TW202105762A - Pn接面及其製備方法及用途 - Google Patents
Pn接面及其製備方法及用途 Download PDFInfo
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- TW202105762A TW202105762A TW109111325A TW109111325A TW202105762A TW 202105762 A TW202105762 A TW 202105762A TW 109111325 A TW109111325 A TW 109111325A TW 109111325 A TW109111325 A TW 109111325A TW 202105762 A TW202105762 A TW 202105762A
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- Prior art keywords
- thin film
- film layer
- semiconductor thin
- semiconductor
- indium gallium
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- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000010409 thin film Substances 0.000 claims abstract description 140
- 239000004065 semiconductor Substances 0.000 claims abstract description 138
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 14
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 12
- 229910052738 indium Inorganic materials 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 78
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 claims description 55
- 239000010949 copper Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000758 substrate Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims description 24
- 150000004706 metal oxides Chemical class 0.000 claims description 24
- 239000011669 selenium Substances 0.000 claims description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 20
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 claims description 20
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 16
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 15
- 238000000137 annealing Methods 0.000 claims description 15
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 7
- 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 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 230000004297 night vision Effects 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910016001 MoSe Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000002096 quantum dot Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims 1
- 150000002910 rare earth metals Chemical class 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 17
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- 230000005525 hole transport Effects 0.000 description 11
- 239000005361 soda-lime glass Substances 0.000 description 10
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 9
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 230000031700 light absorption Effects 0.000 description 7
- 239000013077 target material Substances 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 238000001771 vacuum deposition Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 238000010549 co-Evaporation Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 238000012546 transfer 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
