CN104285279B - N-shaped light absorbing zone alloy and its manufacture method and solar cell - Google Patents
N-shaped light absorbing zone alloy and its manufacture method and solar cell Download PDFInfo
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- CN104285279B CN104285279B CN201380025435.5A CN201380025435A CN104285279B CN 104285279 B CN104285279 B CN 104285279B CN 201380025435 A CN201380025435 A CN 201380025435A CN 104285279 B CN104285279 B CN 104285279B
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- absorbing zone
- shaped light
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- 239000000956 alloy Substances 0.000 title claims abstract description 188
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 188
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 102
- 239000011669 selenium Substances 0.000 claims abstract description 74
- 239000010949 copper Substances 0.000 claims abstract description 56
- 239000003708 ampul Substances 0.000 claims abstract description 42
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 41
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 38
- 229910052738 indium Inorganic materials 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 229910052802 copper Inorganic materials 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 32
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005864 Sulphur Substances 0.000 claims abstract description 16
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 16
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical group [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000007789 sealing Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 238000005477 sputtering target Methods 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 24
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 22
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000005083 Zinc sulfide Substances 0.000 claims description 3
- 238000007738 vacuum evaporation Methods 0.000 claims description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 16
- 230000008025 crystallization Effects 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 229910000952 Be alloy Inorganic materials 0.000 abstract 1
- 239000010408 film Substances 0.000 description 37
- 239000004065 semiconductor Substances 0.000 description 37
- 239000010453 quartz Substances 0.000 description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 17
- 239000011701 zinc Substances 0.000 description 17
- 229910052717 sulfur Inorganic materials 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 12
- 229910052951 chalcopyrite Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 229910052793 cadmium Inorganic materials 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- -1 Organometallic zinc compound Chemical class 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000001771 vacuum deposition Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229960002050 hydrofluoric acid Drugs 0.000 description 3
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005842 biochemical reaction Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 229940065285 cadmium compound Drugs 0.000 description 2
- 150000001662 cadmium compounds Chemical class 0.000 description 2
- AQCDIIAORKRFCD-UHFFFAOYSA-N cadmium selenide Chemical group [Cd]=[Se] AQCDIIAORKRFCD-UHFFFAOYSA-N 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 210000000981 epithelium Anatomy 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 2
- 229910000058 selane Inorganic materials 0.000 description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910017435 S2 In Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- 229910001573 adamantine Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L21/0257—Doping during depositing
- H01L21/02573—Conductivity type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L21/02587—Structure
- H01L21/0259—Microstructure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L21/02612—Formation types
- H01L21/02614—Transformation of metal, e.g. oxidation, nitridation
-
- H—ELECTRICITY
- 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
- H01L31/0248—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
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- 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
-
- H—ELECTRICITY
- 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
- H01L31/04—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
- 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
- H01L31/072—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 heterojunction type
- H01L31/0749—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 heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention provide the interface of light absorbing zone and cushion can accurately film forming pn homogeneities bonding layer, the N-shaped CIGS alloys of the conversion efficiency of solar cell or the manufacture method of N-shaped CIGSS alloys and the manufacture method of solar cell can be improved.N-shaped CIGS alloys are manufactured by following operations：Copper, indium, gallium are mixed and vacuum is sealing into ampoule, the 1st operation for making it that CIG alloys are made in high-temperature crystallization, the crushing of CIG alloys is made the 2nd operation of CIG alloy powders；And mix selenium and the compound being made up of IIb races element and VIb races element, the 3rd operation for making it that N-shaped CIGS alloys are made in high-temperature crystallization in CIG alloys after being pulverized.The compound being made up of IIb races element and VIb races element is cadmium selenide or zinc selenide.N-shaped CIGSS5 units be alloy further comprising sulphur, add sulphur in the 3rd operation.
Description
Technical field
Light absorbing zone and p-type light absorbing zone the present invention relates to be used in solar cell carry out the N-shaped light of pn homojunctions
The manufacture method of absorbed layer alloy, and the N-shaped light absorbing zone alloy is formd into N-shaped cigs layer as sputtering target
Solar cell.
Background technology
Solar cell is categorized into silicon systems, series of compounds, organic system generally, and recently, series of compounds solar cell is by the phase
Treat to be uprised for thin, with low uncertainty year in year out, photoelectric transformation efficiency, its exploitation is always in progress.On series of compounds, as light absorbs
The material of layer, uses by copper (hereinafter referred to as Cu), indium (hereinafter referred to as In), gallium (hereinafter referred to as Ga), selenium (hereinafter referred to as instead of silicon
Be Se), the I-III-VI for being referred to as chalcopyrite system of the composition such as sulphur (hereinafter referred to as S)2Compounds of group.It is representational to have two selenizings
Copper and indium CuInSe2, two copper indium gallium selenide Cu (In, Ga) Se2(hereinafter referred to as CIGS), two selenium vulcanization copper and indium gallium Cu (In,
Ga) (S, Se)2(hereinafter referred to as CIGSS) (with reference to patent document 1 etc.).
Chalcopyrite type cpd semiconductor is direct band-gap semicondictor, and optical absorption characteristics are excellent, and energy gap is covered from sulphur
Change aluminum bronze CuAlS23.5eV to tellurium indium copper CuInTe20.8eV wide range of wavelengths, it is also possible to manufacture from region of ultra-red to
The luminous of ultraviolet region, photo detector.Particularly also there are polycrystalline CIGS solar cells to play excellent optical absorption characteristics to cause
Conversion efficiency is 20.3% such report (with reference to non-patent literature 1).
Structure on CIGS thin film solar cell, from light incident side for zinc oxide (ZnO) window layer/cushion/
CIGS light absorbing zones/stepped construction as molybdenum (Mo) electrode is representational structure.On cigs layer, due to In and Se elements
It is constituent, therefore the hair caused by the chemical reaction drastically of In simple substance and Se simple substance may occurs in manufacturing process
Heat, blast.Therefore, it is necessary to make In simple substance and Se simple substance not direct reaction.
Therefore, being following methods for example with the manufacturing process of the CIGS thin film of selenizing method：By splashing on Mo (molybdenum) layer
The stacked film that method forms In, Cu, Ga is penetrated, the stacked film is diluted in 400~550 DEG C of substrate temperature, by Ar (argon)
Contain H2A few hours are processed in the gas of Se (hydrogen selenide), so as to form the CuInSe that particle diameter is for about 3 μm or so2Film.In VI races
In the case that element is S (sulphur), processed in S atmosphere.More than 400 DEG C and H2Se (hydrogen sulfide) gas reactions and obtain Cu
(In, Ga) Se2Film (with reference to patent document 2).
Improve the open-circuit voltage of the high efficiency for realizing CIGS solar cells, it is known that the Gao Pin of light absorbing zone
Matterization is certainly important, and the control of its surface-interface becomes important, and cushion is with cigs layer interface for pn homojunctions are suitable for high efficiency
Change.Relative to heterogeneous engagement, the energy conversion efficiency of the CIGS solar cells of pn homojunctions is good, used as reason, it is believed that
Because homojunction Carrier recombination compared with heterogeneous engagement is few.
Cushion is the n-type semiconductors such as cadmium sulfide (CdS), ZnO, and CIGS forms pn-junction as p-type semiconductor.Generally,
The cushion formed by CdS forms by solution growth method to manufacture, and in the joint interface with the cigs layer of p-type, Cd is with Cd
(OH)2Form be present in surface, and replace Cu sites in CIGS bulks.Therefore, Cd is diffused into cigs layer and surface n
Type, forms shallow homojunction.On the pn homojunctions, there are various motions, it is as described below.
First, in order in the semiconductive thin film formed by the p-type chalcopyrite type cpd semiconductor containing sulphur and/or selenium
Surface part, formation is diffused with the impurity diffusion zone domain of zinc and/or cadmium, by by the p-type chalcopyrite chemical combination containing sulphur and/or selenium
The precursor film that thing semiconductor is formed, enters in the atmosphere containing Organometallic zinc compound and/or organic metal cadmium compound
Row heat treatment.It is consequently formed pn homojunctions (with reference to patent document 3).
