CN102918004B - 溅射靶 - Google Patents
溅射靶 Download PDFInfo
- Publication number
- CN102918004B CN102918004B CN201180027030.6A CN201180027030A CN102918004B CN 102918004 B CN102918004 B CN 102918004B CN 201180027030 A CN201180027030 A CN 201180027030A CN 102918004 B CN102918004 B CN 102918004B
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- Prior art keywords
- metal
- sintered body
- oxidate sintered
- gallium
- indium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000005477 sputtering target Methods 0.000 title claims description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 48
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 36
- 229910052738 indium Inorganic materials 0.000 claims abstract description 28
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 26
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004065 semiconductor Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000006104 solid solution Substances 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229910052732 germanium Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 150000002259 gallium compounds Chemical class 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- 150000002472 indium compounds Chemical class 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000010408 film Substances 0.000 description 44
- 238000004544 sputter deposition Methods 0.000 description 18
- 239000010409 thin film Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 15
- 229910052710 silicon Inorganic materials 0.000 description 15
- 239000010703 silicon Substances 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 238000002425 crystallisation Methods 0.000 description 13
- 230000008025 crystallization Effects 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- 238000005245 sintering Methods 0.000 description 11
- 238000001354 calcination Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004453 electron probe microanalysis Methods 0.000 description 4
- -1 halogenide (muriate Chemical compound 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229910001195 gallium oxide Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000000803 paradoxical effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N97/00—Electric solid-state thin-film or thick-film devices, not otherwise provided for
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B33/326—Burning methods under pressure
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
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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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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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
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- H01—ELECTRIC ELEMENTS
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
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- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/66007—Multistep manufacturing processes
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- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
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- 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
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
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- 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
- C04B2235/3287—Germanium oxides, germanates or oxide forming salts thereof, e.g. copper germanate
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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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Abstract
