CN104285279A - N-type light-absorbing layer alloy, method for producing same, and solar cell - Google Patents
N-type light-absorbing layer alloy, method for producing same, and solar cell Download PDFInfo
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- CN104285279A CN104285279A CN201380025435.5A CN201380025435A CN104285279A CN 104285279 A CN104285279 A CN 104285279A CN 201380025435 A CN201380025435 A CN 201380025435A CN 104285279 A CN104285279 A CN 104285279A
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- absorbing zone
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 185
- 239000000956 alloy Substances 0.000 title claims abstract description 185
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 108
- 239000011669 selenium Substances 0.000 claims abstract description 78
- 239000010949 copper Substances 0.000 claims abstract description 55
- 229910052738 indium Inorganic materials 0.000 claims abstract description 44
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 43
- 239000003708 ampul Substances 0.000 claims abstract description 40
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 229910052802 copper Inorganic materials 0.000 claims abstract description 33
- 238000002425 crystallisation Methods 0.000 claims abstract description 32
- 230000008025 crystallization Effects 0.000 claims abstract description 32
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 26
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 18
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical group [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000007789 sealing Methods 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 7
- 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 4
- 238000000034 method Methods 0.000 claims description 91
- 238000000576 coating method Methods 0.000 claims description 52
- 239000011248 coating agent Substances 0.000 claims description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 238000005477 sputtering target Methods 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 27
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical group OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 21
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 21
- 239000005864 Sulphur Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 230000000903 blocking effect Effects 0.000 claims description 7
- 238000007738 vacuum evaporation Methods 0.000 claims description 3
- 239000005083 Zinc sulfide Substances 0.000 claims description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical group [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 abstract description 17
- 239000011593 sulfur Substances 0.000 abstract 2
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 39
- 239000010408 film Substances 0.000 description 37
- 239000010453 quartz Substances 0.000 description 27
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 17
- 239000011701 zinc Substances 0.000 description 17
- 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
- 229910052793 cadmium Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229910052725 zinc Inorganic materials 0.000 description 10
- 238000009792 diffusion process Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 238000004544 sputter deposition Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 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
- 239000013078 crystal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001704 evaporation Methods 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
- 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
- 230000008021 deposition Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003595 mist Substances 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
- 239000000779 smoke Substances 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
- 229910000952 Be alloy Inorganic materials 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 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
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 238000005229 chemical vapour deposition Methods 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
- 210000000981 epithelium Anatomy 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon 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
- 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
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- SDBOUNNVMSZUHW-UHFFFAOYSA-N S=[Cu]=[Se] Chemical compound S=[Cu]=[Se] SDBOUNNVMSZUHW-UHFFFAOYSA-N 0.000 description 1
- 229910001370 Se alloy Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical class C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000004020 conductor Substances 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 compound [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
- 230000007423 decrease Effects 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
- 150000002259 gallium compounds Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 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
- 238000009434 installation Methods 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 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
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 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
- 238000005987 sulfurization reaction 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
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
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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
- 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
Provided are: a method for producing an n-type CIGS alloy or an n-type CIGSS alloy able to increase the conversion efficiency of a solar cell and able to highly precisely form a p-n homojunction layer at the interface between a light absorbing layer and a buffer layer; and a method for producing a solar cell. The n-type CIGS alloy is produced by means of: a first step for producing a CIG alloy by mixing copper, indium, and gallium, vacuum sealing the result in an ampoule, and causing crystallization at a high temperature; a second step for pulverizing the CIG alloy to produce a CIG alloy powder; and a third step for producing an n-type CIGS alloy by admixing selenium and a compound comprising a group IIb element and a group VIb element to the pulverized CIG alloy, and causing crystallization at a high temperature. The compound comprising a group IIb element and a group VIb element is cadmium selenide or zinc selenide. The n-type CIGSS5 alloy further includes sulfur, and the sulfur is added in the third step.
Description
Technical field
The present invention relates to the light absorbing zone being used in solar cell, the manufacture method of carrying out the N-shaped light absorbing zone alloy of pn homojunction with p-type light absorbing zone, and this N-shaped light absorbing zone alloy is defined the solar cell of N-shaped cigs layer as sputtering target.
Background technology
Solar cell is categorized into silicon system, series of compounds, organic system generally, recently, series of compounds solar cell be expected for thin, year in year out with low uncertainty, photoelectric conversion efficiency uprise, its exploitation always in progress.About series of compounds, as the material of light absorbing zone, replace silicon and use the I-III-VI being called as chalcopyrite system be made up of copper (hereinafter referred to as Cu), indium (hereinafter referred to as In), gallium (hereinafter referred to as Ga), selenium (hereinafter referred to as Se), sulphur (hereinafter referred to as S) etc.
2compounds of group.Representational have two copper indium diselenide CuInSe
2, two copper indium gallium selenide Cu (In, Ga) Se
2(hereinafter referred to as CIGS), two selenium copper sulfide indiums gallium Cu (In, Ga) (S, Se)
2(hereinafter referred to as CIGSS) (with reference to patent documentation 1 etc.).
Chalcopyrite type cpd semiconductor is direct gap semiconductor, and optical absorption characteristics is excellent, and energy gap covers from sulfuration aluminum bronze CuAlS
23.5eV to tellurium indium copper CuInTe
2the wide range of wavelengths of 0.8eV, also can manufacture the luminescence from region of ultra-red to ultraviolet region, photo detector.Particularly also having polycrystalline CIGS solar cell to play excellent optical absorption characteristics makes conversion efficiency be 20.3% such report (with reference to non-patent literature 1).
About the structure of CIGS thin film solar cell, for the stepped construction that zinc oxide (ZnO) window layer/resilient coating/CIGS light absorbing zone/molybdenum (Mo) electrode is such is representational structure from light incident side.About cigs layer, because In and Se element is constituent, the heating that therefore may occur to be caused by the chemical reaction sharply of In simple substance and Se simple substance in manufacturing process, blast.Therefore, In simple substance and Se simple substance must be made directly not to react.
For this reason, the manufacturing process such as adopting the CIGS thin film of selenizing method is following method: the stacked film being formed In, Cu, Ga on Mo (molybdenum) layer by sputtering method, by this stacked film substrate temperature 400 ~ 550 DEG C, diluted by Ar (argon) containing H
2process a few hours in the gas of Se (hydrogen selenide), thus form the CuInSe that particle diameter is about about 3 μm
2film.When VI race element is S (sulphur), process in S atmosphere.More than 400 DEG C and H
2se (hydrogen sulfide) gas reaction and obtain Cu (In, Ga) Se
2film (with reference to patent documentation 2).
Improve the open circuit voltage of the high efficiency realizing CIGS solar cell, it is known that the high-qualityization of light absorbing zone is certainly important, its surface-interface controls to become important, and resilient coating and cigs layer interface are that pn homojunction is suitable for high efficiency.Relative to heterogeneous joint, the energy conversion efficiency of the CIGS solar cell of pn homojunction is good, as reason, can think because homojunction Carrier recombination compared with heterogeneous joint is few.