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- -1 sulfide ions Chemical class 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- 229910005543 GaSe Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- QMXBEONRRWKBHZ-UHFFFAOYSA-N [Na][Mo] Chemical compound [Na][Mo] QMXBEONRRWKBHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 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
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 208000037805 labour Diseases 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 210000004508 polar body Anatomy 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by at least one potential-jump barrier or surface barrier, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier or surface barrier
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
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- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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- C—CHEMISTRY; METALLURGY
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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
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- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
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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
- C23C14/34—Sputtering
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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
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
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- H01L31/0323—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2 characterised by the doping material
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- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
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- H01L31/14—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto the light source or sources being controlled by the semiconductor device sensitive to radiation, e.g. image converters, image amplifiers or image storage devices
- H01L31/147—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto the light source or sources being controlled by the semiconductor device sensitive to radiation, e.g. image converters, image amplifiers or image storage devices the light sources and the devices sensitive to radiation all being semiconductor devices characterised by at least one potential or surface barrier
- H01L31/153—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto the light source or sources being controlled by the semiconductor device sensitive to radiation, e.g. image converters, image amplifiers or image storage devices the light sources and the devices sensitive to radiation all being semiconductor devices characterised by at least one potential or surface barrier formed in, or on, a common substrate
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/12—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto
- H01L31/16—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto the semiconductor device sensitive to radiation being controlled by the light source or sources