本发明提供一种氧化物烧结体,其特征在于,含有铟(In)、镓(Ga)和正三价和/或正四价的金属X的氧化物,相对于In和Ga的总量,金属X的配合量为100~10000ppm(重量)。
Description
技术领域
本发明涉及氧化物烧结体、由其形成的溅射靶、使用该靶制作的氧化物薄膜及含有该氧化物薄膜的氧化物半导体元件。
背景技术
近年来,显示装置的发展显著,正积极地将液晶显示装置、EL显示装置等各种显示装置引入个人电脑、文字处理器等OA设备。这些显示装置都具有用透明导电膜夹持显示元件的夹芯结构。
驱动这些显示装置的开关元件现在硅系半导体膜占主流。这是因为硅系薄膜的稳定性、加工性优良,而且开关速度快等。该硅系薄膜一般地采用化学气相沉积法(CVD)法制作。
但是,硅系薄膜为非晶的情况下,开关速度比较慢,显示高速的动画等的情况下具有不能显示图像的难点。此外,结晶的硅系薄膜的情况下,开关速度比较快,但结晶化需要800℃以上的高温、采用激光器的加热等,对于制造需要大量的能量和工序。此外,硅系薄膜虽然作为电压元件,性能也优异,但流过电流的情况下,其特性的经时变化成为问题。
因此,研究了硅系薄膜以外的膜。提出了与硅系薄膜相比稳定性优异,同时具有与ITO(氧化铟锡)膜同等的光透射率的透明半导体膜,以及作为用于得到该膜的靶的由氧化铟、氧化镓和氧化锌形成的透明半导体薄膜、由氧化锌和氧化镁形成的透明半导体薄膜(例如专利文献1)。
现有技术文献
专利文献
专利文献1:日本特开2004-149883号公报
发明内容
本发明的目的在于提供能够用于氧化物半导体元件的非硅系半导体薄膜以及用于形成该非硅系半导体薄膜的氧化物烧结体和溅射靶。此外,本发明的目的还在于提供使用了新型的非硅系半导体薄膜的氧化物半导体元件。
根据本发明,提供以下的氧化物烧结体等。
1.氧化物烧结体,其特征在于,含有铟(In)、镓(Ga)和正三价和/或正四价的金属X的氧化物,相对于In和Ga的总量,金属X的配合量为100~10000ppm(重量)。
2.如1所述的氧化物烧结体,其特征在于,金属X为从Sn、Zr、Ti、Ge、Hf中选择的1种以上的金属。
3.如1或2所述的氧化物烧结体,其特征在于,所述金属X至少含有Sn。
4.如1~3的任一项所述的氧化物烧结体,其特征在于,原子比Ga/(Ga+In)为0.005~0.15。
5.如1~4的任一项所述的氧化物烧结体,其特征在于,体积电阻为10mΩcm以下。
6.如1~5的任一项所述的氧化物烧结体,其特征在于,分散的镓的粒径为1μm以下。
7.如1~6的任一项所述的氧化物烧结体,其特征在于,在In2O3的方铁锰矿结构中镓和金属X固溶分散。
8.如1~7的任一项所述的氧化物烧结体的制造方法,其特征在于,包括:将平均粒径小于2μm的铟化合物粉末和平均粒径小于2μm的镓化合物粉末及平均粒径小于2μm的金属X的化合物的粉末,以镓和铟的原子比Ga/(In+Ga)=0.001~0.10、且相对于In和Ga的总量,金属X的配合量为100~10000ppm的方式进行混合的工序;将混合物成型来调制成型体的工序;和将所述成型体在1200℃~1600℃下烧成2~96小时的工序。
9.如8所述的氧化物烧结体的制造方法,其特征在于,在氧气氛中或加压下进行烧成。
10.溅射靶,其特征在于,其是由如1~7的任一项所述的氧化物烧结体形成的。
11.氧化物薄膜,其特征在于,其是使用如10所述的溅射靶而成膜的。
12.氧化物薄膜,其特征在于,含有铟(In)、镓(Ga)和正三价和/或正四价的金属X的氧化物,相对于In和Ga的总量,金属X的配合量为100~10000ppm(重量)。
13.氧化物半导体元件,其特征在于,活性层是由11或12所述的氧化物薄膜形成的。
根据本发明,能够提供能够用于氧化物半导体元件的非硅系半导体薄膜以及用于形成该非硅系半导体薄膜的氧化物烧结体和溅射靶。根据本发明,能够提供使用了新型的非硅系半导体薄膜的氧化物半导体元件。
附图说明
图1为表示实施例2的由X射线衍射得到的曲线的图。
图2为表示实施例3的由X射线衍射得到的曲线的图。
图3为表示实施例2的采用EPMA(电子束微量分析器)的观察结果的图。
