CN113555419B - 氧化镓系半导体及其制造方法 - Google Patents
氧化镓系半导体及其制造方法 Download PDFInfo
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- CN113555419B CN113555419B CN202110428555.6A CN202110428555A CN113555419B CN 113555419 B CN113555419 B CN 113555419B CN 202110428555 A CN202110428555 A CN 202110428555A CN 113555419 B CN113555419 B CN 113555419B
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- gallium oxide
- oxide semiconductor
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- equal
- substrate
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- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 101
- 239000004065 semiconductor Substances 0.000 title claims abstract description 100
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000013078 crystal Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000004549 pulsed laser deposition Methods 0.000 claims abstract description 13
- 238000002441 X-ray diffraction Methods 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 59
- 239000000523 sample Substances 0.000 description 44
- 230000000052 comparative effect Effects 0.000 description 25
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 22
- 239000010408 film Substances 0.000 description 22
- 229910052742 iron Inorganic materials 0.000 description 17
- 238000010586 diagram Methods 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 238000006467 substitution reaction Methods 0.000 description 10
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 8
- 229910052733 gallium Inorganic materials 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000011573 trace mineral Substances 0.000 description 4
- 235000013619 trace mineral Nutrition 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- ISQINHMJILFLAQ-UHFFFAOYSA-N argon hydrofluoride Chemical compound F.[Ar] ISQINHMJILFLAQ-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-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
- 238000000227 grinding Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/24—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only semiconductor materials not provided for in groups H01L29/16, H01L29/18, H01L29/20, H01L29/22
- H01L29/247—Amorphous materials
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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
- H01L21/02521—Materials
- H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
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- 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
- C23C14/08—Oxides
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- 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
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
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- 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
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02414—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/0242—Crystalline insulating materials
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- H01L21/02367—Substrates
- H01L21/02433—Crystal orientation
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/0257—Doping during depositing
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- H01L21/02576—N-type
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/0257—Doping during depositing
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- H01L21/02579—P-type
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/0257—Doping during depositing
- H01L21/02573—Conductivity type
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- H01L21/0259—Microstructure
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02587—Structure
- H01L21/0259—Microstructure
- H01L21/02595—Microstructure polycrystalline
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
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Abstract
提供带隙被充分缩小的氧化镓系半导体及其制造方法。提供一种氧化镓系半导体,具有组成由(Ga(1‑x)Fex)2yO3(其中,0.10≤x≤0.40且0.8≤y≤1.2)表示的混晶,并且所述混晶具有β‑gallia构造。另外,提供一种氧化镓系半导体的制造方法,包括采用脉冲激光沉积法来在基板表面形成组成由(Ga(1‑x)Fex)2yO3(其中,0.10≤x≤0.40且0.8≤y≤1.2)表示的混晶的膜,在将所述基板的温度设为T℃时,所述x和所述T满足由500x+800≤T<1000表示的关系。
Description
技术领域
本公开涉及氧化镓系半导体及其制造方法。本公开尤其涉及带隙被缩小的氧化镓系半导体及其制造方法。
背景技术
半导体功率器件被搭载于家电、汽车、铁路车辆(电车)和产业用设备等各种各样的电气设备,作为控制电压和/或电流的器件来使用。在控制电压和/或电流时,电在半导体功率器件中流动。此时,若半导体功率器件的电阻大,则会产生电能损失。例如,在电动汽车的情况下,若在半导体功率器件的电力转换中产生电能损失,则通过一次充电能够行驶的距离变短。因此,在半导体功率器件中,使电阻下降而使电能损失下降是重要的。
作为如上所述的半导体功率器件用的材料,迄今为止,碳化硅和/或氮化镓被开发及实用化。作为与这些材料相比损失更低的半导体功率器件用材料,近年来,氧化镓受到关注。
氧化镓存在具有α、β、γ、δ和ε这5种类型的晶体构造的相。其中最稳定相是具有β型晶体构造的相,即β-Ga2O3相。β-Ga2O3相具有特有的单斜晶系β-gallia构造(以下,有时简称作“β-gallia构造”)。
作为具有β-gallia构造的氧化镓系半导体,例如非专利文献1中公开了组成为(Ga(1-x)Fex)2O3的氧化镓系半导体。另外,非专利文献1中公开了上述氧化镓系半导体使用脉冲激光沉积法形成于750℃的基板上。
现有技术文献
非专利文献1:Yuanqi Huang等,“High-insulatingβ-Ga2O3thin films by dopingwith a valence controllable Fe element”,应用物理学(Applied Physics), A (2018)124:611.