Cd is mainly manufactured, but it is also proposed energetically in cigs layer to the diffusion of cigs layer by solution growth method
The method of middle doping Cd.Mo films are formed with 1 μm of thickness by sputtering method on soda-lime glass substrate, as Mo electricity
Pole.Next, using Cu：In：Ga：Se=1：0.5：0.5：The sputtering target of 2 composition is by ion beam sputtering with 1.6 μm
Thickness forms CIGS films, then, continually by by Cu：In：Ga：Se：Cd=1：0.5：0.5：2：X (Cd concentration x=50ppm)
The target that is formed of composition, form the Cd doped layers (with reference to patent document 4) of thickness 56nm.
Additionally, in solar cells, the p-type thin layer of the semiconductor of identical type and the straight surfaces brought into contact of N-shaped thin layer and shape
Highly desirable into pn-junction, therefore, in a vacuum, base feed gas on monocrystal substrate after the heating and make chalcopyrite thin
Layer in grown on substrates, by unstrpped gas individually or multiple combination simultaneously be supplied in substrate with being repeated in such that it is able to essence
The thickly chemical composition of key-course, as a result, foring the chalcopyrite monocrystalline thin layer of high-quality.Thus, there is p-type of the same race
Chalcopyrite thin film and N-shaped chalcopyrite thin film carry out face contact and form the method (with reference to patent document 5) of homogeneous pn junction.
The structure of the CIGSS layer solar cells of raising conversion efficiency is sought on adding S in CIGS, it is incident from light
Rise as zinc oxide (ZnO) window layer/cushion/CIGSS light absorbing zones/stepped construction as molybdenum (Mo) electrode is representational side
Structure.As the manufacture method of CIGSS films, it is proposed that the method by being manufactured including following operations, the operation is：Using as
Functional group has the compound of amino and hydroxyl as solvent, dissolves the respective chalcogenide of Cu, In and Ga, modulation bag
The operation of the complex containing at least a kind in Cu, In and Ga and S and Se as the constituent of chalcogenide；
The complex is coated into the surface of substrate and is dried, manufacture the operation of the epithelium of complex；And be coordinated this
It is heat-treated in the reducing atmosphere of any gas of the epithelium of compound in comprising hydrogen, nitrogen and their mixed gas, in substrate
Surface form operation (reference patent document 6) using at least a kind in Cu, In and Ga and S and Se as the layer of principal component.
And then, as p-type semiconductor and n-type semiconductor using CIGSS as mother metal, there is provided electric conductivity semiconductor high,
High performance semiconductor element is realized by using such p-type semiconductor and n-type semiconductor.Mo is coated with the glass substrate
Electrode, thereon, p-type CuInS is formd by vacuum vapour deposition2Layer.Then, the supply as the Sb of n-type impurity is only stopped,
To be supplied with the form of CuI as the I of p-type impurity, so as in p-type CuInS2N-shaped CuInS is formed on layer2Layer.Thus, identical
Vacuum plant in be continuously manufactured by with CuInS2As the pn homojunctions of mother metal, in N-shaped CuInS2ITO electrode is formed on layer
(with reference to patent document 7).
And then, using the pn-junction of solar cell as by p shapes compound semiconductor layer (p shapes light absorbing zone) and n shape chemical combination
Homojunction or intend homojunction that thing semiconductor layer is constituted, and n shapes compound semiconductor layer is optimal with the combination of n shape cushions
Change and seek high efficiency.The composition of solar cell is included：Substrate；Conductive layer；Containing Ib races element, IIIb races element and
The p shape compound semiconductor layers of VIb races element；N shapes compound containing Ib races element, IIIb races element and VIb races element half
Conductor layer；N shape cushions；N shape window layer；And n shapes transparency conducting layer (with reference to patent document 8).
Prior art literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2004-047917 publications
Patent document 2:Japanese Unexamined Patent Publication 2006-049768 publications
Patent document 3:Japanese Unexamined Patent Publication 2008-235794 publications
Patent document 4:Japanese Unexamined Patent Publication 2000-150932 publications
Patent document 5:Japanese Unexamined Patent Publication 10-74968 publications
Patent document 6:Japanese Unexamined Patent Publication 2010-129660 publications
Patent document 7:Japanese Unexamined Patent Publication 11-87750 publications
Patent document 8:Japanese Unexamined Patent Publication 2005-228975 publications
Non-patent literature
Non-patent literature 1:Philip Jackson, Dimitrios Hariskos, Erwin Lotter, Stefan
Paetel, Roland Wuerz, Richard Menner, Wiltraud Wischmann and Michael Powalla：
Prog.Photov.Res.Appl.2011；19：894-897
The content of the invention
Invent problem to be solved
However, in the manufacture method of above-mentioned conventional solar cell, even if passing through sputtering method shape as cushion
Into CdS films, also only obtain the conversion efficiency of several % or so, additionally, as cushion, in addition to CdS can also using ZnO,
Other compounds such as ZnS, but in the case where cushion is formed as with these materials, even if passing through solution growth method, sputtering method
Any one, can also be produced because of manufacturing condition Cd spread deviation, cannot stablize pn homojunctions, particularly in volume production
There is problem.
The precursor film that will be formed by p-type chalcopyrite type cpd semiconductor, containing Organometallic zinc compound and/or
Heat-treating methods in the atmosphere of organic metal cadmium compound, the method for the Cd that adulterates is asked as there is also its precision control hardly possible
Topic.
The p-type thin layer of the semiconductor of identical type and N-shaped thin layer directly carry out face contact and form the composition of pn-junction,
In the case of CIGS, can be compared by Cu/ (In+Ga) and carry out pn controls.To be easiest to the Cu holes of generation as acceptor,
Cu/ (In+Ga) manufactures p-type CIGS than the region for 0.8~0.9.N-shaped CIGS is In surplus regions, and In fills Cu holes, as
The In holes of alms giver increase.The carrier concentration of such N-shaped CIGS is low, is unsuitable for high efficiency.
Additionally, the p-type thin layer of the semiconductor of identical type and N-shaped thin layer directly carry out face contact and form the composition of pn-junction
In, in the case of CIGSS, pn controls can be carried out by Cu/ (In+Ga) ratios.Using be easiest to generation Cu holes as
Acceptor and in Cu/ (In+Ga) than the region manufacture p-type CIGSS for 0.8~0.9.N-shaped CIGSS is In surplus regions, In landfills
Cu holes, the In holes as alms giver increase.The carrier concentration of such N-shaped CIGSS is low, is unsuitable for high efficiency.
Therefore, by the p-type thin layer of the semiconductor of identical type and the method for N-shaped thin layer film forming while impurity is supplied
There are problems that accurate control is difficult such.
The present invention be in view of such aspect and propose, its object is to provide to improve light conversion efficiency, in light
The interface of absorbed layer and cushion being capable of accurately film forming pn homojunctions layer, it is possible to increase the conversion efficiency of solar cell
The manufacture method of N-shaped light absorbing zone alloy and the manufacture method of solar cell.
Means for solving the problems
The present invention is formed by N-shaped light absorbing zone alloy between the p-type light absorbing zone and cushion of solar cell
Pn homojunctions layer seeks high efficiency.
N-shaped light absorbing zone alloy is the alloy comprising copper, indium, gallium, selenium and IIb races element, is the CIGS alloys of N-shaped.
The N-shaped light absorbing zone alloy is by the compound that makes copper, indium, gallium, selenium and be made up of IIb races element and VIb races element in height
The CIGS that temperature is crystallized and forms N-shaped crystallizes to manufacture.The compound being made up of IIb races element and VIb races element is cadmium selenide
Or zinc selenide.