图4为表示比较例1的由X射线衍射得到的曲线的图。
具体实施方式
本发明的氧化物烧结体含有铟(In)、镓(Ga)和正三价和/或正四价的金属X的氧化物。此外,相对于In和Ga的总量,X的配合量(以下称为“X/(In+Ga)”)为100~10000ppm(重量)。
金属X优选为从Sn、Zr、Ti、Ge、Hf中选择的1种以上的元素。金属X优选至少含有Sn。
原子比Ga/(In+Ga)优选为0.001~0.15。
如果Ga/(In+Ga)小于0.001,氧化铟结晶的晶格常数的变化变小,有时没有显现添加镓的效果,如果超过0.15,有时InGaO3等析出。InGaO3等越析出,靶的电阻越升高,越难以进行生产性优异的采用直流溅射的生产。
优选Ga/(In+Ga)=0.005~0.15,更优选Ga/(In+Ga)=0.01~0.12,进一步优选Ga/(In+Ga)=0.03~0.10。
此外,如果X/(In+Ga)小于100ppm,靶的电阻升高。超过10,000ppm时,变得不能控制氧化物半导体的电阻。
本发明的氧化物烧结体,优选基本上只由铟、镓和金属X的氧化物组成。优选不含硅。
本发明中,所谓“基本上”,意味着作为氧化物烧结体的效果起因于上述氧化物,或者氧化物烧结体的95重量%以上100重量%以下(优选98重量%以上100重量%以下)为铟、镓和金属X的氧化物。
如上所述,本发明的氧化物烧结体基本上由铟、镓和金属X的氧化物组成,在不损害本发明的效果的范围内可含有其他的不可避免的杂质。
此外,本发明的氧化物烧结体,优选在In2O3的方铁锰矿结构中镓和金属X固溶分散。Ga通常固溶分散于In位点,有时一部分Ga2O3残留,这在烧结体制造时成为开裂等的原因。因此,通过添加微量的元素X(X=从Sn、Zr、Ge、Ti中选择的1种以上),能够使Ga2O3不存在。此外,由于导热性也提高,因此将大型的烧结体与背板结合时变得难以断裂。
本发明的氧化物烧结体的密度,优选为6.5~7.2g/cm3。如果密度低,有时由氧化物烧结体形成的溅射靶的表面变黑,诱发异常放电,溅射速度降低。
为了提高烧结体的密度,优选使用原料的粒径为10μm以下的原料,将原料均质地混合。如果粒径大,有可能铟化合物与镓化合物的反应不进行。与没有均质地混合的情形也同样地,有可能存在未反应、异常粒生长的粒子,密度没有提高。
此外,本发明的氧化物烧结体,通常Ga分散于氧化铟,分散的Ga的集合体的直径优选为1μm以下。这里所说的分散,可以是镓离子在氧化铟结晶中固溶的情形,也可以在氧化铟粒内Ga化合物粒子细小地分散。通过Ga细小地分散,能够进行稳定的溅射放电。Ga的集合体的直径能够采用EPMA(电子束微量分析器)测定。
本发明的氧化物烧结体的体积电阻优选为10mΩcm以下。Ga没有完全固溶,观察到Ga2O3等的情形下,有时成为异常放电的原因。更优选为5mΩcm以下。对下限并无特别限制,没有必要小于1mΩcm。
本发明的氧化物烧结体,相对于In和Ga,含100~10000ppm的正三价和/或正四价的金属X。通过含正三价和/或正四价的金属,将烧结体的电阻控制得低成为可能。其中优选锡,其浓度优选100ppm~5000ppm。
金属X与铟金属的原子比优选为X/(In+Ga)=200~5000ppm。更优选为X/(In+Ga)=300~3000ppm,进一步优选为X/(In+Ga)=500~1000ppm。
本发明的氧化物烧结体的制造方法包括:
(a)将平均粒径小于2μm的In化合物粉末、平均粒径小于2μm的Ga化合物粉末及平均粒径小于2μm的金属X的化合物粉末以镓与铟的原子比Ga/(In+Ga)=0.001~0.10、X与铟·镓的原子比X/(In+Ga)=100~10000ppm的方式进行混合来调制混合物的工序;
(b)将上述混合物成型来调制成型体的工序;和
(c)将上述成型体在1200℃~1600℃下烧成2~96小时的工序。
应予说明,平均粒径采用JISR1619中记载的方法测定。
将原料化合物粉末混合的工序中,使用的原料粉末的铟化合物、镓化合物和金属X的化合物可以为氧化物或烧成后成为氧化物的物质(氧化物前体)。作为铟氧化物前体和金属X的氧化物前体,可列举铟或金属X的硫化物、硫酸盐、硝酸盐、卤化物(氯化物、溴化物等)、碳酸盐、有机酸盐(醋酸盐、丙酸盐、环烷酸盐等)、醇盐(甲醇盐、乙醇盐等)、有机金属络合物(乙酰丙酮合物等)等。