发明内容
半导体功率器件用材料基本上要求具有宽的带隙。氧化镓系半导体具有宽的带隙,但根据半导体功率器件的种类,有时带隙过宽而难以应用。因此,有时想要缩小氧化镓系半导体的带隙。
已知要缩小氧化镓系半导体的带隙,将氧化镓中的部分镓用铁置换是有效的。但是,若铁的置换比例变高,则难以维持β-gallia构造。若氧化镓系半导体中的β-gallia构造受损,则使用了氧化镓系半导体的器件的导电率、耐电压、稳定性及制造成品率受损。因此,如非专利文献1记载的氧化镓系半导体那样,仅做到了向氧化镓添加微量铁作为掺杂剂,尚不能充分缩小带隙。
因此,本发明人发现了期望带隙被充分缩小的氧化镓系半导体及其制造方法这一课题。
本公开是为了解决上述课题而完成的。即,本公开的目的在于提供带隙被充分缩小的氧化镓系半导体及其制造方法。
本发明人为了达成上述目的而反复锐意研究,完成了本公开的氧化镓系半导体及其制造方法。本公开的氧化镓系半导体及其制造方法包括以下方案。
<1>一种氧化镓系半导体,
具有组成由(Ga(1-x)Fex)2yO3(其中,0.10≤x≤0.40且0.8≤y≤1.2)表示的混晶,并且,
所述混晶具有β-gallia构造。
<2>根据<1>项所述的氧化镓系半导体,来源于所述β-gallia构造的X射线衍射峰的半高宽为1度以下。
<3>根据<1>或<2>项所述的氧化镓系半导体,所述x为0.10≤x≤0.30。
<4>根据<1>~<3>项中任一项所述的氧化镓系半导体,所述y为1.0。
<5>一种氧化镓系半导体的制造方法,是制造<1>项所述的氧化镓系半导体的方法,
包括采用脉冲激光沉积法在基板表面形成组成由(Ga(1-x)Fex)2yO3(其中,0.10≤x≤0.40且0.8≤y≤1.2)表示的混晶的膜,
在将所述基板的温度设为T℃时,所述x和所述T满足由500x+800≤T<1000表示的关系。
<6>根据<5>项所述的氧化镓系半导体的制造方法,所述x和所述T满足由500x+800≤T≤950表示的关系。
<7>根据<5>或<6>项所述的氧化镓系半导体的制造方法,所述脉冲激光沉积法中使用的激光是紫外线脉冲激光。
<8>根据<5>~<7>项中任一项所述的氧化镓系半导体的制造方法,所述x为0.10≤x≤0.30。
<9>根据<5>~<8>项中任一项所述的氧化镓系半导体的制造方法,所述y为1.0。
根据本公开,通过采用脉冲激光沉积法在预定的基板温度下成膜,即使用比较多的铁置换镓,也可维持β-gallia构造,能够提供带隙被充分缩小的氧化镓系半导体及其制造方法。
附图说明
图1是示意性地表示本公开的氧化镓系半导体的制造方法中使用的脉冲激光沉积法的说明图。
图2是示出氧化镓系半导体中的混晶的组成、基板温度及结晶性的关系的坐标图。
图3是表示比较例1的试料的X射线衍射图案的图。
图4是表示比较例2的试料的X射线衍射图案的图。
图5是表示实施例1的试料的X射线衍射图案的图。
图6是表示实施例2的试料的X射线衍射图案的图。
图7是表示实施例3的试料的X射线衍射图案的图。
图8是表示比较例3的试料的X射线衍射图案的图。
图9是表示氧化镓系半导体中的混晶的组成与带隙的关系的坐标图。
附图标记说明
12 氛围气体导入装置
14 真空排气装置
20 靶
30 基板
40 激光导入口
50 氧化镓系半导体
100 脉冲激光沉积装置100
具体实施方式
以下,详细说明本公开的氧化镓系半导体及其制造方法的实施方式。再者,以下所示实施方式并不限定本公开的氧化镓系半导体及其制造方法。
以往,脉冲激光沉积法中,认为优选使基板温度成为500~750℃而进行对象物的成膜。即使在上述基板温度的范围内,若基板温度成为600℃以上,则沉积于基板的原子的脱离会被促进,因此成膜速度急剧下降。因而,认为使基板温度成为500~600℃的低温范围进行对象物的成膜更优选。