- H01L31/167—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto the semiconductor device sensitive to radiation being controlled by the light source or sources the light sources and the devices sensitive to radiation all being semiconductor devices characterised by at least one potential or surface barrier
- H01L31/173—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto the semiconductor device sensitive to radiation being controlled by the light source or sources the light sources and the devices sensitive to radiation all being semiconductor devices characterised by at least one potential or surface barrier formed in, or on, a common substrate
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/548—Amorphous silicon PV cells
Abstract
本發明係關於一種PN接面及其製備方法及用途,包含所述的PN接面的半導體薄膜元件(尤其是光電二極體元件)及包含所述的半導體薄膜元件的光電感測模組及其廣泛用途。所述的PN接面包含P型銅銦鎵硒半導體薄膜層及N型銅銦鎵硒半導體薄膜層,所述的N型銅銦鎵硒半導體薄膜層由銅銦鎵硒等元素構成,其中銅相較于銦的莫耳數比在1.1至1.5的範圍內且具有化學式Cu(Inx
Ga1-x
)Se2
,其中x的數值在0.6至0.9的範圍內。製備所述的PN接面的方法使用四元靶材、為乾式製程、無須硒化處理且可將所述的PN接面製作於可撓性基板上。
Description
本案係關於一種PN接面及其製備方法及用途、包含所述的PN接面的半導體薄膜元件(尤其是光電二極體元件)及包含所述的半導體薄膜元件的光電感測模組及其廣泛用途。
銅銦鎵硒半導體薄膜不僅對可見光具有優異的感光特性,其對紅外光至近紅外光範圍(780至1100 nm)內的光相較於一般半導體薄膜材料亦具有較佳的感光能力。因此,銅銦鎵硒半導體薄膜可用於製造寬波段的光電二極體元件。
傳統的銅銦鎵硒光電二極體元件包含(1)作為陽極的金屬電極薄膜層、(2)作為吸光層的P型銅銦鎵硒半導體薄膜層、(3)作為緩衝層的N型化合物半導體薄膜層、(4)作為導電層的透明金屬氧化物導電薄膜層及(5)作為陰極的透明金屬氧化物薄膜層(圖1)。
作為陽極的金屬電極薄膜層常以濺鍍使用鉬金屬製備。
作為吸光層、具有高光電轉換特性的P型銅銦鎵硒半導體薄膜層常透過真空磁控濺射鍍膜、真空共蒸鍍鍍膜、印刷鍍膜或電鍍鍍膜等方式、使用選自銅、銦、鎵及硒等元素的二元、三元或四元化合物靶材,將銅銦鎵硒薄膜沉積在鍍有金屬陽極薄膜層的基板上後,再進行硒化製程而得。硒化製程是銅銦鎵硒製程中最重要的一道製程,硒化製程的目的在於提高硒的比例,以提高元件表面能隙,從而解決開路電壓過低的問題。硒化製程亦決定銅銦鎵硒的晶粒大小、組成分佈,從而影響銅銦鎵硒的光電轉換效率。硒化製程主要是在硒的化學氣氛下,將金屬前驅物,轉換成硒化物半導體材料。常見的硒化製程分兩種,分別為快速熱處理(即:Rapid Thermal Process,簡稱RTP)硒化與硒化氫(H2Se)熱處理。RTP熱處理使用固態硒源加熱,優點是產速快,缺點是氣氛均勻性控制不易,所以無法調整晶粒組成導致效率不高。H2
Se熱處理使用硒化氫進行硒化,優點是可控制氣氛,從而得到高效率元件,缺點是批次管狀爐反應產速慢造成反應時間長(8-10小時)。
作為緩衝層的N型化合物半導體薄膜層必須與吸光層的能隙匹配,以形成足夠厚度的空乏區。緩衝層可避免吸光層在後續製程中受到高能量的濺鍍鍍膜製程破壞且可保護吸光層內部的晶體結構。P型銅銦鎵硒半導體薄膜層具有直接能隙,表面可利用鎵或硫離子摻雜來提高能隙,常使用硫化鎘(CdS)作為N型化合物半導體層的材料。然,基於環保考慮,需要一種不含鎘的N型化合物半導體層的半導體薄膜元件。
CN 108470783 A揭露一種感光元件,包含P型銅銦鎵硒半導體薄膜層、本徵銅銦鎵硒薄膜層及N型銅銦鎵硒半導體薄膜層。本徵銅銦鎵硒的薄膜能帶寬約Eg=1.37eV,其化學結構為β-Cu0.49
(In0.56
Ga0.44
)3
Se5
。由此可知本徵銅銦鎵硒的薄膜鍍製需要過量的硒元素,須使用高溫硒化的製程才能夠達成,單純只用濺射或蒸鍍的鍍膜方式是無法達成的。在所述的PIN感光元件中,P型銅銦鎵硒半導體薄膜層的製作,是建立在本徵銅銦鎵硒薄膜層鍍製後,透過與銅或銅合金電極接觸,及經高溫退火使電極的銅元素擴散到本徵銅銦鎵硒薄膜層裡,才形成的。此種製法中的銅元素擴散深度不足,導致金屬電極與P型銅銦鎵硒半導體薄膜層間的介面產生缺陷結構,無法形成良好的歐姆接觸。再者,CN 108470783 A提到本徵銅銦鎵硒薄膜層是主要用於吸收光,使接收的光形成電子-空穴對後,再經過PIN結構的內建電場形成電流轉換成電訊號。然而,本徵銅銦鎵硒薄膜層具有非常多的晶體結構缺陷,且在所述的專利中記載本徵銅銦鎵硒薄膜層厚度範圍三百奈米到三千奈米,P型銅銦鎵硒半導體薄膜層及N型銅銦鎵硒半導體薄膜層為五十奈米到三百奈米,因此本徵銅銦鎵硒薄膜層內部缺陷結構多。缺陷結構會使得電子-空穴對形成的效率低,及金屬電極與P型銅銦鎵硒半導體薄膜層的接著面無法形成良好的歐姆接觸,因此內建電場無法有效地使電子-空穴對分離形成載子電流,PIN的銅銦鎵硒元件結構無法有效運作。此外,由於本徵銅銦鎵硒熱力學不穩定,退火處理時易相分離,因此難以藉由退火減少結構缺陷。
所述的P型銅銦鎵硒半導體薄膜層的硒化製程及使用硫化鎘的N型化合物半導體層的鍍製皆涉及高溫化學反應,使薄膜內部的結構受到影響,從而損害所產生的光電二極體元件的光電轉換效率。因此,技術領域中需要一種無須硒化處理且不含鎘的PN接面,所述的PN接面適用於半導體薄膜元件中。
本發明的一目的在於提供一種無須硒化處理且使用無鎘緩衝層的PN接面。
本發明的另一個目的在於提供一種包含所述的PN接面的半導體薄膜元件,尤其是半導體光電二極體元件。根據本發明的一個實施例,所述的半導體薄膜光電二極體元件進一步包含含有鉬金屬化合物的層。根據本發明的另一個實施例,所述的半導體薄膜光電二極體元件進一步包含發射具有350 nm至1300 nm波長的光的光轉換薄膜層。根據本發明的又一個實施例,所述的半導體薄膜光電二極體元件進一步同時包含含有鉬金屬化合物的層及發射具有350 nm至1300 nm波長的光的光轉換薄膜層。
本發明的又一個目的在於提供一種光電感測模組,包含具有所述的PN接面的半導體薄膜元件,尤其是半導體薄膜光電二極體元件。
本發明的再一個目的在於提供一種所述的光電感測模組的用途,其用於生物辨識、紅外光影像夜視系統感測、近紅外光光電開關或X-光感測。