其中,为了在低温下完全热分解,使杂质不残存,优选硝酸盐、有机酸盐、醇盐或有机金属络合物。再有,使用各金属的氧化物最适合。
上述各原料的纯度,通常为99.9质量%(3N)以上,优选为99.99质量%(4N)以上,更优选为99.995质量%以上,特别优选为99.999质量%(5N)以上。如果各原料的纯度为99.9质量%(3N)以上,不会由于金属X以外的正四价以上的金属和/或Fe、Ni、Cu等杂质而使半导体特性降低,能够充分地确保可靠性。特别地,如果Na、K、Ca的含量为100ppm以下,制作薄膜时电阻不经年劣化,因此优选。
混合优选采用(i)溶液法(共沉法)或(ii)物理混合法实施。为了降低成本,更优选为物理混合法。
对于物理混合法,将含上述的铟化合物、镓化合物和金属X的化合物的原料粉体装入球磨机、喷射磨、珠磨机、玻珠研磨机等混合器,均一地混合。
混合时间优选为1~200小时。如果小于1小时,有可能分散的元素的均一化变得不充分,如果超过200小时,过度花费时间,有可能生产性变差。特别优选的混合时间为10~60小时。
混合的结果,优选得到的原料混合粉末的平均粒径成为0.01~1.0μm。如果粒径小于0.01μm,粉末容易凝聚,处理性差,而且有时无法获得致密的烧结体。另一方面,如果超过1.0μm,有时无法获得致密的烧结体。
本发明中,原料粉末的混合后,可包含对得到的混合物进行煅烧的工序。煅烧工序中,将在上述工序中得到的混合物煅烧。通过进行煅烧,提高最终得到的溅射靶的密度变得容易。
煅烧工序中,优选在200~1000℃、1~100小时、更优选2~50小时的条件下对(a)工序中得到的混合物进行热处理。如果是200℃以上并且1小时以上的热处理条件,原料化合物的热分解充分地进行。热处理条件如果为1000℃以下和100小时以下,粒子也不会粗大化。
优选地进一步在接下来的成型工序和烧结工序之前将这里得到的煅烧后的混合物粉碎。该煅烧后的混合物的粉碎,使用球磨机、辊磨机、珠磨机、喷射磨等进行是适当的。粉碎后得到的煅烧后的混合物的平均粒径,例如,为0.01~3.0μm,优选0.1~2.0μm是适当的。如果得到的煅烧后的混合物的平均粒径为0.01μm以上,能够得到充分的堆积比重,并且处理变得容易,因此优选。此外,如果煅烧后的混合物的平均粒径为3.0μm以下,使最终得到的溅射靶的密度提高变得容易。应予说明,原料粉末的平均粒径能够采用JISR1619中记载的方法测定。
混合的原料粉末的成型能够采用公知的方法,例如加压成型、冷静水压加压。
加压成型能够使用冷压(ColdPress)法、热压(HotPress)法等公知的成型方法。例如,将得到的混合粉填充到模具中,用冷压机进行加压成型。加压成型在例如常温(25℃)下、100~100000kg/cm2下进行。
通过对原料粉末的成型体进行烧成,从而制造氧化物烧结体。
烧结温度为1200~1600℃,优选为1250~1580℃,特别优选为1300~1550℃。
上述的烧结温度的范围中,在氧化铟中镓容易固溶,能够降低体积电阻。此外,通过使烧结温度为1600℃以下,能够抑制Ga、Sn的蒸散。
烧结时间为2~96小时,优选为10~72小时。
通过使烧结时间为2小时以上,能够提高得到的氧化物烧结体的烧结密度,表面的加工成为可能。此外,通过使烧结时间为96小时以下,能够用适当的时间进行烧结。
烧结优选在氧气气氛下进行。通过在氧气气氛下进行烧结,能够提高得到的氧化物烧结体的密度,能够抑制氧化物烧结体的溅射时的异常放电。氧气气氛可为氧浓度为例如10~100体积%的气氛。不过,也可在非氧化性气氛,例如真空或氮气氛下进行。
此外,烧结能够在大气压下或加压下进行。压力为例如9800~1000000Pa、优选100000~500000Pa。
本发明的氧化物烧结体,能够采用上述的方法制造。本发明的氧化物烧结体能够作为溅射靶使用。本发明的氧化物烧结体由于具有高导电性,因此制成溅射靶的情形下能够采用成膜速度快的DC溅射法。
本发明的溅射靶,除了上述DC溅射法以外,RF溅射法、AC溅射法、脉冲DC溅射法等任何溅射法都能够适用,能够进行无异常放电的溅射。
