material as claimed in claim 5, it is characterised in that：The atom content percentage of aluminium, which is more than, in the accessory ingredient is somebody's turn to do
The atom content percentage of aluminium in principal component.
7. sputtering target material as claimed in claim 1, it is characterised in that：It it is 33.0 ° in the angle of diffraction by X-ray diffraction measure
~35.0 ° of position has diffraction wave crest.
8. sputtering target material as claimed in claim 1, it is characterised in that：The resistivity of the sputtering target material is more than 5 × 10-3Ω·
Cm, and less than 10-1Ω·cm。
9. sputtering target material as claimed in claim 1, it is characterised in that：The absolute density of the sputtering target material is more than 6g/cm3。
10. a kind of conductive metal oxide film, it is characterised in that as the sputtering target described in above-mentioned 1st~9 any of which item
Material is formed through sputtering.
11. conductive metal oxide film as claimed in claim 10, it is characterised in that：The conductive metal oxide film
Resistivity is between 0.1 Ω cm between 1 Ω cm.
12. conductive metal oxide film as claimed in claim 10, it is characterised in that：The conductive metal oxide film
Light transmittance is more than 85%.
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| TW101145245 | 2012-12-03 | ||
| TW101145245A TW201422835A (en) | 2012-12-03 | 2012-12-03 | Sputtering target and conductive metal oxide film |
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| KR (1) | KR20140074163A (en) |
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| JP5688179B1 (en) * | 2014-09-10 | 2015-03-25 | Jx日鉱日石金属株式会社 | Oxide sintered body, sputtering target, thin film, and method for producing oxide sintered body |
| JP5876172B1 (en) * | 2014-10-06 | 2016-03-02 | Ｊｘ金属株式会社 | Oxide sintered body, oxide sputtering target, conductive oxide thin film, and method for producing oxide sintered body |
| JP5735190B1 (en) * | 2015-01-22 | 2015-06-17 | Jx日鉱日石金属株式会社 | Oxide sintered body, sputtering target, and oxide thin film |
| JP6869157B2 (en) * | 2017-09-29 | 2021-05-12 | 出光興産株式会社 | Oxide sintered body, sputtering target, amorphous oxide semiconductor thin film, and thin film transistor |
| JP6858107B2 (en) * | 2017-09-29 | 2021-04-14 | 出光興産株式会社 | Oxide sintered body, sputtering target, amorphous oxide semiconductor thin film, and thin film transistor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1397661A (en) * | 2001-06-26 | 2003-02-19 | 三井金属矿业株式会社 | Sputtering target for high resistance transparent conductive membrane and mfg. method of high resistance transparent conductive membrane |
| CN1621558A (en) * | 2003-11-25 | 2005-06-01 | 株式会社日矿材料 | Sputtering target and optical information recording medium and manufacturing method thereof |
| CN101481790A (en) * | 2009-01-20 | 2009-07-15 | 李丹之 | ZAO semiconductor nano conductive film and preparation thereof |
| CN101548343A (en) * | 2007-09-05 | 2009-09-30 | 株式会社村田制作所 | Transparent conductive film and method for producing transparent conductive film |
| WO2012153507A1 (en) * | 2011-05-10 | 2012-11-15 | 出光興産株式会社 | In2O3-SnO2-ZnO SPUTTERING TARGET |
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| JP3644647B2 (en) * | 1995-04-25 | 2005-05-11 | Ｈｏｙａ株式会社 | Conductive oxide and electrode using the same |
| JP5188182B2 (en) * | 2005-09-27 | 2013-04-24 | 出光興産株式会社 | Sputtering target, transparent conductive film, and transparent electrode for touch panel |
| JP5244331B2 (en) * | 2007-03-26 | 2013-07-24 | 出光興産株式会社 | Amorphous oxide semiconductor thin film, manufacturing method thereof, thin film transistor manufacturing method, field effect transistor, light emitting device, display device, and sputtering target |
| KR20170092716A (en) * | 2010-04-22 | 2017-08-11 | 이데미쓰 고산 가부시키가이샤 | Deposition method |
| JP6284710B2 (en) * | 2012-10-18 | 2018-02-28 | 出光興産株式会社 | Sputtering target, oxide semiconductor thin film, and manufacturing method thereof |
-
2012
- 2012-12-03 TW TW101145245A patent/TW201422835A/en unknown
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2013
- 2013-03-21 CN CN201310092782.1A patent/CN103849842B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1397661A (en) * | 2001-06-26 | 2003-02-19 | 三井金属矿业株式会社 | Sputtering target for high resistance transparent conductive membrane and mfg. method of high resistance transparent conductive membrane |
| CN1621558A (en) * | 2003-11-25 | 2005-06-01 | 株式会社日矿材料 | Sputtering target and optical information recording medium and manufacturing method thereof |
| CN101548343A (en) * | 2007-09-05 | 2009-09-30 | 株式会社村田制作所 | Transparent conductive film and method for producing transparent conductive film |
| CN101481790A (en) * | 2009-01-20 | 2009-07-15 | 李丹之 | ZAO semiconductor nano conductive film and preparation thereof |
| WO2012153507A1 (en) * | 2011-05-10 | 2012-11-15 | 出光興産株式会社 | In2O3-SnO2-ZnO SPUTTERING TARGET |
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| TWI460299B (en) | 2014-11-11 |
| KR20140074163A (en) | 2014-06-17 |
| TW201422835A (en) | 2014-06-16 |
| JP2014109071A (en) | 2014-06-12 |
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