Resilient coating is the n-type semiconductor such as cadmium sulfide (CdS), ZnO, and CIGS forms pn knot as p-type semiconductor.Usually, the resilient coating formed by CdS is formed and is manufactured by solution growth method, and at the joint interface of the cigs layer with p-type, Cd is with Cd (OH)
2form be present in surface, and replace Cu site in CIGS bulk.Therefore, Cd is diffused into surface n type in cigs layer, forms shallow homojunction.About this pn homojunction, there is various motion, as described below.
First, in order to the surface part at the semiconductive thin film formed by the p-type chalcopyrite type cpd semiconductor containing sulphur and/or selenium, form the Impurity Diffusion region that diffusion has zinc and/or cadmium, by the precursor film formed by the p-type chalcopyrite type cpd semiconductor containing sulphur and/or selenium, heat-treat in the atmosphere containing Organometallic zinc compound and/or organic metal cadmium compound.Form pn homojunction (with reference to patent documentation 3) thus.
Cd manufactures to the diffusion of cigs layer mainly through solution growth method, but it is also proposed the method for the Cd that adulterates in cigs layer energetically.Soda-lime glass substrate forms Mo film by sputtering method with the thickness of 1 μm, it can be used as Mo electrode.Next, the sputtering target of the composition of Cu:In:Ga:Se=1:0.5:0.5:2 is used to form CIGS film by ion beam sputtering with the thickness of 1.6 μm, then, continually by forming by Cu:In:Ga:Se:Cd=1:0.5:0.5:2:x (Cd concentration x=50ppm) target formed, form the Cd doped layer (with reference to patent documentation 4) of thickness 56nm.
In addition, 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 to form that pn ties be extremely desirable, for this reason, in a vacuum, base feed gas and make chalcopyrite thin layer when grown on substrates on monocrystal substrate after the heating, by unstrpped gas separately or multiple combination be repeatedly supplied in substrate successively simultaneously, thus can the chemical composition of critically key-course, as its result, define the chalcopyrite monocrystalline thin layer of high-quality.Thus, have p-type chalcopyrite thin film of the same race and N-shaped chalcopyrite thin film to carry out face to contact and the method (with reference to patent documentation 5) that forms homogeneous pn junction.
The structure of the CIGSS layer solar cell improving conversion efficiency is sought, for the stepped construction that zinc oxide (ZnO) window layer/resilient coating/CIGSS light absorbing zone/molybdenum (Mo) electrode is such is representational structure from light incident side about adding S in CIGS.As the manufacture method of CIGSS film, propose the method manufactured by comprising following operation, described operation is: will have the compound of amino and hydroxyl as functional group as solvent, Cu, In and Ga chalcogenide is separately dissolved, and modulation comprises Cu, In and Ga and the operation as the complex of at least a kind in S and Se of the constituent of chalcogenide; This complex is coated the surface of substrate and dry, manufacture the operation of the epithelium of complex; And by the heat treatment in the reducing atmosphere comprising the arbitrary gas in hydrogen, nitrogen and their mist of the epithelium of this complex, form the operation (with reference to patent documentation 6) of the layer using at least a kind in Cu, In and Ga and S and Se as principal component on the surface of substrate.
And then, as using CIGSS as the p-type semiconductor of mother metal and n-type semiconductor, providing the semiconductor that conductivity is high, realizing high performance semiconductor element by using such p-type semiconductor and n-type semiconductor.Be coated with Mo electrode on the glass substrate, define p-type CuInS by vacuum vapour deposition thereon
2layer.Then, only stop the supply of the Sb as p-type impurity, the I as N-shaped impurity is supplied with the form of CuI, thus at p-type CuInS
2layer forms N-shaped CuInS
2layer.Thus, manufacture continuously with CuInS in identical vacuum plant
2as the pn homojunction of mother metal, at this N-shaped CuInS
2layer is formed ITO electrode (with reference to patent documentation 7).
And then, the pn of solar cell is tied as the homojunction be made up of p shape compound semiconductor layer (p shape light absorbing zone) and n shape compound semiconductor layer or plan homojunction, and the combination optimization of n shape compound semiconductor layer and n shape resilient coating is sought high efficiency.The formation of solar cell comprises: substrate; Conductive layer; P shape compound semiconductor layer containing Ib race element, IIIb race element and VIb race element; N shape compound semiconductor layer containing Ib race element, IIIb race element and VIb race element; N shape resilient coating; N shape window layer; And n shape transparency conducting layer (with reference to patent documentation 8).
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2004-047917 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2006-049768 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2008-235794 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2000-150932 publication
Patent documentation 5: Japanese Unexamined Patent Publication 10-74968 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2010-129660 publication
Patent documentation 7: Japanese Unexamined Patent Publication 11-87750 publication
Patent documentation 8: Japanese Unexamined Patent Publication 2005-228975 publication
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
Summary of the invention
Invent problem to be solved
But, in the manufacture method of above-mentioned solar cell in the past, even if form CdS film as resilient coating by sputtering method, also the conversion efficiency of several about % is only obtained, in addition, as resilient coating, other compound such as ZnO, ZnS can also be used except CdS, but when being formed as resilient coating with these materials, even if by solution growth method, sputtering method any one, also can produce the deviation of Cd diffusion because of manufacturing condition, can not get stable pn homojunction, particularly have problems in volume production.
By the precursor film formed by p-type chalcopyrite type cpd semiconductor, heat-treating methods in the atmosphere containing Organometallic zinc compound and/or organic metal cadmium compound, also there is the difficult such problem of its precise hard_drawn tuhes in the method for doping Cd.
P-type thin layer and the N-shaped thin layer of the semiconductor of identical type directly carry out face and contact and formed in the formation that pn ties, in cases of cigs, can pass through Cu/ (In+Ga) than and carry out pn control.Using the Cu hole being easy to most generate as acceptor, manufacture p-type CIGS at Cu/ (In+Ga) than the region being 0.8 ~ 0.9.N-shaped CIGS is In surplus region, In landfill Cu hole, and the In hole as alms giver increases.The carrier concentration of such N-shaped CIGS is low, is unsuitable for high efficiency.
In addition, p-type thin layer and the N-shaped thin layer of the semiconductor of identical type directly carry out face and contact and formed in the formation that pn ties, and when CIGSS, can pass through Cu/ (In+Ga) than carrying out pn control.P-type CIGSS is manufactured at Cu/ (In+Ga) than the region being 0.8 ~ 0.9 as acceptor using the Cu hole being easy to most generate.N-shaped CIGSS is In surplus region, In landfill Cu hole, and the In hole as alms giver increases.The carrier concentration of such N-shaped CIGSS is low, is unsuitable for high efficiency.
Therefore, while supply impurity, also be there is the difficult such problem of precise hard_drawn tuhes in the method for the p-type thin layer of the semiconductor of identical type and N-shaped thin layer film forming.
The present invention proposes in view of such aspect, its object is to provide to improve light conversion efficiency, can film forming pn homojunction layer accurately at the interface of light absorbing zone and resilient coating, the manufacture method of N-shaped light absorbing zone alloy and the manufacture method of solar cell of the conversion efficiency of solar cell can be improved.
For solving the means of problem
The present invention, by N-shaped light absorbing zone alloy, forms pn homojunction layer to seek high efficiency between the p-type light absorbing zone and resilient coating of solar cell.