但是,在氧化镓(Ga2O3)的成膜的情况下,若在500~600℃的低温范围成膜,则难以抑制具有刚玉构造的准稳定相(α-Ga2O3)的生成,其结果,难以得到具有β-gallia构造的最稳定相(β-Ga2O3)。因而,在进行具有β-gallia构造的氧化镓(β-Ga2O3)的成膜的情况下,在650~750℃的高温范围成膜。
另一方面,与氧化镓(Ga2O3)相比,氧化铁(Fe2O3)的带隙窄。因此,通过将镓(Ga2O3)和氧化铁(Fe2O3)混晶化,即,将氧化镓中的部分镓用铁置换而混晶化,能够缩小氧化镓系半导体的带隙。
在进行将氧化镓中的部分镓用铁置换而成的混晶的成膜的情况下,作为靶,使用氧化镓(Ga2O3)和氧化铁(Fe2O3)。氧化镓(Ga2O3)的最稳定相具有单斜晶系β-gallia构造,氧化铁(Fe2O3)的最稳定相具有三方晶系刚玉构造。因而,关于氧化镓(Ga2O3),即使为了得到β-gallia构造而在650~750℃的高温范围成膜,也存在因氧化铁(Fe2O3)而使混晶得不到β-gallia构造这种担心。另外,还存在铁在混晶中偏析的担心。
但是,本发明人发现:实际上,若铁的置换比例(靶的氧化铁(Fe2O3)的配合比例)为预定范围,则通过在超过650~750℃的高温范围与铁的置换比例增加成比例地使基板温度上升,能够进行具有β-gallia构造的相的成膜。
接着,基于这些见解,对本公开的氧化镓系半导体及其制造方法的构成要件进行说明。
《氧化镓系半导体》
首先,对本公开的氧化镓系半导体的构成要件进行说明。
<混晶的组成>
本公开的氧化镓系半导体具有由(Ga(1-x)Fex)2yO3表示的混晶。在该混晶中,氧化镓(Ga2O3)的部分镓被铁置换,铁固溶于氧化镓(Ga2O3)。
铁的置换比例由x表示,满足0.1≤x≤0.4。若x为0.1以上,则相对于氧化镓(Ga2O3),能够将带隙缩小期望量。从该观点来看,x优选为0.15以上,更优选为0.20以上。期望的缩小量是1~2eV。
另一方面,若x为0.40以下,则能够得到具有β-gallia构造的相。从该观点来看,x优选为0.35以下,更优选为0.30以下。
本公开的氧化镓系半导体典型地具有组成由(Ga(1-x)Fex)2yO3(y=1.0)即(Ga(1-x)Fex)2O3表示的混晶,也可以是在0.8≤y≤1.2的范围由y=1.0以外表示的组成的混晶。本公开的氧化镓半导体理想的是所有混晶具有由(Ga(1-x)Fex)2O3表示的组成。但是,因晶格缺陷等,也可以局部地包含不是(Ga(1-x)Fex)2O3的混晶。从该观点来看,y可以为0.85以上、0.90以上或0.95以上,也可以为1.15以下、1.10以下或1.05以下。
本公开的氧化镓系半导体可以在上述混晶之外还含有微量元素等。作为微量元素,典型地可举出掺杂剂。
作为n型掺杂剂,可举出锡(Sn)、钛(Ti)、锆(Zr)、铪(Hf)、钒(V)、铌(Nb)、钽(Ta)、钼(Mo)、钨(W)、钌(Ru)、铑(Rh)、铱(Ir)、碳(C)、硅(Si)、锗(Ge)、锰(Mn)、砷(As)、锑(Sb)、铋(Bi)、氟(F)、氯(Cl)、溴(Br)和碘(I)等。也可以将它们组合使用。
作为p型掺杂剂,可举出镁(Mg)、氢(H)、锂(Li)、钠(Na)、钾(K)、铷(Rb)、铯(Cs)、钫(Fr)、铍(Be)、钙(Ca)、锶(Sr)、钡(Ba)、镭(Ra)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、钯(Pd)、铜(Cu)、银(Ag)、金(Au)、锌(Zn)、镉(Cd)、汞(Hg)、铊(Tl)、氮(N)和磷(P)等。也可以将它们组合使用。