氧化物薄膜,能够通过使用上述的氧化物烧结体,采用蒸镀法、溅射法、离子镀法、脉冲激光蒸镀法等制作。作为溅射的方法,可列举例如RF磁控管溅射法、DC磁控管溅射法、AC磁控管溅射法、脉冲DC磁控管溅射法等。
作为溅射气体,能够使用氩气等惰性气体与氧、水、氢等反应性气体的混合气体。其中,溅射时的反应性气体的分压因放电方式、功率而异,优选为大致0.1%以上、20%以下。如果小于0.1%,刚成膜后的透明非晶膜具有导电性,有时难以作为氧化物半导体使用。另一方面,如果超过20%,透明非晶膜成为绝缘体,有时难以作为氧化物半导体使用。优选为1~10%。
本发明的氧化物薄膜通过使用上述的本发明的溅射靶而成膜。
此外,本发明的氧化物薄膜含有铟(In)、镓(Ga)和正三价和/或正四价的金属X的氧化物,X/(In+Ga)为100~10000ppm。原子比Ga/(In+Ga)优选为0.005~0.08。优选氧化物薄膜基本上只由铟、镓和金属X的氧化物组成,不含硅。
金属X优选为从Sn、Zr、Ti、Ge、Hf中选择的1种以上。此外,优选本发明的氧化物薄膜具有In2O3的方铁锰矿结构,镓在氧化铟中固溶,原子比Ga/(In+Ga)为0.001~0.15。
镓具有使氧化铟的晶格常数变小的效果,因此具有使迁移率变大的效果。此外,与氧的结合力强,具有使多晶化氧化铟薄膜的氧损失量减少的效果。镓具有与氧化铟完全固溶的区域,与结晶化的氧化铟完全一体化,能够降低晶格常数。如果加入固溶极限以上的镓,有时析出的氧化镓成为电子的散射原因,阻碍氧化铟的结晶化。
此外,添加元素X具有提高靶的热传导的效果。因此,将生产性优异的大型的烧结体结合时,能够防止开裂等破裂。
如果Ga/(Ga+In)的比超过0.10,靶的热传导极端地降低,但通过添加X,能够防止其发生。
本发明的氧化物薄膜通常由方铁锰矿结构的单相组成,对于方铁锰矿结构的晶格常数,对下限并无特别限定,优选为以上且小于晶格常数低意味着使晶格缩小,金属间距离小。通过使金属间距离变小,在金属的轨道上移动的电子的运动速度加快,得到的薄膜晶体管的迁移率变快。如果晶格常数过大,变得与氧化铟自身的晶格相等,迁移率没有提高。
本发明的氧化物薄膜,优选分散的Ga的集合体的直径小于1μm。
本发明的氧化物薄膜能够作为氧化物半导体元件的活性层使用。作为氧化物半导体元件,可列举薄膜晶体管、功率晶体管、相变化存储器等。
本发明的氧化物薄膜,优选能够用于薄膜晶体管。特别地能够用作沟道层。氧化物薄膜能够直接或进一步热处理而使用。
薄膜晶体管可以是沟道蚀刻型。本发明的薄膜为结晶质,具有耐久性,因此使用了本发明的薄膜的薄膜晶体管的制造中,将Al等的金属薄膜蚀刻形成源·漏电极、沟道部的光刻工序也成为可能。
此外,薄膜晶体管也可以是蚀刻阻止层型。本发明的薄膜,蚀刻阻止层能够保护由半导体层形成的沟道部,并且成膜时使大量氧进入半导体层,因此使得经由蚀刻阻止层从外部供给氧变得不必要。此外,由于成膜后即刻为非晶膜,因此将Al等的金属薄膜蚀刻形成源·漏电极、沟道部的同时,能够蚀刻半导体层,缩短光刻工序也成为可能。
此外,薄膜晶体管可以是顶部接触型,也可以是底部接触型。不过,底部接触的情况下,由于附着于源·漏电极表面的水分、氧化被膜的影响,在与氧化物半导体的界面容易产生接触电阻。因此,在氧化物半导体溅射成膜前,通过进行逆溅射或者真空加热将这些除去,从而减小接触电阻,容易得到良好的晶体管。
薄膜晶体管的制造方法包括:使用本发明的溅射靶形成氧化物薄膜的工序;在氧气氛中对上述氧化物薄膜进行热处理的工序;和在上述热处理的氧化物薄膜上形成氧化物绝缘体层的工序。通过热处理而结晶化。
薄膜晶体管中,优选在热处理的氧化物薄膜上,为了防止半导体特性的经时劣化,形成氧化物绝缘体层。
优选地在氧的含量为10体积%以上的成膜气体中,形成氧化物薄膜。作为成膜气体,使用例如氩和氧的混合气体、氩和水蒸汽的混合气体。
通过使成膜气体中的氧浓度为10体积%以上、或者使水蒸汽的浓度为1体积%以上,能够使随后接着的结晶化变得稳定。
特别地在成膜中导入水蒸汽时,为了得到良好的晶体管特性是有效的。如果将水蒸汽导入等离子体中,产生氧化力强的OH自由基(OH·),能够将氧化铟例如如下所述高效地氧化。
In2O3-x+2xOH·→In2O3+xH2O