本案實施例的額外層面及優點將部分地在後續說明中描述、顯示、或是經由本案實施例的實施而闡釋。
本案的實施例將會被詳細的描示在下文中。在本案說明書全文中,將相同或相似的元件以及具有相同或相似的功能的元件通過類似附圖標記來表示。在此所描述的有關附圖的實施例為說明性質的、圖解性質的且用於提供對本案的基本理解。本案的實施例不應被解釋為對本案的限制。
為便於理解本文所陳述的揭示內容,茲於下文中定義若干術語。
術語「約」意謂如由一般熟習此項技術者所測定的特定值的可接受誤差,誤差範圍視如何量測或測定的值而定。
在本文中,除非特別限定,單數形「一」和「所述的」亦包括其複數形。本文中任何和所有實施例和例示性用語(「例如」和「如」)目的僅為了更加突顯本發明,並非針對本發明的範圍構成限制,本案說明書中的用語不應被視為暗示任何未請求的方法及條件可構成實施本發明時的必要特徵。
在具體實施方式及申請專利範圍中,由術語“中的一者”、“中的一個”、“中的一種”或其他相似術語所連接的項目的列表可意味著所列項目中的任一者。例如,如果列出項目A及B,那麼短語“A及B中的一者”意味著僅A或僅B。在另一實例中,如果列出專案A、B及C,那麼短語“A、B及C中的一者”意味著僅A;僅B;或僅C。專案A可包含單個元件或多個元件。專案B可包含單個元件或多個元件。專案C可包含單個元件或多個元件。
在具體實施方式及申請專利範圍中,由術語“中的至少一者”、“中的至少一個”、“中的至少一種”或其他相似術語所連接的項目的列表可意味著所列專案的任何組合。例如,如果列出項目A及B,那麼短語“A及B中的至少一者”意味著僅A;僅B;或A及B。在另一實例中,如果列出專案A、B及C,那麼短語“A、B及C中的至少一者”意味著僅A;或僅B;僅C;A及B (排除C);A及C (排除B);B及C (排除A);或A、B及C的全部。專案A可包含單個元件或多個元件。專案B可包含單個元件或多個元件。專案C可包含單個元件或多個元件。
以下將就本發明內容進行詳細說明。[PN 接面 ]
本發明的PN接面包含下列半導體薄膜層:
(a) P型銅銦鎵硒半導體薄膜層;及
(b) N型銅銦鎵硒半導體薄膜層。
所述的PN接面(圖2)藉由以N型銅銦鎵硒半導體薄膜層取代習知的N型化合物半導體薄膜層,以達減少硒化製程及降低製程溫度的目的。a. P 型銅銦鎵硒半導體薄膜層
本發明所用的P型銅銦鎵硒半導體薄膜層的P型銅銦鎵硒半導體材料中銅相較於銦的莫耳數比在1.6至2的範圍內,例如可為1.60、1.65、1.70、1.75、1.80、1.85、1.90、1.95或2,較佳1.65至1.90,更佳1.75至1.80。當所述的莫耳數比高於2時,膜層內部的晶體結構會形成過多的CuIn
受子缺陷,影響吸光效率及空穴載子傳輸能力;當所述的莫耳數比低於1.6時則無法產生P型銅銦鎵硒半導體。使用所述的莫耳數比的P型銅銦鎵硒半導體具有較低的晶體結構缺陷、及較高的光吸收係數及空穴載子傳輸能力。
根據本發明的一個態樣,所述的P型銅銦鎵硒半導體材料具有化學式Cu(Inx
Ga1-x
)Se2
,其中0.5<
x<
0.625,較佳0.52<
x<
0.62。例如但不限於0.5、0.501、0.503、0.505、0.507、0.509、0.511、0.513、0.515、0.517、0.519、0.521、0.523、0.525、0.527、0.529、0.531、0.533、0.535、0.537、0.539、0.541、0.543、0.545、0.547、0.549、0.551、0.553、0.555、0.557、0.559、0.561、0.563、0.565、0.567、0.569、0.571、0.573、0.575、0.577、0.579、0.581、0.583、0.585、0.587、0.589、0.591、0.593、0.595、0.597、0.599、0.601、0.603、0.605、0.607、0.609、0.611、0.613、0.615、0.617、0.619、0.621、0.623或0.625。b. N 型銅銦鎵硒半導體薄膜層
本發明所用的N型銅銦鎵硒半導體薄膜層的N型銅銦鎵硒半導體中銅相較於銦的莫耳數比在1.1至1.5的範圍內,例如可為1.1、1.15、1.2、1.25、1.3、1.35、1.4、1.45或1.5,較佳1.1至1.35,更佳1.2至1.25。當所述的莫耳數比高於1.5時會無法產生N型銅銦鎵硒半導體,當所述的莫耳數比低於1.1時,膜層內部晶體結構的InCu
施子缺陷會過多,影響電子載子傳輸能力。使用所述的莫耳數比的N型銅銦鎵硒半導體不需硒化處理。
根據本發明的一個態樣,所述的N型銅銦鎵硒半導體材料具有化學式Cu(Inx
Ga1-x
)Se2
,其中0.63<
x<
0.9,較佳0.7<
x<
0.8。例如但不限於0.63、0.631、0.633、0.635、0.637、0.639、0.641、0.643、0.645、0.647、0.649、0.651、0.653、0.655、0.657、0.659、0.661、0.663、0.665、0.667、0.669、0.671、0.673、0.675、0.677、0.679、0.681、0.683、0.685、0.687、0.689、0.691、0.693、0.695、0.697、0.699、0.701、0.703、0.705、0.707、0.709、0.711、0.713、0.715、0.717、0.719、0.721、0.723、0.725、0.727、0.729、0.731、0.733、0.735、0.737、0.739、0.741、0.743、0.745、0.747、0.749、0.751、0.753、0.755、0.757、0.759、0.761、0.763、0.765、0.767、0.769、0.771、0.773、0.775、0.777、0.779、0.781、0.783、0.785、0.787、0.789、0.791、0.793、0.795、0.797、0.799、0.801、0.803、0.805、0.807、0.809、0.811、0.813、0.815、0.817、0.819、0.821、0.823、0.825、0.827、0.829、0.831、0.833、0.835、0.837、0.839、0.841、0.843、0.845、0.847、0.849、0.851、0.853、0.855、0.857、0.859、0.861、0.863、0.865、0.867、0.869、0.871、0.873、0.875、0.877、0.879、0.881、0.883、0.885、0.887、0.889、0.891、0.893、0.895、0.897、0.899或0.9。
根據本發明的PN接面可用於半導體薄膜元件,例如但不限於半導體電晶體元件或半導體光電二極體元件,尤其是半導體光電二極體元件。[ 半導體薄膜光電二極體元件 ]
本發明的半導體薄膜光電二極體元件包含下列部分(圖3):
(a) 作為陽極的金屬電極薄膜層;
(b) 根據本發明的PN接面;