也可以在如上所述的微量元素之外还含有不可避免的杂质。不可避免的杂质是指本公开的氧化镓系半导体的原材料所含的杂质或在制造工序中混入的杂质等无法避免其含有或者为了避免会导致显著的制造成本上升的杂质。在制造工序中混入的杂质等包括因制造上的情况而在实质上不对本公开的氧化镓系半导体的特性造成影响的范围内含有的物质。
本公开的氧化镓系半导体的组成的分析方法没有限制。尤其是本公开的氧化镓系半导体中的混晶组成例如能够使用电子探针微量分析器(EPMA)来分析。由此,能够高精度地分析混晶的成分,尤其是铁的置换比例x。
<混晶的晶体构造>
本公开的氧化镓系半导体中的混晶具有β-gallia构造。由此,导电率和耐电压以及它们的稳定性提高。本公开的氧化镓系半导体的β-gallia构造与氧化镓的最稳定相(β-Ga2O3)具有的晶体构造同等。
β-gallia构造能够通过对本公开的氧化镓系半导体例如进行X射线衍射分析而确认。本公开的氧化镓系半导体的来源于β-gallia构造的X射线衍射峰的半高宽优选为1度以下。由此,本公开的氧化镓系半导体中的β-gallia构造的晶格缺陷少,导电率和耐电压以及它们的稳定性进一步提高。从该观点来看,X射线衍射峰的半高宽优选为0.8度以下、0.6度以下、0.4度以下或0.2度以下。另一方面,X射线衍射的峰的半高宽越小,β-gallia构造的晶格缺陷就越少,但即使晶格缺陷不是全消失,在实用上也没有问题。从该观点来看,X射线衍射峰的半高宽可以为0.1度以上。
《制造方法》
接着,对本公开的氧化镓系半导体的制造方法进行说明。本公开的氧化镓系半导体的制造方法包括成膜工序。以下,对成膜工序进行说明。
<成膜工序>
采用脉冲激光沉积法在基板表面来形成组成由(Ga(1-x)Fex)2yO3(其中,0.10≤x≤0.40且0.8≤y≤1.2)表示的混晶的膜,得到本公开的氧化镓半导体。使用附图对此进行说明。
图1是示意性地表示本公开的氧化镓系半导体的制造方法中使用的脉冲激光沉积法的说明图。
本公开的氧化镓系半导体的制造方法例如使用图1所示的脉冲激光沉积装置100。脉冲激光沉积装置100具备真空腔。在真空腔连结有氛围气体导入装置12和真空排气装置14。
在真空腔的内部设置有靶20、基板30和激光导入口40。靶20和基板30对向。在基板30的未与靶20对向一侧的面设置有基板加热装置32。从脉冲激光振荡器(未图示)发射出的脉冲激光42穿过激光导入口40向真空腔的内部导入。
本公开的氧化镓系半导体的制造方法中,向靶20照射从激光导入口40导入的脉冲激光42,使靶20的一部分蒸发或升华(消融)。另外,利用基板加热装置32加热基板30。于是,蒸发或升华(消融)后的物质沉积在基板30的表面。该沉积物是氧化镓系半导体50。
只要可得到具有组成由(Ga(1-x)Fex)2yO3(其中,0.10≤x≤0.40且0.8≤y≤1.2)表示的混晶的氧化镓系半导体,靶20就没有特别制限。典型地,使用氧化镓(Ga2O3)的粉末与氧化铁(Fe2O3)的粉末的混合粉末的压粉烧结体。以在氧化镓系半导体中的混晶中铁的置换比例x成为期望值的方式,将氧化镓(Ga2O3)的粉末和氧化铁(Fe2O3)的粉末配合。
脉冲激光42的种类没有特别限制。从得到高输出这一观点来看,优选是紫外线脉冲激光。作为激光振荡器,能够使用惰性气体激元激光振荡器和卤素气体激光振荡器等。典型地,能够使用氩气激元激光振荡器和氩氟激元激光振荡器等。
若向靶20照射脉冲激光42,则从靶20中的氧化镓(Ga2O3)和氧化铁(Fe2O3)向真空腔的内部放出镓原子、铁原子和氧原子。此时,优选从氛围气体导入装置12向真空腔的内部供给氧气,以使得镓原子和铁原子被切实地氧化而沉积。