The cadmium or zinc of IIb races are diffused into CIGS crystallizations and CIGS are carried out into N-shaped, are conduct as VIb races element
CIGS4 units are the selenium of the composition of alloy, so that the effect in the selenium hole with landfill CIGS.
Additionally, the CIGSS that N-shaped light absorbing zone alloy is the N-shaped comprising copper, indium, gallium, selenium, sulphur and IIb races element is closed
Gold.The N-shaped light absorbing zone alloy is by making copper, indium, gallium, selenium, sulphur and compound comprising IIb races element and VIb races element
The CIGSS for forming N-shaped in high-temperature crystallization crystallizes to manufacture.The compound being made up of IIb races element and VIb races element is selenium
Cadmium, cadmium sulfide, zinc selenide or zinc sulphide.The cadmium or zinc of IIb races are diffused into CIGSS crystallizations and CIGSS are crystallized into N-shaped,
It is the selenium or sulphur of the composition for being alloy as CIGS4 units as VIb races element, so that selenium hole, sulphur with landfill CIGSS
The effect in hole.
The manufacture method of the N-shaped light absorbing zone alloy comprising copper, indium, gallium, selenium and IIb races element, it is characterised in that tool
Standby following operations：Make the compound comprising copper, indium, gallium that the 1st operation of CIG alloys is made in high-temperature crystallization；By CIG alloys
Crush and be made the 2nd operation of CIG alloy powders；And in CIG alloys after being pulverized mix selenium and by IIb races element with
The compound that VIb races element is constituted, the 3rd operation for making it that N-shaped CIGS alloys are made in high-temperature crystallization.
During manufacture CIG3 units are the 1st operation of alloy and the 3rd operation of manufacture N-shaped CIGS alloys, by mixed material
Make crystalline growth from liquation at 1000~1100 DEG C and form polycrystalline.In the 1st operation and manufacture N-shaped CIGS of manufacture CIG alloys
In 3rd operation of alloy, mixed raw material are sealing into ampoule by vacuum.Ampoule is the quartz glass covered by carbon.
The manufacture method of the N-shaped light absorbing zone alloy comprising copper, indium, gallium, selenium, sulphur and IIb races element, its feature exists
In copper, indium, gallium to be mixed the 1st operation for making that its manufactures CIG alloys in high-temperature crystallization；CIG alloys are crushed and is manufactured
2nd operation of CIG alloy powders；And mix selenium, sulphur and by IIb races element and VIb races element in CIG alloys after being pulverized
The compound of composition, the 3rd operation for making it that N-shaped CIGSS alloys are manufactured in high-temperature crystallization.
During manufacture CIG3 units are the 1st operation of alloy, make crystalline growth from liquation at 1000~1100 DEG C and generate polycrystalline,
The 3rd operation for manufacturing N-shaped CIGSS alloys possesses following step：Temperature is maintained by certain hour at 180~220 ° by intensification
First step；And temperature is maintained the second step of certain hour at 1000~1100 °.
In manufacture CIG3 units are the 1st operation of alloy and the 3rd operation of manufacture N-shaped CIGSS alloys, mixed former material
Material is sealing into ampoule by vacuum.Ampoule is the quartz glass covered by carbon.
The N-shaped CIGS alloys for producing and the N-shaped light absorbing zone alloy as N-shaped CIGSS alloys, by slicing process
And be sliced, it is fabricated to N-shaped light absorbing zone sputtering target.Additionally, in order that shape is adapted for use with device, it is also possible under
State operation to manufacture N-shaped light absorbing zone sputtering target, the operation is：N-shaped light absorbing zone is crushed and powdered with alloy
Powdered operation；By the bulk chemical industry sequence of powdery N-shaped CIGS alloys bulk by pressure processing；And by bulk
The slicing process of the N-shaped light absorbing zone alloy section changed.
Solar cell of the present invention, using the N-shaped light absorbing zone sputtering target for producing, by sputter equipment,
N-shaped light absorbing zone is formed with the light absorbing zone of the p-type being laminated on substrate.N-shaped light absorbs layer by layer be laminated in the N-shaped light
The cushion that absorption is gone up layer by layer has identical IIb races element.
The manufacture method of solar cell possesses following N-shaped light absorbing zone film formation process：Use the N-shaped light absorbs for producing
Layer sputtering target, by sputter equipment, in the light absorbing zone film forming N-shaped light absorbing zone of the p-type being laminated on substrate.
In addition it is also possible to using the N-shaped light absorbing zone alloy for producing, by vacuum evaporation, be laminated in the p-type of substrate
Light absorbing zone on film forming N-shaped light absorbing zone.
The effect of invention
According to the present invention, possess pn homojunctions layer between the light absorbing zone and cushion of the p-type of solar cell, therefore
The high efficiency of solar cell can be realized.
For pn homojunctions layer, due to using the n by addition and cushion identical IIb race's elements and N-shaped
Type light absorbing zone with alloy to sputter or vacuum evaporation is come film forming, therefore, it is possible to critically control the amount and pn of IIb races element same
The thickness of matter knot layer.
For the manufacture of N-shaped light absorbing zone alloy, it is to avoid In simple substance mixes with the direct of Se simple substance, make first In with
It is mixed into Se and CdSe etc. and crystallizes it after Cu and Ga crystallization, therefore the blast not caused by chemical reaction drastically
Worry, can safely manufacture.
Brief description of the drawings
Fig. 1 is the figure of the structure for illustrating CIGS solar cells.
Fig. 2 is the figure of the structure for illustrating CIGSS solar cells.
Fig. 3 is the figure of the energy spectrum band for showing CIGS solar cells.
Fig. 4 is the figure for illustrating the state that Cd spreads from the CdS layer of CIGS solar cells to cigs layer.
Fig. 5 is the figure of the structure of the solar cell that explanation is provided with N-shaped cigs layer.
Fig. 6 is the figure of the structure of the solar cell that explanation is provided with N-shaped CIGSS layers.
Fig. 7 is the flow chart of the summary of the manufacture method for showing N-shaped CIGS alloys.
Fig. 8 is the flow chart of the manufacture method for showing N-shaped CIGS alloys.
Fig. 9 is the figure of the manufacture state for illustrating the N-shaped CIGS alloys in electric furnace.
Figure 10 is the figure for illustrating the temperature control status in electric furnace.
Figure 11 is the flow chart of the summary of the manufacture method for showing N-shaped CIGSS alloys.
Figure 12 is the flow chart of the manufacture method for showing N-shaped CIGSS alloys.
Figure 13 is the figure for showing the temperature control status in electric furnace.
Figure 14 is the figure for showing the temperature control status in the electric furnace in the manufacture of 1 technique.
Figure 15 is the flow chart of the manufacture method of sputtering target.
Figure 16 is the use of the schematic diagram that the N-shaped cigs layer of N-shaped CIGS alloy sputtering targets is formed.
Figure 17 is the figure for showing the manufacture state using the N-shaped cigs layer of sputter equipment.
Figure 18 is the use of the flow of the manufacture method of the solar cell of N-shaped CIGS alloy sputtering targets of the present invention
Figure.
Figure 19 is the plan for illustrating vacuum deposition apparatus.
Figure 20 is the figure of the manufacture state for showing the N-shaped cigs layer in vacuum chamber.
Specific embodiment
The compound semiconductor worked as the light absorbing zone of solar cell is p-type semiconductor, make use of following property
Matter：If being in equally spaced 2 kinds of elements with IV races and being formed chemical combination by clipping IV races (Si, Ge etc.) in the periodic table of elements
Thing, then form same chemical bond and turn into semiconductor.To belong to the I-III-VI of adamantine series2Race's element, crystal
Structure is chalcopyrite structure.
In chalcopyrite crystal structure, the Cu of I races, each atom of S, Se of Ga, In, VI race of III form 4 and are coordinated, tool
There is tetragonal crystal structure.The energy gap of the semiconductor of chalcopyrite throughout 0.26~3.5eV wide scope, but I-
III-VI2Ionic strong, the another aspect mobility ratio I-IV-V of race's element2Race is weak, therefore, what is used in the past is representational
CIS, CIGS are acted with the value lower than preferred energy gap.