(c) 視需要,作為導電層的透明金屬氧化物導電薄膜層;及
(d) 作為陰極的透明金屬氧化物薄膜層。
所述的半導體薄膜光電二極體元件,在製備過程中因無須硒化處理且不涉及硫化鎘的N型化合物半導體層,因此不涉及高溫化學反應,可使用約150o
C至450o
C的溫度處理即可,避免使薄膜內部的結構受到影響,相較於傳統的光電二極體元件具有更高的光電轉換效率。a. 作為陽極的金屬電極薄膜層
所述的金屬陽極薄膜層,並無特殊限制,可為任何本發明所屬技術領域中具有通常知識者已知的金屬電極材料,例如但不限於包含鉬(Mo)的材料,例如但不限於Mo、Ti/Mo、Cr/Mo、Al/Mo、Au/Mo,或含鈦、金、銀、銅或鉻的材料。b. PN 接面
所述的PN接面為根據本發明的PN接面,包含作為吸光層的P型銅銦鎵硒半導體薄膜層及作為緩衝層的N型銅銦鎵硒半導體薄膜層。所述的P型銅銦鎵硒半導體薄膜層作為吸光層具備有光電轉換能力、具有高光吸收係數(大於105 cm-1
),可吸收具有350 nm至1300 nm波長範圍的光,較佳為700 nm至1100 nm波長範圍的光,更佳為780 nm至900 nm波長範圍的光。所述的N型銅銦鎵硒半導體薄膜層作為緩衝層,與吸光層的能隙匹配形成足夠厚度的空乏區,並避免吸光層在後續製程中受到因高能量的濺鍍鍍膜製程破壞、保護薄膜內部的晶體結構。c. 作為導電層的透明金屬氧化物薄膜層
根據本發明的一個態樣,可使用所述的作為導電層的透明金屬氧化物導電薄膜層,而所述的作為導電層透明金屬氧化物薄膜層並無特殊限制,可為任何本發明所屬技術領域中具有通常知識者已知的金屬電極材料,例如但不限於i-ZnO/ITO、i-ZnO/AZO、i-ZnO/BZO (ZnO:B)、i-ZnO/IWO (In2
O3
:W)、i-ZnO/IWZO (In2
O3
:W:ZnO)。d. 作為陰極的透明金屬氧化物薄膜層
所述的作為陰極的透明金屬氧化物薄膜層並無特殊限制,可為任何本發明所屬技術領域中具有通常知識者已知的金屬電極材料,例如但不限於i-ZnO/ITO、i-ZnO/AZO、i-ZnO/BZO (ZnO:B)、i-ZnO/IWO (In2
O3
:W)、i-ZnO/IWZO (In2
O3
:W:ZnO)。
所述的作為導電層的透明金屬氧化物導電薄膜層和所述的作為陰極的透明金屬氧化物薄膜層的材料可以相同或不同。
根據本發明的一個態樣,所述的半導體薄膜光電二極體元件進一步包含作為空穴傳輸薄膜層的含有鉬金屬化合物的層。所述的空穴傳輸薄膜層較佳介於所述的金屬陽極薄膜層及所述的PN接面中的P型銅銦鎵硒半導體薄膜層之間(圖4),其用以降低鉬金屬薄膜陽極層與P型銅銦鎵硒半導體薄膜層之間的電位差,從而提升空穴傳輸到陽極的效率。所述的空穴傳輸薄膜層為含有鉬金屬化合物的層,其材料例如但不限於二氧化鉬(MoO2
)、二硒化鉬(MoSe2
)或摻雜微量鋰、鈉、鉀、銣、銫等元素中至少一者的鉬金屬化合物。
製作銅銦鎵硒光電二極體時,因鈉鈣玻璃基板中的鹼金屬離子,在高溫製程下可擴散至銅銦鎵硒半導體薄膜層內部,進而改善半導體薄膜層的電性能,常使用鈉鈣玻璃基板,所述的空穴傳輸薄膜層適用於鈉鈣玻璃基板。另一方面,製作薄膜電晶體時,為避免鈉鈣玻璃基板中鹼金屬離子在高溫製程下擴散至薄膜電晶體內部的氧化層內,進而降低薄膜電晶體的電性能,常使用非鈉鈣玻璃基板。所述的空穴傳輸薄膜層習知中可應用於鈉鈣玻璃的基板,而當所述的空穴傳輸薄膜層應用於非鈉鈣玻璃的基板上時,也能保持高光電轉換效率。
根據本發明的另一個態樣,所述的半導體薄膜光電二極體元件進一步包含光轉換薄膜層(圖5)。所述的光轉換薄膜層主要用以將所吸收的不同波長的入射光,轉換為易被作為吸光層的P型銅銦鎵硒半導體薄膜層吸收的光,例如具有350 nm至1300 nm範圍內的波長的光,較佳為700至1100 nm波長範圍的光,更佳為具有780至900 nm波長的光,從而增加P型銅銦鎵硒薄膜層的光吸收,促進光電二極體組件的光電轉換效應。所述的光轉換薄膜層亦具有保護陰極/透明導電氧化物薄膜層不被水氣、酸鹼液體的化學侵蝕的功能,從而提升光電二極體組件壽命。所述的光轉換薄膜層材料並無特殊限制,可為任何本發明所屬技術領域中具有通常知識者已知的發光材料,例如但不限於包含選自由量子點、有機磷光或螢光材料及稀土材料組成的群的光發射材料。
根據本發明的另一個態樣,所述的半導體薄膜光電二極體元件同時包含作為空穴傳輸薄膜層的含有鉬金屬化合物的層及光轉換薄膜層(圖6)。[ 光電感測模組 ]
本發明的光電感測模組包含具有根據本發明的PN接面的半導體薄膜元件。
根據本發明的一個態樣,所述的半導體薄膜元件為半導體薄膜光電二極體元件,該光電感測模組進一步包含半導體薄膜電晶體元件及半導體發光元件。
根據本發明的一個態樣,所述的半導體薄膜光電二極體元件、所述的半導體薄膜電晶體元件及所述的半導體發光元件經整合製作在同一個基板上。
根據本發明的一個態樣,所述的基板例如但不限於玻璃基板或不銹鋼基板,或可撓性基板,例如但不限於塑膠薄膜基板。
根據本發明的一個態樣,所述的半導體薄膜光電二極體元件中金屬陽極薄膜層的材料及所述的半導體薄膜電晶體元件中源漏電極的材料是相同的鉬金屬化合物,可以同時製備。
根據本發明的一個態樣,所述的半導體發光元件可為但不限於X-RAY、UV LED、IR LED、IR LD或RGB OLED光源。
根據本發明的光電感測模組可用於生物辨識、紅外光影像夜視系統感測、近紅外光光電開關或X-光感測。[PN 接面的製備方法 ]
本案中提供一種製造所述的PN接面的方法,其包括以下步驟:
(a) 透過多個連續式真空磁控濺射鍍膜腔室,使用包含銅、銦、鎵及硒等元素的一或多者的靶材逐一鍍上P型銅銦鎵硒半導體薄膜層及N型銅銦鎵硒半導體薄膜層;及
(b) 在惰性氣體氛圍下以350°C至450°C溫度範圍內的溫度進行退火,
其中所述的鍍膜腔室具有兩個靶位。
其中所述的靶材可為二元、三元或四元包含銅、銦、鎵及硒等元素的一或多者的靶材,較佳為三元或四元包含銅、鎵及硒等元素的三元靶材,或包含銅、銦、鎵及硒等元素的四元靶材。例如但不限定為Cuy
GaSez
、Cuy
(Inx
Ga1-x
)Sez
,其中0.5<
x<