N-shaped light absorbing zone alloy is the alloy comprising copper, indium, gallium, selenium and IIb race element, is the CIGS alloy of N-shaped.This N-shaped light absorbing zone alloy is manufactured by the CIGS crystallization making copper, indium, gallium, selenium and the compound that is made up of IIb race element and VIb race element and to form N-shaped at high-temperature crystallization.The compound be made up of IIb race element and VIb race element is cadmium selenide or zinc selenide.
The cadmium of IIb race or zinc to be diffused in CIGS crystallization and CIGS are carried out N-shaped, as VIb race element, for being the selenium of the composition of alloy as CIGS4 unit, thus have the effect in the selenium hole of landfill CIGS.
In addition, N-shaped light absorbing zone alloy is the CIGSS alloy of the N-shaped comprising copper, indium, gallium, selenium, sulphur and IIb race element.This N-shaped light absorbing zone alloy to form N-shaped by the compound that makes copper, indium, gallium, selenium, sulphur and comprise IIb race element and VIb race element CIGSS crystallization at high-temperature crystallization manufactures.The compound be made up of IIb race element and VIb race element is cadmium selenide, cadmium sulfide, zinc selenide or zinc sulphide.The cadmium of IIb race or zinc to be diffused in CIGSS crystallization and by CIGSS crystallization N-shaped, as VIb race element, for being selenium or the sulphur of the composition of alloy as CIGS4 unit, thus have the selenium hole of landfill CIGSS, the effect in sulphur hole.
Comprise the manufacture method of the N-shaped light absorbing zone alloy of copper, indium, gallium, selenium and IIb race element, it is characterized in that possessing following operation: make to comprise copper, indium, gallium compound make the 1st operation of CIG alloy at high-temperature crystallization; CIG alloy is pulverized and makes the 2nd operation of CIG alloy powder; And the compound mixing selenium and be made up of IIb race element and VIb race element in CIG alloy after being pulverized, make it make the 3rd operation of N-shaped CIGS alloy at high-temperature crystallization.
Manufacture in the 3rd operation of the 1st operation that CIG3 unit is alloy and manufacture N-shaped CIGS alloy, mixed material is made crystalline growth from liquation at 1000 ~ 1100 DEG C and forms polycrystalline.Manufacturing the 1st operation of CIG alloy and manufacturing in the 3rd operation of N-shaped CIGS alloy, mixed raw material are sealing in ampoule by vacuum.Ampoule is by the covered quartz glass of carbon.
Comprise the manufacture method of the N-shaped light absorbing zone alloy of copper, indium, gallium, selenium, sulphur and IIb race element, it is characterized in that, make it manufacture the 1st operation of CIG alloy at high-temperature crystallization copper, indium, gallium mixing; CIG alloy is pulverized and manufactures the 2nd operation of CIG alloy powder; And the compound mixing selenium, sulphur and be made up of IIb race element and VIb race element in CIG alloy after being pulverized, make it manufacture the 3rd operation of N-shaped CIGSS alloy at high-temperature crystallization.
Manufacturing CIG3 unit is in the 1st operation of alloy, make crystalline growth from liquation at 1000 ~ 1100 DEG C and generate polycrystalline, the 3rd operation manufacturing N-shaped CIGSS alloy possesses following step: the first step by intensification, temperature being maintained certain hours at 180 ~ 220 °; And temperature is maintained the second step of certain hour at 1000 ~ 1100 °.
In the 3rd operation manufacturing the 1st operation that CIG3 unit is alloy and manufacture N-shaped CIGSS alloy, mixed raw material are sealing in ampoule by vacuum.Ampoule is by the covered quartz glass of carbon.
The N-shaped CIGS alloy produced and the N-shaped light absorbing zone alloy as N-shaped CIGSS alloy, cut into slices by slicing process, be fabricated to N-shaped light absorbing zone sputtering target.In addition, in order to make shape be suitable for operative installations, also can manufacture N-shaped light absorbing zone sputtering target by following operation, described operation is: pulverized and the powdered operation of powdered by N-shaped light absorbing zone alloy; Powdery N-shaped CIGS alloy is processed and the bulk chemical industry sequence of large blocking by pressurization; And the slicing process of N-shaped light absorbing zone alloy section by large blocking.
The solar cell that the present invention relates to, uses the N-shaped light absorbing zone sputtering target produced, by sputter equipment, the light absorbing zone being laminated in the p-type on substrate is formed with N-shaped light absorbing zone.N-shaped light absorption layer by layer be laminated in the resilient coating that this N-shaped light absorption goes up layer by layer there is identical IIb race element.
The manufacture method of solar cell possesses following N-shaped light absorbing zone film formation process: use the N-shaped light absorbing zone sputtering target produced, by sputter equipment, be laminated in the light absorbing zone film forming N-shaped light absorbing zone of the p-type on substrate.
In addition, the N-shaped light absorbing zone alloy produced can also be used, by vacuum evaporation, film forming N-shaped light absorbing zone on the light absorbing zone of p-type being laminated in substrate.
The effect of invention
According to the present invention, between the light absorbing zone and resilient coating of the p-type of solar cell, possesses pn homojunction layer, therefore, it is possible to realize the high efficiency of solar cell.
With regard to pn homojunction layer, owing to utilizing the N-shaped light absorbing zone alloy by adding the IIb race element identical with resilient coating and N-shaped to sputter or vacuum evaporation carrys out film forming, therefore, it is possible to the critically amount of control IIb race element and the thickness of pn homojunction layer.
With regard to the manufacture of N-shaped light absorbing zone alloy, In simple substance is avoided to mix with the direct of Se simple substance, first be mixed into Se and CdSe etc. after making In and Cu and Ga crystallization and make its crystallization, so there is no the worry of the blast caused by chemical reaction sharply, can manufacture safely.
Accompanying drawing explanation
Fig. 1 is the figure of the structure that CIGS solar cell is described.
Fig. 2 is the figure of the structure that CIGSS solar cell is described.
Fig. 3 is the figure of the energy bands of a spectrum of display CIGS solar cell.
Fig. 4 is the figure that the state that Cd spreads from the CdS layer of CIGS solar cell to cigs layer is described.
Fig. 5 illustrates the figure being provided with the structure of the solar cell of N-shaped cigs layer.
Fig. 6 illustrates the figure being provided with the structure of the solar cell of N-shaped CIGSS layer.
Fig. 7 is the flow chart of the summary of the manufacture method of display N-shaped CIGS alloy.
Fig. 8 is the flow chart of the manufacture method of display N-shaped CIGS alloy.
Fig. 9 is the figure of the manufacture state of the N-shaped CIGS alloy illustrated in electric furnace.
Figure 10 is the figure of the temperature control status illustrated in electric furnace.
Figure 11 is the flow chart of the summary of the manufacture method of display N-shaped CIGSS alloy.
Figure 12 is the flow chart of the manufacture method of display N-shaped CIGSS alloy.
Figure 13 is the figure of the temperature control status in display electric furnace.
Figure 14 is the figure of the temperature control status in the electric furnace in display 1 manufacture technics.