N-shaped light absorbing zone alloy of the invention is inhaled as by the N-shaped light that homojunction is formed for the light absorbing zone with p-type
Receive the material of layer film forming and use.In the present invention, light absorbing zone is using CIGS solar cells and CIGSS solar cells as right
As N-shaped light absorbing zone alloy is used as by the term of N-shaped CIGS alloys and N-shaped CIGSS alloy general names.
It is by CuInSe as the CIGS of the light absorbing zone of CIGS solar cells2The mixed crystal that be instead of with Ga of In sites
Semiconductor.For CIGS, because Cu Holes buffer layer energy is small, generation is easiest to, therefore as Cu- on ratio of components
Poor and constitute stabilization p-type semiconductor.
Fig. 1 is the figure of the structure for showing CIGS solar cells 10.On the substrate 12, it is laminated with Mo as backplate 14
(molybdenum) layer.Light absorbing zone 16 is made up of the CIGS thin film as p-type semiconductor.For the CIGSS of the p-type as light absorbing zone 16
Film, formation forms pn-junction as the cushion 18 of n-type semiconductor, is worked as solar cell.Make in cushion 18
With such as cadmium sulfide (CdS), Zinc oxide (ZnOOHS).And then electricity high is laminated by high-resistance zinc oxide (ZnO) etc.
Resistance cushion 20, the transparency electrode 22 formed by ITO, aluminium etc. is formed with topmost.
On the other hand, now as CIS, the CIGS used light absorbing zone due to using harmful Se more, therefore
It is also contemplated that and reduces Se as far as possible, it is proposed that the CIGSS that a part of Se has been replaced with S.
The CIGSS of light absorbing zone may be considered as CIS, CGS and CuInS of basic 3 crystallizations2Mix and structure
Into structure.That is, energy gap is formed into energy gap for the CIS and energy gap of 1.04eV are the CGS mixing of 1.68eV
The polycrystalline of the CIGS of 1.2eV, and then, in order to reduce the amount of Se, be by energy gap for 1.54eV CuInS2Polycrystalline mix and
The structure for obtaining.CuInS2Mobility it is low up to 15cm2/ Vs, but can make final CIGSS energy gap be 1.4eV.
The CIGSS light absorbing zones of CIGSS solar cells are by CuInSe2The mixed crystal that be instead of with Ga and S of In sites
Semiconductor.Cu Holes buffer layers energy is small in CIGSS, is easiest to generation, therefore constituted surely as Cu-poor on ratio of components
Fixed p-type semiconductor.
Fig. 2 is the figure of the structure 11 for showing CIGSS solar cells.On the substrate 12, it is laminated with as backplate 14
Mo (molybdenum) layer.Light absorbing zone 16 is made up of CIGSS layers as p-type semiconductor.For the p-type as light absorbing zone 16
CIGSS layers, formation forms pn-junction as the cushion 18 of n-type semiconductor, is worked as solar cell.In cushion 18
Such as cadmium sulfide (CdS), low-resistance zinc oxide (ZnO) are used.And then be laminated by high-resistance zinc oxide (ZnO) etc.
High resistance buffer layer 20, the transparency electrode 22 formed by ITO, aluminium etc. is formed with topmost.On CIGSS solar cells,
S compositions are only added in light absorbing zone 16 relative to CIGS solar cells, substantially structure is identical with principle.
Fig. 3 is the energy band diagram of CIGS solar cells.Display fermi level 26, valence band 28 and conduction band 30
Bands of a spectrum state.Depletion layer 24 is formed in the combination interface of light absorbing zone 16 and cushion 18, boundary defect 32 is produced in band gap.
From the side of transparency electrode 22, incident light reaches light absorbing zone 16 by high resistance buffer layer 20, cushion 18.Light absorbing zone 16
In, the electronics of valence band 28 is excited by conductor, generates electron-hole pair.The electronics generated by the CIGS of p-type passes through depletion layer
24 electric field is accelerated and passes through cushion 18, tends to the side of transparency electrode 22, so if wiring can then take out electric current.
Cushion 18 is mainly formed by solution growth method film forming CdS, ZnO layer.By containing Cd, Zn salt and sulphur compound
Alkaline aqueous solution chemically formed, for example CdS is separated out from Cd salt and thiocarbamide, for ZnO systems, precipitation ZnOOHS.Solution growth
Method is the ion species reaction of the chemical reaction based on slaine, sulfide and complex, initial in the growth of CdS cushions
In the stage, the surface oxide layer of CIGS films, superfluous Na are removed by the etching in ammonia spirit.And, Cd2+ ions with
The Cu of CIGS film superficial layers or take off Cu hole displacement.Thus, Cd works as alms giver in CGIS superficial layers and forms N-shaped biography
Lead, form CGIS layers of N-shaped, the cigs layer with the p-type semiconductor as light absorbing zone 16 forms pn homojunctions.
In the case where cushion 18 has used ZnO similarly, Cu the or Cu holes of Zn and CIGS are replaced, as N-shaped
CIGS and form pn homojunctions.
Fig. 4 is displayed in the state that cushion is formed with pn homojunctions with the interface of cigs layer.Fig. 4 (A) is shown by Cd
It is formed with the laminated arrangement of N-shaped CIGS.Boundary face in the side of cushion 18 of depletion layer 24 is formed with N-shaped cigs layer 34.Fig. 4
(B) it is to form the energy band diagram in the state of N-shaped cigs layer 34.On cushion 18 and the boundary of light absorbing zone 16 (cigs layer)
Face is formed with pn homojunctions.The bottom of the conduction band 30 in cushion 18 becomes discontinuous by projection, forms light induced electron
Obstacle and reduce efficiency with the hole-recombination of valence band 28 via boundary defect 32.However, by as light absorbing zone 16
The electronics that excites of CIGS, because the depletion layer 24 before projection has pn homojunctions layer, therefore the compound of carrier tails off, its
Result is can to form efficient CIGS solar cells.
The energy band diagram of CIGSS solar cells and it is formed with pn homojunctions at cushion and CIGSS layers of interface
State, it is also same with CIGS solar cells.
Fig. 5 is to be provided with N-shaped to form pn homojunctions layer between cushion 18 and light absorbing zone 16 (cigs layer)
The CIGS solar cells of cigs layer 34.In the present invention, pn homojunctions layer is not in the cushion 18 using solution growth method
Film forming procedure in the generation of naturally-occurring ground, and be able to critically to control dense with the identical IIb races element of cushion 18
Spend and realize high efficiency, manufacture includes the N-shaped CIGS alloys with the identical IIb races element of cushion 18, cushion 18 with
N-shaped cigs layer 34 is formed between light absorbing zone 16 (cigs layer).N-shaped CIGS alloys are, for example, that Cd or Zn is with the addition of in CIGS
Alloy.
In addition, cushion 18 forms pn-junction as n-type semiconductor with as the cigs layer of p-type semiconductor, but by setting
N-shaped cigs layer 34, it is also possible to be not provided with cushion 18.In this case, that added in N-shaped CIGS alloys can be Cd or Zn
In the IIb races element of any one.
Fig. 6 is to be provided with N-shaped to form pn homojunctions layer between cushion 18 and light absorbing zone 16 (CIGSS layers)
CIGSS layers 34 of CIGSS solar cells.In the present invention, pn homojunctions layer is not in the cushion using solution growth method
Naturally-occurring ground generation in 18 film forming procedure, and be able to critically control and the identical IIb races element of cushion 18
Concentration simultaneously realizes high efficiency, and manufacture includes the N-shaped CIGSS alloys with the identical IIb races element of cushion 18, in cushion 18
N-shaped is formed between light absorbing zone 16 (CIGSS layers) CIGSS layers 34.N-shaped CIGSS alloys are, for example, that Cd is with the addition of in CIGSS
Or the alloy of Zn.