0.9,例如但不限定於0.5、0.501、0.503、0.505、0.507、0.509、0.511、0.513、0.515、0.517、0.519、0.521、0.523、0.525、0.527、0.529、0.531、0.533、0.535、0.537、0.539、0.541、0.543、0.545、0.547、0.549、0.551、0.553、0.555、0.557、0.559、0.561、0.563、0.565、0.567、0.569、0.571、0.573、0.575、0.577、0.579、0.581、0.583、0.585、0.587、0.589、0.591、0.593、0.595、0.597、0.599、0.601、0.603、0.605、0.607、0.609、0.611、0.613、0.615、0.617、0.619、0.621、0.623、0.625、0.63、0.631、0.633、0.635、0.637、0.639、0.641、0.643、0.645、0.647、0.649、0.651、0.653、0.655、0.657、0.659、0.661、0.663、0.665、0.667、0.669、0.671、0.673、0.675、0.677、0.679、0.681、0.683、0.685、0.687、0.689、0.691、0.693、0.695、0.697、0.699、0.701、0.703、0.705、0.707、0.709、0.711、0.713、0.715、0.717、0.719、0.721、0.723、0.725、0.727、0.729、0.731、0.733、0.735、0.737、0.739、0.741、0.743、0.745、0.747、0.749、0.751、0.753、0.755、0.757、0.759、0.761、0.763、0.765、0.767、0.769、0.771、0.773、0.775、0.777、0.779、0.781、0.783、0.785、0.787、0.789、0.791、0.793、0.795、0.797、0.799、0.801、0.803、0.805、0.807、0.809、0.811、0.813、0.815、0.817、0.819、0.821、0.823、0.825、0.827、0.829、0.831、0.833、0.835、0.837、0.839、0.841、0.843、0.845、0.847、0.849、0.851、0.853、0.855、0.857、0.859、0.861、0.863、0.865、0.867、0.869、0.871、0.873、0.875、0.877、0.879、0.881、0.883、0.885、0.887、0.889、0.891、0.893、0.895、0.897、0.899或0.9;
其中0.8<
y<
1.2,例如但不限定於0.80、0.801、0.803、0.805、0.807、0.809、0.811、0.813、0.815、0.817、0.819、0.821、0.823、0.825、0.827、0.829、0.831、0.833、0.835、0.837、0.839、0.841、0.843、0.845、0.847、0.849、0.851、0.853、0.855、0.857、0.859、0.861、0.863、0.865、0.867、0.869、0.871、0.873、0.875、0.877、0.879、0.881、0.883、0.885、0.887、0.889、0.891、0.893、0.895、0.897、0.899、0.901、0.903、0.905、0.907、0.909、0.911、0.913、0.915、0.917、0.919、0.921、0.923、0.925、0.927、0.929、0.931、0.933、0.935、0.937、0.939、0.941、0.943、0.945、0.947、0.949、0.951、0.953、0.955、0.957、0.959、0.961、0.963、0.965、0.967、0.969、0.971、0.973、0.975、0.977、0.979、0.981、0.983、0.985、0.987、0.989、0.991、0.993、0.995、0.997、0.999、1.001、1.003、1.005、1.007、1.009、1.011、1.013、1.015、1.017、1.019、1.021、1.023、1.025、1.027、1.029、1.031、1.033、1.035、1.037、1.039、1.041、1.043、1.045、1.047、1.049、1.051、1.053、1.055、1.057、1.059、1.061、1.063、1.065、1.067、1.069、1.071、1.073、1.075、1.077、1.079、1.081、1.083、1.085、1.087、1.089、1.091、1.093、1.095、1.097、1.099、1.101、1.103、1.105、1.107、1.109、1.111、1.113、1.115、1.117、1.119、1.121、1.123、1.125、1.127、1.129、1.131、1.133、1.135、1.137、1.139、1.141、1.143、1.145、1.147、1.149、1.151、1.153、1.155、1.157、1.159、1.161、1.163、1.165、1.167、1.169、1.171、1.173、1.175、1.177、1.179、1.181、1.183、1.185、1.187、1.189、1.191、1.193、1.195、1.197、1.199或1.2;及
其中1.8<
z<
2.2,例如但不限於1.8、1.801、1.803、1.805、1.807、1.809、1.811、1.813、1.815、1.817、1.819、1.821、1.823、1.825、1.827、1.829、1.831、1.833、1.835、1.837、1.839、1.841、1.843、1.845、1.847、1.849、1.851、1.853、1.855、1.857、1.859、1.861、1.863、1.865、1.867、1.869、1.871、1.873、1.875、1.877、1.879、1.881、1.883、1.885、1.887、1.889、1.891、1.893、1.895、1.897、1.899、1.901、1.903、1.905、1.907、1.909、1.911、1.913、1.915、1.917、1.919、1.921、1.923、1.925、1.927、1.929、1.931、1.933、1.935、1.937、1.939、1.941、1.943、1.945、1.947、1.949、1.951、1.953、1.955、1.957、1.959、1.961、1.963、1.965、1.967、1.969、1.971、1.973、1.975、1.977、1.979、1.981、1.983、1.985、1.987、1.989、1.991、1.993、1.995、1.997、1.999、2.001、2.003、2.005、2.007、2.009、2.011、2.013、2.015、2.017、2.019、2.021、2.023、2.025、2.027、2.029、2.031、2.033、2.035、2.037、2.039、2.041、2.043、2.045、2.047、2.049、2.051、2.053、2.055、2.057、2.059、2.061、2.063、2.065、2.067、2.069、2.071、2.073、2.075、2.077、2.079、2.081、2.083、2.085、2.087、2.089、2.091、2.093、2.095、2.097、2.099、2.101、2.103、2.105、2.107、2.109、2.111、2.113、2.115、2.117、2.119、2.121、2.123、2.125、2.127、2.129、2.131、2.133、2.135、2.137、2.139、2.141、2.143、2.145、2.147、2.149、2.151、2.153、2.155、2.157、2.159、2.161、2.163、2.165、2.167、2.169、2.171、2.173、2.175、2.177、2.179、2.181、2.183、2.185、2.187、2.189、2.191、2.193、2.195、2.197、2.199或2.2。