Figure 15 is the flow chart of the manufacture method of sputtering target.
The schematic diagram that the N-shaped cigs layer that Figure 16 is the use of N-shaped CIGS alloy sputtering targets is formed.
Figure 17 is the figure that display adopts the manufacture state of the N-shaped cigs layer of sputter equipment.
Figure 18 is the use of the flow chart of the manufacture method of the solar cell of the N-shaped CIGS alloy sputtering targets that the present invention relates to.
Figure 19 is the plane graph that vacuum deposition apparatus is described.
Figure 20 is the figure of the manufacture state of the N-shaped cigs layer shown in vacuum chamber.
Embodiment
The compound semiconductor worked as the light absorbing zone of solar cell is p-type semiconductor, make use of following character: if by clipping IV race (Si in the periodic table of elements, Ge etc.) and be in equally spaced 2 kinds of elements with IV race and form compound, then form same chemical bond and become semiconductor.For belonging to the I-III-VI of adamantine series
2race's element, crystal structure is chalcopyrite structure.
In chalcopyrite crystal structure, each atom of S, Se of the Cu of I race, Ga, In, VI race of III forms 4 coordinations, has tetragonal crystal structure.The energy gap of the semiconductor of chalcopyrite is throughout the wide region of 0.26 ~ 3.5eV, but I-III-VI
2race's element by force ionic, on the other hand mobility ratio I-IV-V
2race is weak, and therefore, representational CIS, CIGS of using with the value action lower than preferred energy gap in the past.
N-shaped light absorbing zone alloy of the present invention uses as by the material being used for the N-shaped light absorbing zone film forming forming homojunction with the light absorbing zone of p-type.In the present invention, light absorbing zone is using CIGS solar cell and CIGSS solar cell as object, and N-shaped light absorbing zone alloy uses as by the term of N-shaped CIGS alloy and N-shaped CIGSS alloy general name.
CIGS as the light absorbing zone of CIGS solar cell is by CuInSe
2the alloy semiconductor that instead of of In site Ga.For CIGS, because Cu Holes buffer layer energy is little, be easy to most generate, therefore on ratio of components, form stable p-type semiconductor as Cu-poor.
Fig. 1 is the figure of the structure of display CIGS solar cell 10.On the substrate 12, Mo (molybdenum) layer is laminated with as backplate 14.Light absorbing zone 16 is made up of the CIGS thin film as p-type semiconductor.For the CIGSS film of the p-type as light absorbing zone 16, form the resilient coating 18 as n-type semiconductor and form pn knot, working as solar cell.Such as cadmium sulfide (CdS), Zinc oxide (ZnOOHS) is employed in resilient coating 18.And then by high-resistance zinc oxide (ZnO) etc. stacked high resistance buffer layer 20, be formed with the transparency electrode 60 formed by ITO, aluminium etc. at topmost.
On the other hand, now as CIS, CIGS of the many uses of light absorbing zone owing to using harmful Se, therefore also expect to reduce Se as far as possible, propose a CIGSS part of Se replaced with S.
The CIGSS of light absorbing zone can think CIS, CGS and the CuInS as basic 3 crystallizations
2mix and the structure of formation.That is, the CGS mixing of to be the CIS of 1.04eV and energy gap by energy gap be 1.68eV, forms the polycrystalline of the CIGS of energy gap 1.2eV, and then, in order to reduce the amount of Se, for being the CuInS of 1.54eV by energy gap
2the structure that polycrystalline is obtained by mixing.CuInS
2mobility lowly reach 15cm
2/ Vs, but the energy gap of final CIGSS can be made to be 1.4eV.
The CIGSS light absorbing zone of CIGSS solar cell is by CuInSe
2the alloy semiconductor that instead of of In site Ga and S.In CIGSS, Cu Holes buffer layer energy is little, is easy to most generate, and therefore on ratio of components, forms stable p-type semiconductor as Cu-poor.
Fig. 2 is the figure of the structure 11 of display CIGSS solar cell.On the substrate 12, Mo (molybdenum) layer is laminated with as backplate 14.Light absorbing zone 16 is made up of the CIGSS layer as p-type semiconductor.For the CIGSS layer of the p-type as light absorbing zone 16, form the resilient coating 18 as n-type semiconductor and form pn knot, working as solar cell.Such as cadmium sulfide (CdS), low-resistance zinc oxide (ZnO) is employed in resilient coating 18.And then by high-resistance zinc oxide (ZnO) etc. stacked high resistance buffer layer 20, be formed with the transparency electrode 60 formed by ITO, aluminium etc. at topmost.About CIGSS solar cell, be only in light absorbing zone 16, add S composition relative to CIGS solar cell, structure is identical with principle substantially.
Fig. 3 is the energy band diagram of CIGS solar cell.The bands of a spectrum state of display Fermi level 26, valence band 28 and conduction band 30.Form depletion layer 24 at light absorbing zone 16 and the combination interface of resilient coating 18, in band gap, produce boundary defect 32.From the light of transparency electrode 22 side incidence by high resistance buffer layer 20, resilient coating 18 and reach light absorbing zone 16.In light absorbing zone 16, the electronics of valence band 28 is excited by conductor, generates electron-hole pair.By the electric field of depletion layer 24 is accelerated, by resilient coating 18, trend transparency electrode 22 side, if therefore wiring, can take out electric current to the electronics generated by the CIGS of p-type.
Resilient coating 18 is mainly through solution growth method film forming CdS, ZnO layer and being formed.Chemically formed by the alkaline aqueous solution containing Cd, Zn salt and sulphur compound, such as, separate out CdS from Cd salt and thiocarbamide, for ZnO system, separate out ZnOOHS.Solution growth method is reacted based on the ion species of the chemical reaction of slaine, sulfide and complex, in the initial stage of growth of CdS resilient coating, removed the surface oxide layer of CIGS film, superfluous Na by the etching in ammonia spirit.And the Cu of Cd2+ ion and CIGS film superficial layer or the hole of taking off Cu are replaced.Thus, Cd to work as alms giver at CGIS superficial layer and forms N-shaped conduction, forms N-shaped CGIS layer, forms pn homojunction with the cigs layer of the p-type semiconductor as light absorbing zone 16.
When resilient coating 18 employs ZnO too, Cu or the Cu hole displacement of Zn and CIGS, becomes N-shaped CIGS and forms pn homojunction.
The interface that Fig. 4 is presented at resilient coating and cigs layer is formed with the state of pn homojunction.Fig. 4 (A) display is formed with the laminated arrangement of N-shaped CIGS by Cd.N-shaped cigs layer 34 is formed in the boundary face of resilient coating 18 side of depletion layer 24.Figure b (b) for define N-shaped cigs layer 34 state under energy band diagram.Pn homojunction is formed at resilient coating 18 and the interface of cigs layer 16.The end of the conduction band 30 in resilient coating 18, becomes discontinuous by projection, form the obstacle of light induced electron and via boundary defect 32 and the hole-recombination of valence band 28, efficiency reduced.But the electronics excited by the CIGS as light absorbing zone 16, because the depletion layer 24 before projection has pn homojunction layer, therefore the compound of charge carrier tails off, and consequently can form high efficiency CIGS solar cell.