作为基板30,可以使用能够进行具有β-gallia构造的氧化镓(β-Ga2O3)的成膜的基板。作为这样的基板,例如可举出β-Ga2O3、(0001)面α-Al2O3和c面蓝宝石等。从基板的晶体构造与膜的晶体构造的匹配性的观点来看,优选β-Ga2O3基板。从在成膜后调查膜的组成及晶体构造时区分来自基板的信息和来自膜的信息的观点来看,优选(0001)面α-Al2O3基板。
如上所述,成膜中,基板30被加热。若基板温度T为600℃以上,则能够进行晶质的氧化镓系半导体的成膜。另一方面,若基板温度T为1000℃以下,则能够抑制很多构成元素从已成膜的氧化镓系半导体脱离,因此能够抑制成膜速度显著下降。并且,若铁的置换比例x与基板温度T的关系满足0.10≤x≤0.40和500x+800≤T<1000,则成膜后的氧化镓系半导体中的混晶具有β-gallia构造。而且,若铁的置换比例x与基板温度T的关系满足0.10≤x≤0.30和500x+800≤T≤950,则在对成膜后的氧化镓系半导体进行了X射线衍射分析时,来源于β-gallia构造的峰的半高值成为1度以下。即,能够得到晶格缺陷少的β-gallia构造。从该观点来看,在上式中,T可以满足(500x+800)以上且为930以下、900以下、870以下或850以下。
<变形>
即使在到此为止说明的内容以外,本公开的氧化镓系半导体及其制造方法也能够在权利要求书所记载的内容的范围内施加各种变形。如上所述,本公开的氧化镓系半导体在基板上成膜。本公开的氧化镓半导体可以带着基板使用,也可以除去基板而使用。在除去基板而使用的情况下,对本公开的氧化镓系半导体的制造方法追加基板除去工序。基板除去的方法能够应用周知的方法,例如研磨和抛光等。
【实施例】
以下,通过实施例和比较例来进一步具体说明本公开的氧化镓系半导体及其制造方法。再者,本公开的氧化镓系半导体及其制造方法不限定于在以下实施例中使用的条件。
《试料的准备》
使用图1所示脉冲激光沉积装置100,通过以下步骤准备了实施例1~6和比较例1~7的试料。
<实施例1的试料的准备>
在真空腔的内部设置靶20和基板30,使用真空排气装置14对真空腔的内部抽真空。从氛围气体导入装置12向真空腔的内部供给了氧气。氧气的流量是0.6sccm,真空腔的内部压力是0.8Pa。
使用基板加热装置32将基板30加热到850℃(基板温度T是850℃)。向靶20照射脉冲激光42,在加热中的基板30进行了氧化镓系半导体50的成膜。
作为基板30,使用α-Al2O3,沉积面是(0001)。作为脉冲激光42,使用了紫外线脉冲激光。作为脉冲激光振荡器,使用了氩氟激元激光振荡器。作为靶20,使用了氧化镓(Ga2O3)的粉末与氧化铁(Fe2O3)的粉末的混合粉末的压粉烧结体。以铁的置换比例x成为0.10的方式,配合氧化镓(Ga2O3)的粉末和氧化铁(Fe2O3)。
<实施例2的试料的准备>
基板温度T是900℃,并且铁的置换x是0.20,除此以外与实施例1同样地准备了实施例2的试料。
<实施例3的试料的准备>
基板温度T是950℃,并且铁的置换比例x是0.30,除此以外与实施例1同样地准备了实施例3的试料。
<实施例4的试料的准备>
基板温度T是900℃,除此以外与实施例1同样地准备了实施例4的试料。
<实施例5的试料的准备>
基板温度T是950℃,除此以外与实施例1同样地准备了实施例5的试料。
<实施例6的试料的准备>
基板温度T是950℃,除此以外与实施例2同样地准备了实施例6的试料。
<比较例1的试料的准备>
基板温度T是750℃,除此以外与实施例2同样地准备了比较例1的试料。
<比较例2的试料的准备>
基板温度T是850℃,除此以外与实施例2同样地准备了比较例2的试料。
<比较例3的试料的准备>
基板温度T是950℃,并且铁的置换比例x是0.40,除此以外与实施例1同样地准备了比较例3的试料。
<比较例4的试料的准备>