其中所述的退火使用綠光雷射或電加熱器作為加熱源且其中所述的製程為完全乾式製程且無須硒化處理。
所述的惰性氣體並無特殊限制,可為任何本發明所屬技術領域中具有通常知識者已知的惰性氣體,例如但不限為氮氣、氬氣。
所述的快速退火並非硒化、不涉及含硒物質。所使用的加熱源例如但不限於綠光雷射或電加熱器。
根據本發明的一個態樣,使用綠光雷射作為加熱源時,退火時間範圍為10~120秒。 根據本發明的另一個態樣,使用電加熱器作為加熱源時,退火時間範圍為180~600秒。
根據本發明的一個態樣,該PN接面製作於可撓性基板上。[ 半導體薄膜光電二極體元件的製備方法 ]
所述的半導體薄膜光電二極體元件是由真空磁控濺射鍍膜方式製備,當光轉換薄膜層存在時,該光轉換薄膜層採取噴印鍍膜、網印鍍膜、旋轉塗布鍍膜、狹縫式塗布鍍膜、熱轉印鍍膜或轉印貼膜等方式製備。
因為溫度控制在450℃以內,且無須硒化製作工序,所以在光電二極體元件的製作過程中,不會對基板上已經製作好的薄膜電晶體元件薄膜層結構或內部金屬線路,產生化學反應作用,或熱老化作用,導致兩個元件整合在同一基板上喪失使用功能。可以減少製作過程上的工序,又能確保兩種元件整合後的元件工作能力。製備例 製備 PN 接面
1. 將基板置於鍍製P型銅銦鎵硒半導體薄膜層的真空鍍膜腔體裡,此腔體具有兩個靶位,該等靶位使用包含銅、銦、鎵及硒等原子的四元靶材(Cu(In0.63
Ga0.27
)Se2
)。透過共濺射的方式,以每分鐘0.1微米至0.2微米厚度的鍍膜速率沉積薄膜。所得的P型銅銦鎵硒半導體薄膜層的薄膜厚度在1微米至2微米範圍內;
2. 將自步驟1所得的基板傳送至鍍製N型銅銦鎵硒半導體薄膜層的真空鍍膜腔體裡,在此腔體具有兩個靶位,其中一個靶位使用包含銅、鎵及硒等原子的三元靶材(無In,CuGaSe2
),另一個靶位使用包含銅、銦、鎵及硒等原子的四元靶材(Cu(In0.63
Ga0.27
)Se2
)。透過共濺射的方式以每分鐘0.01微米至0.02微米厚度的鍍膜速率沉積薄膜。所得的N型銅銦鎵硒半導體薄膜層的薄膜厚度在0.05微米至0.1微米範圍內。
製備包含所述的PN接面的半導體薄膜光電二極體元件
1. 將玻璃基板置於鍍製鉬金屬薄膜的真空鍍膜腔體裡,加熱至250度後,採用磁控濺射的鍍膜方式,鍍製0.8微米厚的鉬(Mo)金屬薄膜層,作為陽極的金屬電極薄膜層;鍍膜時的腔內壓力在1.0至5.0 x 10-3
mbar範圍內;
2. 將自步驟1所得的鍍有鉬金屬陽極薄膜的基板,傳送至鍍製鉬化鈉(Mo:Na)的真空鍍膜腔裡,鍍製0.01微米至0.03微米厚的鉬化鈉薄膜,作為空穴傳輸薄膜層,其中鈉占使用的鉬化鈉金屬化合物靶材的總重量為12%;
3. 將自步驟2所得的基板使用所述的製備PN接面的步驟製備PN接面;
4. 將自步驟3所得的基板傳送至進行快速退火的真空腔體裡,在惰性氣體氛圍下以350°C至450°C溫度範圍內的溫度進行退火,退火時間範圍為100至300秒;
5. 將自步驟4所得的基板傳送至鍍製作為陰極的透明金屬氧化物薄膜層的真空鍍膜腔裡,此腔體內具有兩個靶位,首先在經快速退火處理的N型銅銦鎵硒半導體薄膜層上,鍍製本徵氧化鋅薄膜,厚度約0.01微米至0.02微米,接著在所述的本徵氧化鋅薄膜上,鍍製氧化銦錫薄膜,厚度約0.01微米至0.02微米。
得到包含玻璃基板 /Mo (0.8微米)/Mo:Na (0.03微米)/P型-銅銦鎵硒(2微米)/N型-銅銦鎵硒(0.05微米)/i-ZnO(0.01微米)/ITO(0.02微米)的半導體薄膜光電二極體元件。當所述的光電二極體元件應用於太陽能電池時,其電流密度與電壓的特性曲線呈現於圖7,其中短路電流(Jsc
)為32.716 mA/cm2
、開路電壓(Voc
)為649 mV、填充因數(FF)為75.5%及發電效率(EFF)為16.03%。
實施例與比較例
表1提供本案光電二極體元件的實施例與文獻記載的比較例間的比較,
表1
比較例1:Inline Cu(In,Ga)Se2
Co-evaporation for High-Efficiency Solar Cells and Modules (IEEE JOURNAL OF PHOTOVOLTAICS, VOL. 3, NO. 3, PAGE 1100-1105, JULY 2013)。
比較例2:Surface modification of CIGS film by annealing and its effect on the band structure and photovoltaic properties of CIGS solar cells (CURRENT APPLIED PHYSICS, 15 (2015) 18-24)。
比較例3:Study of thin film solar cells in high temperature condition (ENERGY PROCEDIA 74 (2015) 1410 – 1417)。
比較例4:Deposition Technologies of High-Efficiency CIGS Solar Cells: Development of Two-Step and Co-Evaporation Processes (CRYSTALS 2018, 8, 296)。
比較例1係關於鈉鈣玻璃(soda-lime glasses)/Mo(約0.35±0.02微米)/銅銦鎵硒(1.7±0.3微米)/硫化鎘(0.05微米)/本徵氧化鋅(i-ZnO, 0.09±0.01微米)/氧化鋅鋁(ZnO:Al, 0.35±0.02微米)/氟化鎂MgF2
(0.105±0.005微米)
比較例2係關於鈉鈣玻璃(soda-lime glasses)/Mo/銅銦鎵硒(2.0微米)/硫化鎘(0.05微米)/本徵氧化鋅(i-ZnO, 0.05微米)/氧化鋅鋁ZnO:Al(0.35微米)
比較例3係關於鈉鈣玻璃(soda-lime glasses)/Mo/銅銦鎵硒(3.0微米)/硫化鎘(0.05微米)/氧化鋅(ZnO, 0.2微米)
比較例4係關於鈉鈣玻璃(soda-lime glasses)/Mo(約1.0微米)/銅銦鎵硒(約2.3微米)/硫化鎘(約0.05微米)/本徵氧化鋅(i-ZnO, 約0.08微米)/氧化鋅鋁(ZnO:Al, 0.35微米)
比較例1至4皆涉及包含硫化鎘的N型半導體薄膜層。值得注意的是,根據本發明的光電二極體元件使用完全乾式、無須硒化處理的製程製備、且環境友善不含鎘,在此狀況下其發電效率(16.03%)相較於先前技術(15.72%至18.8%)最多減少2.77%,甚至相較於比較例2可增加0.31%。