The energy band diagram of CIGSS solar cell and be formed with the state of pn homojunction at the interface of resilient coating and CIGSS layer, also same with CIGS solar cell.
Fig. 5 is the CIGS solar cell being provided with N-shaped cigs layer 34 in order to form pn homojunction layer between resilient coating 18 and cigs layer 16.In the present invention, pn homojunction layer is not generate to naturally-occurring in the film forming procedure of the resilient coating 18 adopting solution growth method, but in order to the IIb race concentration of element identical with resilient coating 18 critically can be controlled and realize high efficiency, manufacture the N-shaped CIGS alloy comprising the IIb race element identical with resilient coating 18, between resilient coating 18 and cigs layer 16, form N-shaped cigs layer 34.N-shaped CIGS alloy such as the addition of the alloy of Cd or Zn in CIGS.
In addition, resilient coating 18, as n-type semiconductor, forms pn with the cigs layer as p-type semiconductor and ties, but by arranging N-shaped cigs layer 34, also can not arrange resilient coating 18.In this case, what add in N-shaped CIGS alloy can be the IIb race element of any one in Cd or Zn.
Fig. 6 is the CIGSS solar cell being provided with N-shaped CIGSS layer 34 in order to form pn homojunction layer between resilient coating 18 and CIGSS layer 16.In the present invention, pn homojunction layer is not generate to naturally-occurring in the film forming procedure of the resilient coating 18 adopting solution growth method, but in order to the IIb race concentration of element identical with resilient coating 18 critically can be controlled and realize high efficiency, manufacture the N-shaped CIGSS alloy comprising the IIb race element identical with resilient coating 18, between resilient coating 18 and CIGSS layer 16, form N-shaped CIGSS layer 34.N-shaped CIGSS alloy such as the addition of the alloy of Cd or Zn in CIGSS.
In addition, in the same manner as CIGS solar cell, in CIGSS solar cell, resilient coating 18 forms pn as n-type semiconductor with the CIGSS layer as p-type semiconductor and ties, but by arranging N-shaped CIGSS layer 34, also can not arrange resilient coating 18.In this case, what add at N-shaped CIGSS alloy can be the IIb race element of any one of Cd or Zn.
Next as N-shaped light absorbing zone alloy, the manufacture method of the N-shaped CIGS alloy that CIGS solar cell uses is described.
Mainly employ in resilient coating 18 and can obtain high efficiency CdS, Zn system, with regard to the constitution element of N-shaped CIGS alloy, except Cu, In, Ga, Se are also added with Cd and/or Zn.In this constitution element, if In simple substance mixes with Se simple substance, then there is chemical reaction and generate heat, can explode in significant situation.With regard to In and Se, in order to not make simple substance be mixed with each other, it is made to be separated post crystallization.In addition, Cd uses as IIb race element and the CdSe of the compound of the VIb race Se of one of the constitution element as CIGS, and Zn is used as the ZnSe with the compound of VIb race Se, and the manufacture method adopting safety is necessary.
The cadmium of IIb race or zinc, by being diffused into the CIGS alloy N-shaped as p-type in CIGS crystallization, making VIb race element be the selenium of the composition of alloy as CIGS4 unit, thus have the effect in the selenium hole in landfill CIGS crystallization.
Below, mainly the situation of CdS is used to be described for resilient coating 18.
Fig. 7 is flow process Figure 40 of the outline of the manufacture method of display N-shaped CIGS alloy.In Figure 5, in step sl, the polycrystalline of CIG alloy will be manufactured in the elemental composition of CIGS alloy except Cu, In and Ga mixing of Se.Next, in step s 2, CIG alloy is pulverized, mixes with Se and CdSe.About In, due to as CIG alloy by crystallization, even if therefore mix Se simple substance also chemical reaction does not occur.Next, the polycrystalline of N-shaped CIGS alloy is manufactured in step 3.Thus, N-shaped CIGS alloy is completed by the manufacture method of safety.
Fig. 8 is flow process Figure 42 of the manufacturing process of display N-shaped CIGS alloy.First as in the step S11 prepared, prepare for the manufacture of the ampoule of CIG alloy and the ampoule for the manufacture of N-shaped CIGS alloy.Ampoule uses the ampoule of such as quartz glass, is described below as quartz ampoule, but is not limited to quartz glass.Chloroazotic acid washing and nitric hydrofluoric acid washing are carried out to quartz ampoule, with drying machine, moisture is evaporated in advance.And then soak in acetone, then remove coal smoke with burner heating.Quartz ampoule is covered by carbon thus, can prevent being mixed into of impurity from quartz.
Chloroazotic acid washing and nitric hydrofluoric acid washing are carried out to quartz ampoule, with drying machine, moisture is evaporated in advance.And then soak in acetone, then remove coal smoke with burner heating.Quartz ampoule is covered by carbon thus, can prevent the precipitation of impurity.
In step S12, use hydrochloric acid etc. to wash Cu, In and Ga, carry out weighing and make pantogen subnumber than being sealing into for 1:0.8:0.2 and vacuum by the covered quartz ampoule of carbon.
In step s 13, vacuum is sealed with in the electric furnace that raw-material quartz ampoule puts into for heating.In step S14, make it generate heat to the heater energising being positioned at stove, make temperature rise to 1050 DEG C.And, this condition of high temperature of 1050 DEG C is maintained certain hour, makes liquation crystalline growth and after making raw material polycrystallization, in step S15, make in-furnace temperature drop to room temperature.Thus, CIG alloy can be obtained.
In step s 16, from the quartz ampoule that have decreased to room temperature, take out CIG alloy, this CIG alloy is pulverized.Now, uniform micro mist can be obtained by screen cloth.Due to In and Cu crystallization together with Ga, therefore there is not chemical reaction with Se in such crystal powder.
In step S17, carry out weighing and make chippy CIG alloy be the ratio of pantogen subnumber than 1:2 with the Se pantogen subnumber adding the Se composition having Se simple substance and CdSe.By the addition of the amount control Cd of CdSe now.The material vacuum weighed is sealing into by the covered quartz ampoule of carbon.And then, put in electric furnace in step S18.Next, in step S19, make in-furnace temperature rise to 1050 DEG C, the temperature of 1050 DEG C is maintained certain hour, makes liquation crystalline growth and after polycrystallization, in-furnace temperature dropped to room temperature in step S20, from quartz ampoule, taking out N-shaped CIGS alloy.
Fig. 9 is the figure of the manufacture state 50 of the employing electric furnace shown in N-shaped CIGS alloy manufacturing process illustrated in fig. 8.In electric furnace 52, have the heater 54 of heating, heater 54 is generated heat by the energising from outside and makes in-furnace temperature increase.The quartz ampoule 58 that vacuum has enclosed raw material 56 is placed with in the inside of electric furnace 52.In-furnace temperature is (not shown by the control device from outside.) controlled.