In addition, in the same manner as CIGS solar cells, in CIGSS solar cells, cushion 18 is used as n-type semiconductor
Pn-junction is formed with CIGSS layers as p-type semiconductor, but by setting N-shaped CIGSS layers 34, it is also possible to it is not provided with cushion 18.
In this case, N-shaped CIGSS alloys addition can be Cd or Zn the IIb races element of any one.
Next as N-shaped light absorbing zone alloy, to CIGS solar cells using N-shaped CIGS alloys manufacture
Method is illustrated.
Main use can obtain efficient CdS, Zn system in cushion 18, with regard to N-shaped CIGS alloys constitution element and
Speech, Cd and/or Zn is also added with except Cu, In, Ga, Se.In this composition element, if In simple substance mixes with Se simple substance, send out
It is biochemical reaction and generate heat, significantly in the case of can explode.For In and Se, in order to not make simple substance be mixed with each other, make it
Crystallized after separation.Additionally, it is IIb races element and the compound of the VIb races Se of one of the constitution element as CIGS that Cd is used
CdSe, Zn is used as the ZnSe with the compound of VIb races Se, is necessary using the manufacture method of safety.
The cadmium or zinc of IIb races as the CIGS alloy N-shapeds of p-type, will make unit of VIb races by being diffused into CIGS crystallizations
Element is the selenium of the composition for being alloy as CIGS4 units, so that the effect with the selenium hole in landfill CIGS crystallizations.
Hereinafter, mainly illustrated in case of cushion 18 uses CdS.
Fig. 7 is the flow chart 40 of the outline of the manufacture method for showing N-shaped CIGS alloys.In the figure 7, in step sl, will
The polycrystalline of CIG alloys is manufactured in the elemental composition of CIGS alloys except Cu, In and Ga of Se mix.Next, in step S2
In, CIG alloys are crushed, mix with Se and CdSe.On In, due to being crystallized as CIG alloys, even if therefore mixing
Se simple substance does not also chemically react.Next, manufacturing the polycrystalline of N-shaped CIGS alloys in step 3.Thus, by safety
Manufacture method completes N-shaped CIGS alloys.
Fig. 8 is the flow chart 42 of the manufacturing process for showing N-shaped CIGS alloys.It is accurate first in as S11 the step of preparation
It is ready for use on the ampoule and the ampoule for manufacturing N-shaped CIGS alloys of manufacture CIG alloys.Ampoule uses the peace of such as quartz glass
Small jar, illustrates as quartz ampoule below, but is not limited to quartz glass.Chloroazotic acid washing and nitric acid hydrogen are carried out to quartz ampoule
Fluoric acid is washed, and makes moisture evaporation with drying machine in advance.And then soak in acetone, then heated with burner and remove coal smoke
Son.Thus quartz ampoule is covered by carbon, is prevented from being mixed into for the impurity from quartz.
Chloroazotic acid washing and nitric hydrofluoric acid washing are carried out to quartz ampoule, makes moisture evaporation with drying machine in advance.And then soak
Bubble in acetone, is then heated with burner and removes coal smoke.Thus quartz ampoule is covered by carbon, is prevented from the analysis of impurity
Go out.
In step S12, Cu, In and Ga are washed using hydrochloric acid etc., weigh so that pantogen subnumber ratio is 1：
0.8：0.2 and vacuum is sealing into the quartz ampoule covered by carbon.
In step s 13, vacuum is sealed with into the quartz ampoule of raw material to put into the electric furnace for heating.In step
In S14, the heater being pointed in stove is powered and it is generated heat, and temperature is risen to 1050 DEG C.And, by 1050 DEG C of the height
Temperature state maintains certain hour, makes liquation crystalline growth and after making raw material polycrystallization, in-furnace temperature is declined in step S15
To room temperature.Thus, CIG alloys can be obtained.
In step s 16, CIG alloys are taken out from the quartz ampoule that have decreased to room temperature, the CIG alloys is crushed.This
When, uniform micro mist can be obtained by screen cloth.Such crystal powder is crystallized due to In together with Cu and Ga, thus not with Se send out
Biochemical reaction.
In step S17, weigh so that chippy CIG alloys and addition there are the Se compositions of Se simple substance and CdSe
Se pantogens subnumber compares 1 for pantogen subnumber：2 ratio.The addition of Cd is controlled by the amount of CdSe now.Weigh
Material vacuum is sealing into the quartz ampoule covered by carbon.And then, in putting into electric furnace in step S18.Next, in step
In-furnace temperature is risen to 1050 DEG C in rapid S19,1050 DEG C of temperature is maintained into certain hour, make liquation crystalline growth and polycrystalline
After change, in-furnace temperature is dropped into room temperature in step S20, N-shaped CIGS alloys are taken out from quartz ampoule.
Fig. 9 is the figure of the manufacture state 44 for showing the use electric furnace in N-shaped CIGS alloys manufacturing process illustrated in fig. 8.
There is the heater 48 of heating in electric furnace 46, heater 48 is by the way that generating heat rises in-furnace temperature from outside energization.
The quartz ampoule 52 that vacuum has enclosed raw material 50 is placed with the inside of electric furnace 46.In-furnace temperature is by from outside control
Device is (not shown.) controlled.
The temperature control status 54 in electric furnace in the manufacturing process of Figure 10 display N-shaped CIGS alloys.Exist in room temperature first
The quartz ampoule that vacuum has enclosed raw material Cu, In, Ga is put into stove, heater is powered and in-furnace temperature is increased.Temperature
Rising rose to 1050 DEG C with such as 12 hours.Heating-up time can be less than 12 hours, as long as 6 hours~12 hours i.e.
Can.In this condition, maintained in the state of 1050 DEG C of keeping temperature about 24 hours it is constant.Temperature under the condition of high temperature is 1000
DEG C~1100 DEG C, made liquation crystalline growth and polycrystallization with 12 hours~24 hours or so.The temperature is maintained into the constant time
The free degree it is big, strict time management is not required.Next, stopping makes stove to the energization of heater by Temperature fall
Interior temperature drop.For example on the time declined within 6 hours.
Thus obtained CIG polycrystalline is crushed after room temperature is returned to, and then mixes with Se and CdSe and vacuum is sealing into
In quartz ampoule, it is placed again into stove.
In the manufacturing process of N-shaped CIGS alloys, for example, temperature was set to rise to 1050 DEG C from room temperature with 10 hours.By the temperature
The state of 1050 DEG C of degree is maintained about 24 hours.On the time, strict control is not required yet, and then, afterwards to the temperature of room temperature
Degree reduces the mode that can also be quenched and carries out.
In the manufacture of CIG alloys, 1 is compared as pantogen subnumber using Cu, In and Ga：2 ratio is illustrated, but In with
Ga's is used for 1：x：(1-x) and the scope in 0 ＜ x ＜ 1 is adjusted according to purpose, function.Additionally, being alloy with CIG3 units
Used as the scope of the ratio 1.7~2.3 of 1 Se, it is adjusted also according to purpose, function.
N-shaped CIGS alloys are on the light absorbing zone of CIGS solar cells as the material of pn homojunctions layer formation
Use, therefore in order to form the shape matched with sputter equipment, manufacture the sputtering target of N-shaped CIGS alloys.
Next the manufacture method to N-shaped CIGSS alloys is illustrated.
Main use can obtain efficient CdS, Zn system in cushion 18, with regard to N-shaped CIGSS alloys constitution element and
Speech, Cd and/or Zn is also added with except Cu, In, Ga, Se, S.In this composition element, if In simple substance mixes with Se simple substance,
Generation chemistry and generate heat, significantly in the case of can explode.For In and Se, in order to not make simple substance be mixed with each other, make its point
From rear crystallization.Additionally, Cd use with for IIb races element, as CIGSS one of constitution element VIb races compound
CdSe or CdS, Zn are used as the ZnSe or ZnS with the compound of VIb races, and the manufacture method of safety is necessary.