整個說明書中對“一些實施例”、“部分實施例”、“一個實施例”、“另一舉例”、“舉例”、“具體舉例”或“部分舉例”的引用,其所代表的意思是在本案中的至少一個實施例或舉例包含了所述的實施例或舉例中所描述的特定特徵、結構、材料或特性。因此,在整個說明書中的各處所出現的描述,例如:“在一些實施例中”、“在實施例中”、“在一個實施例中”、“在另一個舉例中”,“在一個舉例中”、“在特定舉例中”或“舉例“,其不必然是引用本案中的相同的實施例或示例。此外,本文中的特定特徵、結構、材料或特性可以以任何合適的方式在一個或多個實施例或舉例中結合。
儘管已經演示和描述了說明性實施例,本領域技術人員應理解所述的實施例不能被解釋為對本案的限制,並且可以在不脫離本案的精神、原理及範圍的情況下對實施例進行改變,替代和修改。
樣品 | 發電效率 (η, %) | 開路電壓 (VOC , mV) | 短路電流 (JSC , mA/cm2 ) | 填充因數 (FF, %) |
實施例 | 16.03 | 649 | 32.716 | 75.5 |
比較例1 | 18.56 ± 0.60 | 722.7 ± 3.6 | 33.76 ± 0.94 | 76.09 ± 0.76 |
比較例2 | 15.72 | 620 | 34.16 | 74 |
比較例3 | 18.8 | 678 | 35.22 | 78.65 |
比較例4 | 17.1 | 617 | 36.3 | 76.3 |
10:光電二極體元件結構
11:陽極-金屬電極薄膜層
12:吸光層-P型CIGS半導體薄膜層
13:緩衝層-N型化合物半導體薄膜層
14:透明金屬氧化物導電薄膜層
15:陰極-透明金屬氧化物薄膜層
20:PN接面
22:P型CIGS半導體薄膜層
28:N型CIGS半導體薄膜層
30:半導體薄膜光電二極體元件
31:陽極-金屬電極薄膜層
34:透明金屬氧化物導電薄膜層
35:陰極-透明金屬氧化物薄膜層
40:半導體薄膜光電二極體元件
41:陽極-金屬電極薄膜層
44:透明金屬氧化物導電薄膜層
45:陰極-透明金屬氧化物薄膜層
46:空穴傳輸薄膜層-鉬金屬化合物薄膜層
50:半導體薄膜光電二極體元件
51:陽極-金屬電極薄膜層
54:透明金屬氧化物導電薄膜層
55:陰極-透明金屬氧化物薄膜層
57:光轉換薄膜層
60:半導體薄膜光電二極體元件
61:陽極-金屬電極薄膜層
64:透明金屬氧化物導電薄膜層
65:陰極-透明金屬氧化物薄膜層
66:空穴傳輸薄膜層-鉬金屬化合物薄膜層
67:光轉換薄膜層
在下文中將簡要地說明為了描述本案實施例或現有技術所必要的附圖以便於描述本案的實施例。顯而易見地,下文描述中的附圖僅只是本案中的部分實施例。對本領域技術人員而言,在不需要進步性勞動的前提下,依然可以根據這些附圖中所例示的結構來獲得其他實施例的附圖。
圖1為先前技術中包含P型銅銦鎵硒半導體薄膜層的光電二極體元件結構。
圖2為根據本發明的PN接面。
圖3為根據本發明的半導體薄膜光電二極體元件。
圖4為根據本發明的半導體薄膜光電二極體元件的一個態樣,其包含含有鉬金屬化合物的層。
圖5為根據本發明的半導體薄膜光電二極體元件的一個態樣,其包含光轉換薄膜層。
圖6為根據本發明的半導體薄膜光電二極體元件的一個態樣,其同時包含含有鉬金屬化合物的層及光轉換薄膜層。
圖7為實例中例示本發明和比較例的光電二極體元件應用於太陽能電池時,其電流密度與電壓的特性曲線。
20:PN接面
22:P型CIGS半導體薄膜層
28:N型CIGS半導體薄膜層
Claims (19)
- 一種PN接面,其包含P型銅銦鎵硒半導體薄膜層及N型銅銦鎵硒半導體薄膜層。
- 如請求項1之PN接面,其中該P型銅銦鎵硒半導體薄膜層中的銅相較於銦的原子莫耳數比在1.6至2的範圍內。
- 如請求項1之PN接面,其中該N型銅銦鎵硒半導體薄膜層中的銅相較於銦的原子莫耳數比在1.1至1.5的範圍內。
- 如請求項1至3中任一項之PN接面,其中該N型銅銦鎵硒半導體由銅銦鎵硒材料構成且具有化學式Cu(Inx Ga1-x )Se2 ,其中0.6< x< 0.9。
- 一種製造如請求項1至4中任一項之PN接面的方法,包含以下步驟: (a) 透過多個連續式真空磁控濺射鍍膜腔室,使用包含銅、銦、鎵及硒等元素的一或多者的靶材逐一鍍上P型銅銦鎵硒半導體薄膜層及N型銅銦鎵硒半導體薄膜層;及 (b) 在惰性氣體氛圍下以350°C至450°C溫度範圍內的溫度進行快速退火, 其中該退火使用綠光雷射或電加熱器作為加熱源,且其中該製程為乾式製程且無須硒化處理。
- 如請求項5之方法,其中該PN接面製作於可撓性基板上。
- 一種半導體薄膜元件,其包含如請求項1至4中任一項之PN接面。
- 如請求項7之半導體薄膜元件,其中該元件為光電二極體元件,其進一步包含金屬陽極薄膜層、透明金屬氧化物導電薄膜層及透明金屬氧化物陰極薄膜層。
- 如請求項8之半導體薄膜元件,其進一步包含含有鉬金屬化合物的層。
- 如請求項9之半導體薄膜元件,其中該含有鉬金屬化合物的層包含二氧化鉬(MoO2 )、二硒化鉬(MoSe2 )或摻雜微量鋰、鈉、鉀、銣、銫等元素中至少一者的鉬金屬化合物。
- 如請求項8之半導體薄膜元件,其進一步包含發射具有350 nm至1300 nm範圍內的波長的光的光轉換薄膜層。
- 如請求項11之半導體薄膜元件,其中該光轉換薄膜層發射具有700 nm至1100 nm波長的光。
- 如請求項11之半導體薄膜元件,其中該光轉換薄膜層包含選自由量子點、有機磷光或螢光材料及稀土材料組成的群的光發射材料。
- 如請求項10之半導體薄膜元件,其中該含有鉬金屬化合物的層係介於該金屬陽極薄膜層及該PN接面中的P型銅銦鎵硒半導體薄膜層之間。
- 一種光電感測模組,其包含如請求項7至14中任一項之半導體薄膜元件。
- 如請求項15之光電感測模組,其該半導體薄膜元件係半導體薄膜光電二極體元件,該光電感測模組進一步包含半導體薄膜電晶體元件及半導體發光元件,其中該半導體薄膜元件、該半導體薄膜電晶體元件及該半導體發光元件經整合製作在同一個基板上。
- 如請求項16之光電感測模組,其中該半導體薄膜光電二極體元件中金屬陽極薄膜層的材料及該半導體薄膜電晶體元件中源漏電極的材料是相同的鉬金屬化合物。
- 如請求項16之光電感測模組,其中該半導體發光元件為X-RAY、UV LED、IR LED、IR LD或RGB OLED光源。
- 一種如請求項15至18中任一之光電感測模組的用途,其用於生物辨識、紅外光影像夜視系統感測、近紅外光光電開關或X-光感測。
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US20090084963A1 (en) * | 2007-10-01 | 2009-04-02 | David, Joseph And Negley | Apparatus and methods to produce electrical energy by enhanced down-conversion of photons |
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