Figure 10 shows the temperature control status 30 in the electric furnace in the manufacturing process of N-shaped CIGS alloy.First in stove, put in room temperature the quartz ampoule that vacuum has enclosed raw material Cu, In, Ga, make in-furnace temperature increase to heater energising.Temperature rises and rose to 1050 DEG C with such as 12 hours.Heating-up time can be less than 12 hours, as long as be 6 hours ~ 12 hours.In this condition, keep temperature 1050 DEG C state under maintain about 24 hours constant.Temperature under this condition of high temperature is 1000 DEG C ~ 1100 DEG C, makes liquation crystalline growth and polycrystallization with 12 hours ~ 24 hours.The degree of freedom this temperature being maintained the constant time is large, does not require strict time management.Next, stop being made in-furnace temperature decline by Temperature fall to the energising of heater.Time such as, declined within 6 hours.
Thus obtained CIG polycrystalline is pulverized after returning to room temperature, and then mixes with Se and CdSe and vacuum is sealing in quartz ampoule, again puts in stove.
In the manufacturing process of N-shaped CIGS alloy, such as, temperature was made to rise to 1050 DEG C from room temperature with 10 hours.The state of this temperature 1050 DEG C is maintained about 24 hours.About this time, do not require strict control yet, and then, reduce to the temperature of room temperature afterwards and also can the mode of quenching carry out.
In the manufacture of CIG alloy, ratio using Cu, In and Ga as pantogen subnumber than 1:2 is illustrated, but the ratio of In and Ga is as 1:x:(1-x) and adjust according to object, function in the scope of 0 < x < 1.In addition, using CIG3 unit be alloy as 1 Se ratio 1.7 ~ 2.3 scope, it also adjusts according to object, function.
This N-shaped CIGS alloy uses as the material of pn homojunction layer formation on the light absorbing zone of CIGS solar cell, therefore in order to form the shape of mating with sputter equipment, manufactures the sputtering target of N-shaped CIGS alloy.
Next the manufacture method of N-shaped CIGSS alloy is described.
Mainly employ in resilient coating 18 and can obtain high efficiency CdS, Zn system, with regard to the constitution element of N-shaped CIGSS alloy, except Cu, In, Ga, Se, S are also added with Cd and/or Zn.In this constitution element, if In simple substance mixes with Se simple substance, then there is chemistry and generate heat, can explode in significant situation.With regard to In and Se, in order to not make simple substance be mixed with each other, it is made to be separated post crystallization.In addition, Cd use be IIb race element, CdSe or CdS as the compound of the VIb race of one of the constitution element of CIGSS, Zn is used as ZnSe or ZnS with the compound of VIb race, and safe manufacture method is necessary.
The cadmium of IIb race or zinc to be diffused into the CIGSS alloy N-shaped as p-type in CIGSS crystallization, make VIb race element be Se or S of the composition as CIGSS alloy, thus have the effect in Se hole in landfill CIGSS crystallization, S hole.
Below, the situation mainly employing CdS for resilient coating 18 is described.
Figure 11 is flow process Figure 56 of the outline of the manufacture method of display N-shaped CIGSS alloy.In fig. 11, in step S31, the polycrystalline of CIG alloy will be manufactured in the elemental composition of CIGSS alloy except Cu, In and Ga mixing of Se and S.Next, in step s 32, CIG alloy is pulverized, mixes with Se, S and CdSe.About In, due to the crystallization as CIG alloy, even if therefore mix Se simple substance also chemical reaction does not occur.Next, in step S33, manufacture the polycrystalline of N-shaped CIGSS alloy.Thus, N-shaped CIGSS alloy is completed by the manufacture method of safety.
Figure 12 is flow process Figure 58 of the manufacture method of display N-shaped CIGSS alloy.First, as in the step S41 prepared, prepare for the manufacture of the ampoule of CIG alloy and the ampoule for the manufacture of N-shaped CIGSS alloy.Ampoule uses the ampoule of such as quartz glass, is described below as quartz ampoule, but is not limited to quartz glass.Chloroazotic acid washing and nitric hydrofluoric acid washing are carried out to quartz ampoule, with drying machine, moisture is evaporated in advance.And then submergence in acetone, then remove coal smoke with burner heating.Quartz ampoule is covered by carbon thus, can prevent being mixed into of impurity from quartz.
In step S42, Cu, In and Ga are used the washings such as hydrochloric acid, carry out weighing and make pantogen subnumber than being 1:0.8:0.2, vacuum is sealing into by the covered quartz ampoule of carbon.
In step S43, vacuum is sealed with in the electric furnace that raw-material quartz ampoule puts into for heating.In step S44, make it generate heat to the heater energising being positioned at stove, make temperature rise to 1050 DEG C.And then, the condition of high temperature of 1050 DEG C is maintained certain hour, makes crystalline growth from liquation and after forming raw-material polycrystalline, in step S45, make in-furnace temperature drop to room temperature.Thus, CIG alloy can be obtained.
In step S46, from the quartz ampoule that have decreased to room temperature, take out CIG alloy, CIG alloy is pulverized.Now, uniform micro mist can be obtained by screen cloth., due to In and Cu crystallization together with Ga, therefore there is not chemical reaction with Se in such crystal powder.
In step S47, carry out weighing and make chippy CIG alloy be the ratio of pantogen subnumber than 1:2 with the Se pantogen subnumber of the Se composition adding Se, S and CdSe.By the addition of the amount control Cd of CdSe now.The material vacuum weighed is sealing into by the covered quartz ampoule of carbon.And then, put in electric furnace in step S48.Next, in step S49, make in-furnace temperature rise to 200 DEG C and after maintaining certain hour, rise to 1050 DEG C in step s 50.Temperature 1050 DEG C is maintained certain hour, after carrying out polycrystallization by liquation growth, makes in-furnace temperature drop to room temperature in step s 51, from quartz ampoule, take out N-shaped CIGSS alloy.
Figure 13 shows the temperature control status 60 in the electric furnace in the manufacturing process of N-shaped CIGSS alloy.First, in stove, put in room temperature the quartz ampoule that vacuum has enclosed C raw material u, In, Ga, make in-furnace temperature increase to heater energising.Temperature rises and such as rose to 1050 DEG C with 12 hours.Heating-up time can be less than 12 hours, as long as be 6 hours ~ 12 hours.In this condition, keep temperature 1050 DEG C state under maintain about 24 hours constant.Temperature under this condition of high temperature is 1000 DEG C ~ 1100 DEG C, forms polycrystalline with 12 hours ~ 24 hours from liquation by crystalline growth.The degree of freedom maintaining the time of this temperature constant is large, does not require strict time management.Next, stop by Temperature fall, in-furnace temperature being declined to the energising of heater.Time declined within 6 hours.
Pulverized after thus obtained CIG polycrystalline returns to room temperature, and then to be mixed with Se, S and CdSe and vacuum is sealing in quartz ampoule, again put in stove.
In the manufacturing process of N-shaped CIGSS alloy, rise to about 200 DEG C as the 1st step.Its reason is, the fusing point of Se and S is low, after 200 DEG C fully melting, make crystalline growth together with other element from liquation.Thereby, it is possible to obtain the polycrystalline of high-quality.Intensification to 200 DEG C rose to 200 DEG C with 2 hours.In this condition, keep about 12 hours, next rose to 1050 DEG C with 6 hours.By this condition of high temperature maintain about 24 hours constant.The degree of freedom of the time of this maintenance is large, does not require strict time management.Then stop the heater of electric furnace and return to room temperature.Stop after the energising of heater, can place until become near room temperature.