The cadmium or zinc of IIb races are diffused into CIGSS crystallizations and as the CIGSS alloy N-shapeds of p-type, will make VIb races element
It is the Se or S of the composition as CIGSS alloys, so that with Se holes, the effect in S holes in landfill CIGSS crystallizations.
Hereinafter, mainly illustrated in case of cushion 18 has used CdS.
Figure 11 is the flow chart 56 of the outline of the manufacture method for showing N-shaped CIGSS alloys.In fig. 11, in step S31
In, the polycrystalline of CIG alloys will be manufactured in the elemental composition of CIGSS alloys except Cu, In and Ga mixing of Se and S.Next,
In step s 32, CIG alloys are crushed, is mixed with Se, S and CdSe.On In, due to being crystallized as CIG alloys, because
Even if this mixing Se simple substance does not also chemically react.Next, manufacturing the polycrystalline of N-shaped CIGSS alloys in step S33.By
This, N-shaped CIGSS alloys are completed by the manufacture method of safety.
Figure 12 is the flow chart 58 of the manufacture method for showing N-shaped CIGSS alloys.First, as S41 the step of preparation
In, prepare the ampoule for manufacturing CIG alloys and the ampoule for manufacturing N-shaped CIGSS alloys.Ampoule uses such as quartz glass
Ampoule, illustrated as quartz ampoule below, but be not limited to quartz glass.Chloroazotic acid washing and nitre are carried out to quartz ampoule
Acid+hydrofluoric acid is washed, and makes moisture evaporation with drying machine in advance.And then submerge in acetone, then heated with burner and remove coal
Soot.Thus quartz ampoule is covered by carbon, is prevented from being mixed into for the impurity from quartz.
In step S42, by Cu, In and Ga using the washing such as hydrochloric acid, weigh so that pantogen subnumber ratio is 1：
0.8：0.2, vacuum is sealing into the quartz ampoule covered by carbon.
In step S43, vacuum is sealed with the quartz ampoule of raw material and is put into the electric furnace for heating.In step
In S44, the heater being pointed in stove is powered and it is generated heat, and temperature is risen to 1050 DEG C.And then, by 1050 DEG C of high temperature
State maintains certain hour, make crystalline growth from liquation and after forming the polycrystalline of raw material, under making in-furnace temperature in step S45
Drop to room temperature.Thus, CIG alloys can be obtained.
In step S46, CIG alloys are taken out from the quartz ampoule that have decreased to room temperature, CIG alloys are crushed.Now,
Uniform micro mist can be obtained by screen cloth.Such crystal powder, because In is crystallized together with Cu and Ga, therefore not with Se occur
Chemical reaction.
In step S47, carry out weighing the Se so that chippy CIG alloys and the Se compositions for adding Se, S and CdSe
Pantogen subnumber compares 1 for pantogen subnumber：2 ratio.The addition of Cd is controlled by the amount of CdSe now.The material of weighing
Material vacuum is sealing into the quartz ampoule covered by carbon.And then, in putting into electric furnace in step S48.Next, in step
After in-furnace temperature is risen to 200 DEG C in S49 and maintaining certain hour, 1050 DEG C are risen in step s 50.By temperature 1050
DEG C maintain certain hour, by liquation grow carry out polycrystallization after, in-furnace temperature is dropped to room temperature in step s 51, from stone
N-shaped CIGSS alloys are taken out in English ampoule.
The temperature control status 60 in electric furnace in the manufacturing process of Figure 13 display N-shaped CIGSS alloys.First, in room temperature
The quartz ampoule that vacuum has enclosed raw material Cu, In, Ga is put into stove, heater is powered and in-furnace temperature is increased.Temperature
Degree rising for example rose to 1050 DEG C with 12 hours.Heating-up time can be less than 12 hours, as long as 6 hours~12 hours i.e.
Can.In this condition, maintained in the state of 1050 DEG C of keeping temperature about 24 hours it is constant.Temperature under the condition of high temperature is 1000
DEG C~1100 DEG C, polycrystalline was formed by crystalline growth from liquation with 12 hours~24 hours or so.Maintain the temperature constant
The free degree of time is big, and strict time management is not required.Next, stopping to the energization of heater that passing through Temperature fall makes
In-furnace temperature declines.Declined within 6 hours on time.
Thus obtained CIG polycrystalline returned to and be crushed after room temperature, and then is mixed with Se, S and CdSe and vacuum is sealing into
In quartz ampoule, it is placed again into stove.
In the manufacturing process of N-shaped CIGSS alloys, about 200 DEG C are risen to as the 1st step.Its reason is that Se's and S is molten
Point is low, and crystalline growth is made from liquation together with other elements after fully being melted at 200 DEG C.Thereby, it is possible to obtain high-quality
Polycrystalline.Intensification to 200 DEG C rose to 200 DEG C with 2 hours.In this condition, kept for about 12 hours, it is next small with 6
When rise to 1050 DEG C.By the condition of high temperature maintain about 24 hours it is constant.The free degree of the time of the maintenance is big, does not require strict
Time management.Then stop the heater of electric furnace and return to room temperature.Stop to the energization of heater after, can place until
It is changed near room temperature.
In addition, as the manufacture method of N-shaped CIGSS alloys, being chemically reacted if In simple substance mixes with Se simple substance
And generate heat, can be exploded in the case of significant, therefore illustrate method that is individually separated and being manufactured with 2 stages, but certainly, fill
Ground is divided to note heating, blast, it is also possible to carry out the manufacture in 1 stage.
In this case, Cu, In, Ga, Se, S and CdSe are weighed and vacuum is sealing into quartz ampoule simultaneously.
Figure 14 shows the temperature control status 62 in the manufacture method of the N-shaped CIGSS alloys in 1 technique.In view of Se and S
Fusing point it is low, rise to 200 DEG C first and by Se and S fully liquation, after maintaining certain hour, be warmed up to 1050 DEG C.Dimension
The free degree for holding the time of high temperature is big, and strict time management is not required.Then stop the heater of electric furnace and return to room temperature.
After stopping to the energization of heater, can place until being changed near room temperature.
In the manufacture of CIG alloys, 1 is compared as pantogen subnumber using Cu, In and Ga：2 ratio is illustrated, but In
1 is used for Ga：x：(1-x) and the scope in 0 ＜ x ＜ 1 is adjusted according to purpose, function.Additionally, being closed with system of CIG3 units
Gold as 1 Se scope of the ratio 1.7~2.3, its also according to purpose, function and adjust.
N-shaped CIGSS alloys are on the light absorbing zone of CIGSS solar cells as the material of pn homojunctions layer formation
And use.Even if in the case where N-shaped CIGSS alloys have been used, the manufacture method of sputtering target and in CIGS solar-electricities
The method that pn homojunctions layer is formed on the light absorbing zone in pond is identical, below, to the system of the sputtering target on N-shaped CIGS alloys
The manufacture method for making method and solar cell is illustrated.
Figure 15 is the manufacture method flow chart 64 of sputtering target.Method by N-shaped CIGS alloys manufacture sputtering target is, in step
In S61, the polycrystalline of N-shaped CIGS alloys is crushed and powdered, in step S62, be filled in the casting for being configured to desired shape
Carry out bulk in mould and by pressure processing, in step S63, N-shaped CIGS alloys section by bulk and formation is splashed
Shoot at the target.
If the profile of the N-shaped CIGS alloys of manufacture is suitable for sputter equipment, bulk is not needed, can only cut into slices
And form sputtering target.
Figure 16 shows and is the use of by N-shaped sputtering target, using sputtering of N-shaped CIGS alloys produced by the present invention
The figure of the concept 66 that CIGS thin film is formed.Overleaf on electrode 14, light absorbing zone 16 is laminated with, flying out sputtered atom and makes its attached
On the light absorbing zone 16, form N-shaped cigs layer.So, except with addition to can be by the feature of 1 technique film forming, Cd be equal
It is diffused into evenly in N-shaped cigs layer, Cd concentration also can critically be controlled when N-shaped CIGS alloys are manufactured, therefore, it is possible to carry out
The manufacture of efficient CIGS solar cells.