基板温度T是800℃,除此以外与实施例1同样地准备了比较例4的试料。
<比较例5的试料的准备>
基板温度T是650℃,除此以外与实施例2同样地准备了比较例5的试料。
<比较例6的试料的准备>
基板温度T是800℃,除此以外与实施例2同样地准备了比较例6的试料。
<比较例7的试料的准备>
基板温度T是900℃,除此以外与比较例3同样地准备了比较例7的试料。
《评价》
对于各试料,进行了X射线衍射分析。另外,对于实施例1~3和比较例3的试料,评价(测定)了带隙。带隙通过测定光的透射率而评价。具体而言,向试料照射能量不同的光,测定了其透射率。由于仅能量比带隙小的光通过(透过)试料,所以根据该透射率的能量依存性而求出了带隙。
将结果在图2中示出。在图2中,进行X射线衍射分析的结果,关于显示β-gallia构造的峰且该峰的半高值为1度以下的试料,作为结晶性良好的实施例而以圆标记示出,关于未显示β-gallia构造的峰的试料,作为结晶性不良好的比较例而以叉标记示出。另外,关于非专利文献1所示结果,作为以往例以四边标记示出。
另外,图3是表示比较例1的试料的X射线衍射图案的图。图4是表示比较例2的试料的X射线衍射图案的图。图5是表示实施例1的试料的X射线衍射图案的图。图6是表示实施例2的试料的X射线衍射图案的图。图7是表示实施例3的试料的X射线衍射图案的图。图8是表示比较例3的试料的X射线衍射图案的图。图9是表示氧化镓系半导体中的混晶的组成与带隙的关系的坐标图。
从图3~图9可知,能够确认到:满足500x+800≤T<1000的实施例1~6的试料的氧化镓系半导体具有期望的β-gallia构造。另外,从图3和图9能够确认到:在具有β-gallia构造的氧化镓系半导体中,若铁的置换比例x为0.1~0.4,则带隙充分缩小。
从上述结果能够确认到本公开的氧化镓系半导体及其制造方法的效果。
Claims (14)
1.一种氧化镓系半导体,
具有组成由(Ga(1-x)Fex)2yO3表示的混晶,并且,
所述混晶具有β-gallia构造,
其中,0.10≤x≤0.40且0.8≤y≤1.2。
2.根据权利要求1所述的氧化镓系半导体,
来源于所述β-gallia构造的X射线衍射峰的半高宽为1度以下。
3.根据权利要求1或2所述的氧化镓系半导体,
所述x为0.10≤x≤0.30。
4.根据权利要求1或2所述的氧化镓系半导体,
所述y为1.0。
5.根据权利要求3所述的氧化镓系半导体,
所述y为1.0。
6.一种氧化镓系半导体的制造方法,是制造权利要求1所述的氧化镓系半导体的方法,
包括采用脉冲激光沉积法在基板表面形成组成由(Ga(1-x)Fex)2yO3表示的混晶的膜,其中,0.10≤x≤0.40且0.8≤y≤1.2,
在将所述基板的温度设为T℃时,所述x和所述T满足由500x+800≤T<1000表示的关系。
7.根据权利要求6所述的氧化镓系半导体的制造方法,
所述x和所述T满足由500x+800≤T≤950表示的关系。
8.根据权利要求6或7所述的氧化镓系半导体的制造方法,
所述脉冲激光沉积法中使用的激光是紫外线脉冲激光。
9.根据权利要求6或7所述的氧化镓系半导体的制造方法,
所述x为0.10≤x≤0.30。
10.根据权利要求8所述的氧化镓系半导体的制造方法,
所述x为0.10≤x≤0.30。
11.根据权利要求6或7所述的氧化镓系半导体的制造方法,
所述y为1.0。
12.根据权利要求8所述的氧化镓系半导体的制造方法,
所述y为1.0。
13.根据权利要求9所述的氧化镓系半导体的制造方法,
所述y为1.0。
14.根据权利要求10所述的氧化镓系半导体的制造方法,
所述y为1.0。
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