氧化反应在氧气单独中也进行,但容易残留氧缺损。如果氧缺损多,作为导电体附近的捕集物、给体发挥作用,有时招致On/Off比的降低、S值的恶化。
此外,为了在溅射中OH·在整个基板均一地遍布,等离子体的扩展方式也重要。特别是大型基板的情况下,通过在端部使磁体的摇动速度变慢,确保均一性成为可能。溅射中导入的水的浓度因溅射装置、制造条件而异,因此并不单纯,依赖于等离子体的扩展方式、放电方式的不同、成膜速度、基板·靶距离等。
还可以替代水而同时导入氢和氧。不过,如果氧不足,氢等离子体产生的还原效果占主导,因此有必要相对于氢以1∶2以上的比例导入氧。这种情况下OH·的浓度的控制也重要。
氧化物薄膜的结晶化工序中,能够在氧的存在下或不存在下使用灯退火装置、激光退火装置、热等离子体装置、热风加热装置、接触加热装置等。
升温速度通常为40℃/分以上,优选为70℃/分以上,更优选为80℃/分,进一步优选为100℃/分以上。加热速度无上限,采用激光加热、热等离子体进行加热的情况下,能够瞬间地升温到所需的热处理温度。
优选冷却速度也高,基板速度过大的情况下,有可能基板断裂,或者由于在薄膜中残留内部应力,因此电特性下降。冷却速度过低的情况下,由于退火效果,有可能结晶异常地生长,优选与加热速度同样地设定冷却速度。冷却速度通常为5~300℃/分,更优选为10~200℃/分,进一步优选为20~100℃/分。
氧化物薄膜的热处理优选在250~500℃、0.5~1200分钟下进行。如果低于250℃,有时无法实现结晶化,如果超过500℃,有时对基板、半导体膜给予损伤。此外,如果不到0.5分钟,热处理时间过短,有时无法实现结晶化,如果超过1200分,则花费时间过多。
[实施例]
接着,通过实施例,与比较例进行对比来对本发明进行说明。应予说明,本实施例表示优选的实例,本发明并不受这些限制。因此,基于本发明的技术思想的变形或其他的实施例包含在本发明中。
实施例1~8
作为原料粉体,使用了下述的氧化物粉末。应予说明,平均粒径采用激光衍射式粒度分布测定装置SALD-300V(岛津制作所制)测定,比表面积采用BET法测定。
(a)氧化铟粉:比表面积6m2/g、平均粒径1.2μm
(b)氧化镓粉:比表面积6m2/g、平均粒径1.5μm
(c)氧化锡粉:比表面积6m2/g、平均粒径1.5μm
(d)氧化锆粉:比表面积6m2/g、平均粒径1.5μm
(e)氧化钛粉:比表面积6m2/g、平均粒径1.5μm
(f)氧化锗粉:比表面积6m2/g、平均粒径1.5μm
由(a)和(b)组成的原料混合粉体全体的比表面积为6.0m2/g。
秤量上述的粉体以成为表1中所示的Ga/(In+Ga)比、X/(In+Ga),使用湿式介质搅拌磨机进行混合粉碎。作为粉碎介质,使用了的氧化锆珠粒。粉碎处理中,边确认混合粉体的比表面积,边使比表面积与原料混合粉体的比表面积相比增加2m2/g。
粉碎后,用喷雾干燥器干燥,将得到的混合粉填充到模具(20mm厚)中,用冷压机加压成型。成型后,边使氧流通边在氧气氛中在表1中所示的温度下烧结20小时,制造烧结体。
由切成的大小的烧结体的重量和外形尺寸算出制造的烧结体的密度。这样,不进行煅烧工序,就能够得到烧结体的密度高的溅射靶用烧结体。
此外,使用电阻率计(三菱油化制、ロレスタ),采用四探针法测定该烧结体的体积电阻(导电性)(mΩcm)。
该烧结体的元素组成比(原子比)采用诱导等离子体发光分析装置(ICP-AES)测定。烧结体的原子比与原料的原子比对应。将结果示于表1。
对于得到的烧结体,实施了X射线衍射。在图1、2中示出实施例2、3的X射线图。
对图进行分析的结果,在实施例2、3的烧结体中观察到In2O3的方铁锰矿结构。此外,几乎未能确认Ga2O3结构。
此外,用EPMA观察实施例2中制作的烧结体,结果确认在In2O3中Ga固溶,Ga的直径为1μm以下。
图3中示出EPMA的观察结果。由图3可知,Ga在In2O3中均匀地固溶。在图3的右上的像中,在一部分中也观察到Ga2O3,但直径为1μm以下。
此外,将得到的烧结体粘贴于背板,形成的溅射革巴。粘贴是在热板上设置铜制的背板,放置0.2mm的铟丝,在其上放置烧结体。然后,将热板加热到250℃,铟熔融粘着,从而得到了溅射靶。