Figure 17 is the figure for illustrating the manufacture state 70 using the light absorbing zone of sputter equipment.Set in sputter equipment 72
Have：Vacuumize 74 opening portion；Inject the opening portion of Ar (argon) gas 76；And the opening portion of injection cooling water 82.
The Mo substrates 86 that substrate is formd backplate by Mo are positioned on sample bench 84.On the top of sputter equipment 72, peace is provided with
The sputtering target 80 formed by N-shaped CIGS alloys loaded on electrode 78.In electrode 78 and sample bench 84, using sample bench 84 as sun
Pole and be connected with dc source 92.
If applying high voltage by dc source 92 and ionizing Ar gases 76, make the Ar elements 88 that have ionized with
The sputtering target 80 formed by N-shaped CIGS alloys is collided, then the sputtered atom on the surface of the sputtering target 80 for being formed by N-shaped CIGS alloys
90 are flown by bullet, the sputtered atom 90 reach Mo substrates 86 and pile up, film forming, the CIGS thin film that Cd has equably spread is by 1 technique
Formed.
In addition, the cigs layer as light absorbing zone, it is also possible to by manufacturing the sputtering target formed by CIGS alloys, using same
The method film forming of sample.
Figure 18 is the manufacture for showing the solar cell using the sputtering target formed by CIGS alloys and N-shaped CIGS alloys
The flow chart of of method 96.
In step S71, sputtering film-forming Mo is passed through in substrate.In step S72, for being connected in series for each unit,
Cut backplate and carry out pattern and formed.And then, in step S73, using the CIGS sputtering targets of light absorbing zone, by splashing
Injection device forms CIGS light absorbing zones by 1 technique.
In step S74, N-shaped CIGS sputtering targets of the present invention are equipped on sputter equipment, n is formed on CIGS films
Type cigs layer.
And then in step S75, the N-shaped cigs layer of formation is immersed in strong alkaline aqueous solution, by solution growth method
And film forming CdS cushions.Then in step S76, CIGS light absorbing zones and cushion is cut and pattern is formed.In step S77
In, on the buffer layer, for example, by MOCVD (Metal Organic Chemical Vapor Deposition：Metal is organic
Chemical vapor deposition) device, film forming high resistance buffer layer and transparent conductive film layer and form electrode.In step S78, again
Cutting conductive film layer and carry out pattern and formed, in step S79, the bus acrylonitrile that will be formed by aluminium etc. in backplate,
For the layer being laminated on substrate, cover glass sealing material is sealed and solar cell is completed.
More than, the manufacture method to the CIGS solar cells with pn homojunctions layer of the present invention is said
It is bright, even if but N-shaped CIGS alloys of the present invention can also be used in light absorbing zone and pn homojunctions by vacuum vapour deposition
The film forming of layer.
Figure 19 is the plan of vacuum deposition apparatus 100, by vacuum chamber 102, diffusion pump 104, mechanical booster pump 106 and oil
Rotary pump 108 is constituted.
In vacuum chamber 102, carry out be by CIGS4 units of the present invention the light absorbing zone that alloy 118 is formed film forming.
In order that be vacuum in vacuum chamber 102, by diffusion pump 104 and oil rotary pump 108, the air of the inside of purging vacuum room 102.
For mechanical booster pump 106,2 cocoon type rotors in housing enter the drive gear of its shaft end and each other along phase negative side
Rotated to the same period.The gas entered from air entry is limited in space between housing and rotor, by the rotation of rotor from
Exhaust side is released in air.Therefore, combined with diffusion pump 104 and oil rotary pump 108 by making mechanical booster pump 106, energy
Enough increase substantially exhaust velocity.
Figure 20 is displayed in the vacuum chamber 102 of vacuum deposition apparatus 100 by the evaporation from N-shaped CIGS alloys 118
It is being laminated in the state 110 of film forming N-shaped cigs layer on the cigs layer of Mo substrates 86.Have in vacuum chamber 102 and be laminated with cigs layer
Mo substrates 86 and the tungsten plate 120, the heater 112 that are equipped with N-shaped CIGS alloys 118.And then possess when the thickness of N-shaped cigs layer becomes
For regulation thickness when stop film forming closer 116.
Tungsten plate 120 will be arranged at as the N-shaped CIGS alloys 118 of evaporation sample first, then, makes diffusion pump 104, oil rotation
Turn pump 108 and mechanical booster pump 106 rotates and carries out vacuum exhaust.It is changed into high vacuum state upon vacuum exhaust, just
Heater power source 114 is connected, electric current is flowed through to heater 112 and is heated.The temperature of N-shaped CIGS alloys 118 reaches evaporating temperature
Turn on closer 116.
Thus, the deposition material from N-shaped CIGS alloys 118 is piled up on the Mo substrates 86 for be laminated with cigs layer and forms
Film.The value that thickness reaches regulation is shut off closer 116, terminates evaporation.
So, N-shaped CIGS alloys of the present invention, even if by using the vacuum vapour deposition of vacuum deposition apparatus
Can be used as the material of pn homojunctions layer film forming.
More than, embodiments of the present invention are illustrated, but the present invention is included and does not damage the suitable of the objects and advantages
Work as deformation, and then, do not limited by above-mentioned implementation method.
The explanation of symbol
The structure of 10 CIGS solar cells
The structure of 11 CIGSS solar cells
12 substrates
14 backplates
16 light absorbing zones
18 cushions
20 high resistance buffer layers
22 transparency electrodes
24 depletion layers
26 fermi levels
28 valence bands
30 conduction bands
32 boundary defects
34 N-shaped cigs layers
The structure of the 36 CIGS solar cells for being provided with N-shaped cigs layer
The structure of the 38 CIGSS solar cells for being provided with N-shaped CIGSS layers
The flow chart of the summary of 40 display N-shaped CIGS alloy manufacturing methods
The manufacture method flow chart of 42 N-shaped CIGS alloys
The 44 manufacture states for using electric furnace
46 electric furnaces
48 heaters
50 raw material
52 quartz ampoules
54 temperature control status
The flow chart of the summary of 56 display N-shaped CIGSS alloy manufacturing methods
The manufacture method flow chart of 58 N-shaped CIGSS alloys
60,62 temperature control status
The manufacture method flow chart of 64 sputtering targets
66 form concept using the N-shaped cigs layer of sputtering
The manufacture state of 70 light absorbing zones for using sputter equipment
72 sputter equipments
74 vacuumize
76 Ar gases
78 electrodes
80 sputtering targets
82 cooling waters
84 sample bench
86 Mo substrates
88 Ar elements
90 sputtered atoms
92 dc sources
The manufacture method flow chart of 96 solar cells
100 vacuum deposition apparatus
102 vacuum chambers
104 diffusion pumps
106 mechanical booster pumps
108 oil rotary pumps
Evaporation state in 110 vacuum chambers
112 heaters
114 heater power sources
116 closers
118 N-shaped CIGS alloys
120 tungsten plates.
Claims (22)
1. a kind of manufacture method of N-shaped light absorbing zone alloy, it is characterised in that be comprising copper, indium, gallium, selenium and IIb races element
N-shaped light absorbing zone alloy manufacture method, it possesses following operations：
Copper, indium, gallium are mixed, it is crystallized at 1000~1100 DEG C and is made the 1st operation of CIG alloys,
CIG alloys crushing is made the 2nd operation of CIG alloy powders, and
Mix selenium and the compound being made up of IIb races element and VIb races element in the chippy CIG alloy powders, make
It crystallizes at 1000~1100 DEG C and makes the 3rd operation of N-shaped CIGS alloys.
2. the manufacture method of N-shaped light absorbing zone alloy according to claim 1, it is characterised in that the 1st operation with
In 3rd operation, make crystalline growth from liquation at 1000~1100 DEG C and generate polycrystalline.