In addition, as the manufacture method of N-shaped CIGSS alloy, if In simple substance mixes with Se simple substance, there is chemical reaction and generate heat, can explode in significant situation, because of herein illustrate each self-separation and with 2 the stages manufacture method, but certainly, note heating, blast fully, also can carry out the manufacture in 1 stage.
In this case, Cu, In, Ga, Se, S and CdSe is weighed and simultaneously vacuum is sealing in quartz ampoule.
Figure 14 shows the temperature control status 62 in the manufacture method of the N-shaped CIGSS alloy in 1 technique.Consider that the fusing point of Se and S is low, first rise to 200 DEG C and by Se and S liquation fully, after maintaining certain hour, be warmed up to 1050 DEG C.The degree of freedom maintaining the time of high temperature is large, does not require strict time management.Then stop the heater of electric furnace and return to room temperature.Stop after the energising of heater, can place until become near room temperature.
In the manufacture of CIG alloy, ratio using Cu, In and Ga as pantogen subnumber than 1:2 is illustrated, but the ratio of In and Ga is as 1:x:(1-x) and adjust according to object, function in the scope of 0 < x < 1.In addition, using CIG3 unit be alloy as 1 Se ratio 1.7 ~ 2.3 scope, it is also according to object, function and adjusting.
This N-shaped CIGSS alloy uses as the material of pn homojunction layer formation on the light absorbing zone of CIGSS solar cell.Even if when employing this N-shaped CIGSS alloy, the manufacture method of sputtering target and the method forming pn homojunction layer on the light absorbing zone of CIGS solar cell are identical, below, be described about the manufacture method of sputtering target of N-shaped CIGS alloy and the manufacture method of solar cell.
Figure 15 is manufacture method flow process Figure 64 of sputtering target.The method being manufactured sputtering target by N-shaped CIGS alloy is, in step S61, the polycrystalline of N-shaped CIGS alloy is pulverized and powdered, in step S62, be filled in the mold being configured to desired shape and also carry out large blocking by pressurization processing, in step S63, the N-shaped CIGS alloy section by large blocking and form sputtering target.
If the profile of the N-shaped CIGS alloy manufactured is suitable for sputter equipment, does not then need large blocking, can only cut into slices and form sputtering target.
The figure of the concept 66 that N-shaped CIGS thin film that Figure 16 display is the use of the sputtering target of the N-shaped CIGS alloy manufactured by the present invention, that adopt sputtering is formed.Overleaf on electrode 14, be laminated with light absorbing zone 16, fly out sputtered atom make it be attached on this light absorbing zone 16, forms N-shaped cigs layer.Like this, can by except the feature of 1 technique film forming except having, Cd is diffused in N-shaped cigs layer equably, and Cd concentration also critically can control when N-shaped CIGS alloy manufactures, therefore, it is possible to carry out the manufacture of high efficiency CIGS solar cell.
Figure 17 is the figure of the manufacture state 70 for illustration of the light absorbing zone adopting sputter equipment.Be provided with in sputter equipment 72: carry out vacuumizing the peristome of 74; Inject the peristome of Ar (argon) gas 76; And inject the peristome of cooling water 82.Sample bench 84 is positioned in substrate is defined backplate Mo substrate 86 by Mo.On the top of sputter equipment 72, be provided with the sputtering target 80 formed by N-shaped CIGS alloy being installed on electrode 82.In electrode 78 and sample bench 84, be connected with DC power supply 92 using sample bench 84 as anode.
If apply high voltage by DC power supply 92 and by Ar gas 76 ionization, the Ar element 88 of ionization is collided with the sputtering target 80 formed by N-shaped CIGS alloy, the sputtered atom 90 on the surface of the sputtering target 80 then formed by N-shaped CIGS alloy is flown by bullet, this sputtered atom 90 reach Mo substrate 86 and pile up, film forming, the CIGS thin film that Cd has spread equably is formed by 1 technique.
In addition, become the cigs layer of light absorbing zone, also can by manufacturing the sputtering target that be formed by CIGS alloy, profit uses the same method film forming.
Figure 18 is the flow chart that display employs an example of the manufacture method 96 of the solar cell of the sputtering target formed by CIGS alloy and N-shaped CIGS alloy.
In step S71, at substrate by sputtering film-forming Mo.In step S72, in order to being connected in series of each unit, cutting backplate and carry out pattern formation.And then, in step S73, use the CIGS sputtering target of light absorbing zone, form CIGS light absorbing zone by sputter equipment by 1 technique.
In step S74, the N-shaped CIGS sputtering target that the present invention relates to is equipped on sputter equipment, CIGS film is formed N-shaped cigs layer.
And then in step S75, the N-shaped cigs layer of formation is immersed in strong alkaline aqueous solution, the film forming CdS resilient coating by solution growth method.Then, in step S76, cut CIGS light absorbing zone and resilient coating and form pattern.In step S77, on the buffer layer, by such as MOCVD (Metal Organic Chemical Vapor Deposition: metal organic chemical vapor deposition) device, film forming high resistance buffer layer and transparent conductive film layer and form electrode.In step S78, again cut conductive film layer and carry out pattern formation, in step S79, by the bus acrylonitrile that formed by aluminium etc. in backplate, for layer stacked on substrate, cover glass sealing material is sealed and completes solar cell.
The N-shaped CIGS alloy that the present invention relates to above, the manufacture method with the CIGS solar cell of pn homojunction layer that the present invention relates to is illustrated, even if but also can be used in the film forming of light absorbing zone and pn homojunction layer by vacuum vapour deposition.
Figure 19 is the plane graph of vacuum deposition apparatus 100, is made up of vacuum chamber 102, diffusion pump 104, mechanical booster pump 106 and oil rotary pump 108.
In vacuum chamber 102, carrying out is the film forming of the light absorbing zone that alloy 118 is formed by the CIGS4 unit that the present invention relates to.Be vacuum to make in vacuum chamber 102, by diffusion pump 104 and oil rotary pump 108, the air of the inside of purging vacuum room 102.With regard to mechanical booster pump 106,2 the cocoon type rotors being positioned at housing enter the driven wheel of its axle head and rotate to the same period one another in opposite directions.The gas entered from air entry is limited in the space between housing and rotor, is released to air from exhaust side by the rotation of rotor.Therefore, by making mechanical booster pump 106 combine with diffusion pump 104 and oil rotary pump 108, exhaust velocity can be made to increase substantially.
Figure 14 to be presented in the vacuum chamber 102 of vacuum deposition apparatus 100 by the evaporation from N-shaped CIGS alloy 118 state 110 of film forming N-shaped cigs layer on the cigs layer being laminated in Mo substrate 86.The Mo substrate 86 being laminated with cigs layer and the tungsten plate 120, the heater 112 that are equipped with N-shaped CIGS alloy 118 is had in vacuum chamber 102.And then possess the closer 116 stopping film forming when the thickness of N-shaped cigs layer becomes the thickness of regulation.