在带有100nm厚的热氧化膜(SiO2膜)的导电性硅基板上和石英玻璃基板上,分别使用实施例1~8中得到的靶,在表1中所示的条件下采用溅射法形成了50nm的半导体膜(as-depo)。对这样得到的薄膜的XRD(X射线衍射)进行测定,结果全部为非晶。
接下来,设置金属掩模,形成L:200μm、W:1000μm的沟道部,蒸镀金而形成源·漏电极。
将该元件在空气中、加热到300℃的加热炉内退火1小时,测定沟道部分的XRD(X射线衍射),结果全部结晶化。
对得到的晶体管的特性进行测定,结果如实施例1~8一起示于表1那样,显示良好的晶体管特性。
[表1]
比较例1~3
除了以表2中所示的比将原料粉末混合,烧结以外,与实施例1同样地制造烧结体,进行评价。将结果示于表2。
图4中示出由比较例1的X射线衍射得到的图。在X射线衍射图中,除了In2O3的方铁锰矿结构以外,也确认了Ga2O3结构。
比较例1和3的靶,在结合的位置产生了开裂。推测这是因为2种结晶混合存在而使热传导差,变脆。
使用没有开裂的比较例2的靶,与实施例8同样地制作晶体管,进行评价。其结果,比较例2的半导体由于锡的添加量多,因此导电性高,阈值电压为-10V,比其他半导体差。
[表2]
产业上的利用可能性
本发明的氧化物烧结体能够作为溅射靶使用。使用本发明的溅射靶形成的薄膜能够用于薄膜晶体管。
上述对几个本发明的实施方式和/或实施例进行了详细说明,但本领域技术人员在基本上不脱离本发明的新的教导和效果的情况下,在这些例示的实施方式和/或实施例中引入大量的变形是容易的。因此,这些大量的变形包含在本发明的范围内。
将本说明书中记载的文献的内容全部援用于本文。
Claims (13)
1.一种氧化物烧结体,其特征在于,实质上仅含有铟In、镓Ga和正三价和/或正四价的金属X的氧化物,所述金属X为从Sn、Zr、Ti、Ge、Hf中选择的1种以上的金属,原子比Ga/(Ga+In)为0.005~0.15,相对于In和Ga的总量,金属X的配合量,以重量计为100~5000ppm,镓分散在氧化铟中,且分散的Ga的粒径为1μm以下,在所述氧化物烧结体的X射线图中,观察到了In2O3的方铁锰矿结构,未确认到Ga2O3结构的存在。
2.如权利要求1所述的氧化物烧结体,其特征在于,金属X为从Sn、Zr、Ti、Ge中选择的1种以上的金属。
3.如权利要求1或2所述的氧化物烧结体,其特征在于,所述金属X至少含有Sn。
4.如权利要求1所述的氧化物烧结体,其特征在于,体积电阻为10mΩcm以下。
5.如权利要求1所述的氧化物烧结体,其特征在于,体积电阻为5mΩcm以下。
6.如权利要求1所述的氧化物烧结体,其特征在于,在In2O3的方锰铁矿结构中镓和金属X固溶分散。
7.如权利要求1所述的氧化物烧结体,其特征在于,密度为6.5~7.2g/cm3。
8.如权利要求1~7的任一项所述的氧化物烧结体的制造方法,其特征在于,包括:
将平均粒径小于2μm的铟化合物粉末和平均粒径小于2μm的镓化合物粉末及平均粒径小于2μm的金属X的化合物的粉末,以镓和铟的原子比Ga/(In+Ga)=0.005~0.15、且相对于In和Ga的总量金属X的配合量为100~5000ppm的方式进行混合的工序;
将混合物成型来调制成型体的工序;和
在1200℃~1600℃下将所述成型体烧成2~96小时的工序。
9.如权利要求8所述的氧化物烧结体的制造方法,其特征在于,
在氧气氛中或加压下进行烧成。
10.一种溅射靶,其特征在于,其是由权利要求1~7的任一项所述的氧化物烧结体形成的。
11.一种氧化物薄膜,其特征在于,其是使用权利要求10所述的溅射靶而成膜的。
12.一种氧化物薄膜,其特征在于,实质上仅含有铟In、镓Ga和正三价和/或正四价的金属X的氧化物,所述金属X为从Sn、Zr、Ti、Ge、Hf中选择的1种以上的金属,原子比Ga/(Ga+In)为0.005~0.15,相对于In和Ga的总量,金属X的配合量,以重量计为100~5000ppm,分散的Ga的集合体的直径小于1μm,所述氧化物薄膜仅由In2O3的方铁锰矿结构的单相构成。
13.一种氧化物半导体元件,其特征在于,活性层是由权利要求11或12所述的氧化物薄膜形成的。
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