3. the manufacture method of N-shaped light absorbing zone alloy according to claim 1, it is characterised in that described by unit of IIb races
Element is cadmium selenide with the compound of VIb races element composition.
4. the manufacture method of N-shaped light absorbing zone alloy according to claim 1, it is characterised in that described by unit of IIb races
Element is zinc selenide with the compound of VIb races element composition.
5. the manufacture method of N-shaped light absorbing zone alloy according to claim 1, it is characterised in that by IIb races element with
The compound that VIb races element is constituted is cadmium sulfide.
6. the manufacture method of N-shaped light absorbing zone alloy according to claim 1, it is characterised in that by IIb races element with
The compound that VIb races element is constituted is zinc sulphide.
7. the manufacture method of N-shaped light absorbing zone alloy according to claim 1, it is characterised in that
In the 1st operation and the 3rd operation, mixed raw material are sealing into ampoule by vacuum.
8. the manufacture method of N-shaped light absorbing zone alloy according to claim 7, it is characterised in that the ampoule is by carbon
Covering.
9. the manufacture method of N-shaped light absorbing zone alloy according to claim 7, it is characterised in that the ampoule is stone
English glass.
10. a kind of manufacture method of N-shaped light absorbing zone alloy, it is characterised in that be comprising copper, indium, gallium, selenium, sulphur and IIb races
The manufacture method of the N-shaped light absorbing zone alloy of element,
It possesses following operations：Copper, indium, gallium are mixed the 1st work for making it be crystallized at 1000~1100 DEG C and manufacturing CIG alloys
Sequence,
CIG alloys crushing is manufactured the 2nd operation of CIG alloy powders, and
Mix selenium, sulphur and the compound being made up of IIb races element and VIb races element in the chippy CIG alloy powders,
It is crystallized at 1000~1100 DEG C and manufacture the 3rd operation of N-shaped CIGSS alloys.
The manufacture method of 11. N-shaped light absorbing zone alloys according to claim 10, it is characterised in that
In the 1st operation of the manufacture CIG alloys, make crystalline growth from liquation at 1000~1100 DEG C and generate polycrystalline,
3rd operation of the manufacture N-shaped CIGSS alloys possesses following step：Make temperature by heating up in 180~220 DEG C of maintenances
The first step of certain hour；And temperature is maintained the second step of certain hour at 1000~1100 DEG C.
The manufacture method of 12. N-shaped light absorbing zone alloys according to claim 10, it is characterised in that
In the 1st operation and the 3rd operation, mixed raw material are sealing into ampoule by vacuum.
The manufacture method of 13. N-shaped light absorbing zone alloys according to claim 12, it is characterised in that the ampoule quilt
Carbon is covered.
The manufacture method of 14. N-shaped light absorbing zone alloys according to claim 12, it is characterised in that the ampoule is
Quartz glass.
The manufacture method of 15. N-shaped light absorbing zone alloys according to claim 10, it is characterised in that described by IIb races
Element is cadmium selenide with the compound of VIb races element composition.
The manufacture method of 16. N-shaped light absorbing zone alloys according to claim 10, it is characterised in that described by IIb races
Element is zinc selenide with the compound of VIb races element composition.
The manufacture method of 17. N-shaped light absorbing zone alloys according to claim 10, it is characterised in that by IIb races element
It is cadmium sulfide with the compound that VIb races elements is constituted.
The manufacture method of 18. N-shaped light absorbing zone alloys according to claim 10, it is characterised in that by IIb races element
It is zinc sulphide with the compound that VIb races elements is constituted.
19. a kind of manufacture methods of N-shaped light absorbing zone sputtering target, it is characterised in that possess：Will be by claim 1 or 10
The N-shaped light absorbing zone that described N-shaped light absorbing zone is manufactured with the manufacture method of alloy manufactures N-shaped light absorbing zone with alloy section
With the slicing process of sputtering target.
20. a kind of manufacture methods of N-shaped light absorbing zone sputtering target, it is characterised in that possess following operations：
The N-shaped light absorbing zone alloyed powder that N-shaped light absorbing zone described in claim 1 or 10 is manufactured with the manufacture method of alloy
The broken and powdered operation of powdered,
By the bulk chemical industry sequence of powdery N-shaped light absorbing zone alloy bulk by pressure processing, and
The slicing process that the N-shaped light absorbing zone by bulk is cut into slices with alloy.
21. a kind of manufacture methods of solar cell, it is characterised in that using by the method system described in claim 19 or 20
The N-shaped light absorbing zone sputtering target made, by sputter equipment, forms N-shaped light absorbs on the light absorbing zone being laminated on substrate
Layer.
22. a kind of manufacture methods of solar cell, it is characterised in that possess following N-shaped light absorbing zone film formation process：The right to use
Profit requires the N-shaped light absorbing zone alloy that the N-shaped light absorbing zone described in 1 or 10 is manufactured with the manufacture method of alloy, by vacuum
Evaporation, the film forming N-shaped light absorbing zone on the light absorbing zone for be laminated in substrate.
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| JP2012-111778 | 2012-05-15 | ||
| PCT/JP2013/063086 WO2013172253A1 (en) | 2012-05-15 | 2013-05-09 | n-TYPE LIGHT-ABSORBING LAYER ALLOY, METHOD FOR PRODUCING SAME, AND SOLAR CELL |
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| KR101735498B1 (en) | 2015-11-06 | 2017-05-15 | 영남대학교 산학협력단 | thin film solar cell and method of manufacturing the same |
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| US6107562A (en) * | 1998-03-24 | 2000-08-22 | Matsushita Electric Industrial Co., Ltd. | Semiconductor thin film, method for manufacturing the same, and solar cell using the same |
| CN102201495A (en) * | 2011-05-04 | 2011-09-28 | 苏州瑞晟太阳能科技有限公司 | CuInGaSe (CIGS) thin-film solar cell prepared by all-solution method |
| TW201200270A (en) * | 2010-05-24 | 2012-01-01 | Ulvac Inc | Method of manufacturing Cu-In-Ga alloy powder, method of manufacturing Cu-In-Ga-Se alloy powder, method of manufacturing Cu-In-Ga-Se alloy sintered compact, Cu-In-Ga alloy powder and Cu-In-Ga-Se alloy powder |
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| JP2000150931A (en) * | 1998-11-11 | 2000-05-30 | Fujikura Ltd | Manufacture of solar battery |
| JP2004111664A (en) * | 2002-09-19 | 2004-04-08 | Shinto Fine Co Ltd | Forming method of compound semiconductor thin film |
| JP2008235794A (en) * | 2007-03-23 | 2008-10-02 | Tokyo Univ Of Science | Photoelectric conversion material and method of manufacturing the same, semiconductor device, and solar battery |
| JP5418832B2 (en) * | 2009-11-25 | 2014-02-19 | 三菱マテリアル株式会社 | Method for producing Cu-In-Ga-Se quaternary alloy sputtering target |
| JP2011187885A (en) * | 2010-03-11 | 2011-09-22 | Fujifilm Corp | Photoelectric conversion element and solar cell |
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| US6107562A (en) * | 1998-03-24 | 2000-08-22 | Matsushita Electric Industrial Co., Ltd. | Semiconductor thin film, method for manufacturing the same, and solar cell using the same |
| TW201200270A (en) * | 2010-05-24 | 2012-01-01 | Ulvac Inc | Method of manufacturing Cu-In-Ga alloy powder, method of manufacturing Cu-In-Ga-Se alloy powder, method of manufacturing Cu-In-Ga-Se alloy sintered compact, Cu-In-Ga alloy powder and Cu-In-Ga-Se alloy powder |
| CN102201495A (en) * | 2011-05-04 | 2011-09-28 | 苏州瑞晟太阳能科技有限公司 | CuInGaSe (CIGS) thin-film solar cell prepared by all-solution method |
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