First the N-shaped CIGS alloy 118 as evaporation sample is arranged at tungsten plate 120, then, makes diffusion pump 104, oil rotary pump 108 and mechanical booster pump 106 rotate and carry out vacuum exhaust.Once become high vacuum state by vacuum exhaust, just connect heater power source 114, electric current is flow through to heater 112 and heats.The temperature of N-shaped CIGS alloy 118 reaches evaporating temperature and just opens closer 116.
Thus, to be piled up in from the deposition material of N-shaped CIGS alloy 118 on the Mo substrate 86 being laminated with cigs layer and film forming.The value that thickness reaches regulation just closes closer 116, terminates evaporation.
Like this, the N-shaped CIGS alloy that the present invention relates to, even if also can use as the material of pn homojunction layer film forming by the vacuum vapour deposition employing vacuum deposition apparatus.
Above, embodiments of the present invention are illustrated, but the present invention comprises the suitable distortion not damaging this object and advantage, and then, not by the restriction of above-mentioned execution mode.
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 resilient coatings
20 high resistance buffer layer
22 transparency electrodes
24 depletion layers
26 Fermi levels
28 valence bands
30 conduction bands
32 boundary defects
34 N-shaped cigs layers
36 structures being provided with the CIGS solar cell of N-shaped cigs layer
38 structures being provided with the CIGSS solar cell of N-shaped CIGSS layer
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 manufacture state of 44 employing electric furnaces
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 adopt the N-shaped cigs layer of sputtering to form concept
The manufacture state of the light absorbing zone of 70 employing sputter equipments
72 sputter equipments
74 vacuumize
76 Ar gases
78 electrodes
80 sputtering targets
82 cooling waters
84 sample benchs
86 Mo substrates
88 Ar elements
90 sputtered atoms
92 DC power supply
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 (21)
1., as the N-shaped light absorbing zone alloy that the filmogen of solar cell uses, it comprises copper, indium, gallium, selenium and IIb race element.
2. N-shaped light absorbing zone alloy according to claim 1, is characterized in that, make copper, indium, gallium, selenium and the compound that is made up of IIb race element and VIb race element at high temperature crystallization make.
3., as the N-shaped light absorbing zone alloy that the filmogen of solar cell uses, it is included in the composition adding sulphur in copper, indium, gallium, selenium and IIb race element further.
4. N-shaped light absorbing zone alloy according to claim 3, is characterized in that, make copper, indium, gallium, selenium, sulphur and the compound that is made up of IIb race element and VIb race element at high temperature crystallization make.
5. the N-shaped light absorbing zone alloy according to claim 2 or 4, is characterized in that, the described compound be made up of IIb race element and VIb race element is cadmium selenide.
6. the N-shaped light absorbing zone alloy according to claim 2 or 4, is characterized in that, the described compound be made up of IIb race element and VIb race element is zinc selenide.
7. N-shaped light absorbing zone alloy according to claim 4, is characterized in that, the compound be made up of IIb race element and VIb race element is cadmium sulfide.
8. N-shaped CIGSS alloy according to claim 4, is characterized in that, the compound be made up of IIb race element and VIb race element is zinc sulphide.
9. a manufacture method for N-shaped light absorbing zone alloy, is characterized in that, be the manufacture method of the N-shaped light absorbing zone alloy comprising copper, indium, gallium, selenium and IIb race element, it possesses following operation:
By copper, indium, gallium mixing, make its at high temperature crystallization and make the 1st operation of CIG alloy,
Described CIG alloy is pulverized and makes the 2nd operation of CIG alloy powder, and
The compound mixing selenium and be made up of IIb race element and VIb race element in chippy described CIG alloy, makes its at high temperature crystallization and make the 3rd operation of N-shaped CIGS alloy.
10. the manufacture method of N-shaped light absorbing zone alloy according to claim 9, is characterized in that, in described 1st operation and described 3rd operation, makes crystalline growth at 1000 ~ 1100 DEG C and generates polycrystalline from liquation.
The manufacture method of 11. 1 kinds of N-shaped light absorbing zone alloys, is characterized in that, is the manufacture method of the N-shaped light absorbing zone alloy comprising copper, indium, gallium, selenium, sulphur and IIb race element,
It possesses following operation: copper, indium, gallium mixing are made its at high temperature crystallization and manufacture the 1st operation of CIG alloy,
Described CIG alloy is pulverized and manufactures the 2nd operation of CIG alloy powder, and
The compound mixing selenium, sulphur and be made up of IIb race element and VIb race element in chippy described CIG alloy, makes its at high temperature crystallization and manufacture the 3rd operation of N-shaped CIGSS alloy.
The manufacture method of 12. N-shaped C light absorbing zone alloys according to claim 11, is characterized in that,
Be in the 1st operation of alloy in described manufacture CIG3 unit, make crystalline growth from liquation at 1000 ~ 1100 DEG C and generate polycrystalline,
3rd operation of described manufacture N-shaped CIGSS alloy possesses following step: make temperature maintain the first step of certain hour at 180 ~ 220 ° by heating up; And temperature is maintained the second step of certain hour at 1000 ~ 1100 °.
The manufacture method of 13. N-shaped light absorbing zone alloys according to claim 9 or 11, is characterized in that,
In described 1st operation and described 3rd operation, mixed raw material are sealing in ampoule by vacuum.
The manufacture method of 14. N-shaped light absorbing zone alloys according to claim 13, it is characterized in that, described ampoule is covered by carbon.
The manufacture method of 15. N-shaped light absorbing zone alloys according to claim 13, it is characterized in that, described ampoule is quartz glass.
The manufacture method of 16. 1 kinds of N-shaped light absorbing zone sputtering targets, it is characterized in that possessing: the slicing process section of the N-shaped light absorbing zone alloy of the manufacture method manufacture of the N-shaped light absorbing zone alloy described in any one by claim 9 or 11 being manufactured N-shaped light absorbing zone sputtering target.
The manufacture method of 17. 1 kinds of N-shaped light absorbing zone sputtering targets, is characterized in that, possesses following operation:
N-shaped light absorbing zone described in any one of claim 9 or 11 alloy is pulverized and the powdered operation of powdered,
Powdery described N-shaped light absorbing zone alloy is processed and the bulk chemical industry sequence of large blocking by pressurization, and
The slicing process of the described N-shaped light absorbing zone alloy section by large blocking.
18. 1 kinds of solar cells, is characterized in that, use the N-shaped light absorbing zone sputtering target manufactured by method described in any one of claim 16 or 17, by sputter equipment, are formed with N-shaped light absorbing zone being laminated on the light absorbing zone on substrate.
19. solar cells according to claim 18, is characterized in that, N-shaped light absorbing zone and the resilient coating be laminated on this N-shaped light absorbing zone have identical IIb race element.
The manufacture method of 20. 1 kinds of solar cells, it is characterized in that, use the N-shaped light absorbing zone sputtering target manufactured by the method described in any one of claim 16 or 17, by sputter equipment, form N-shaped light absorbing zone being laminated on the light absorbing zone on substrate.
The manufacture method of 21. 1 kinds of solar cells, it is characterized in that, possess following N-shaped light absorbing zone film formation process: the N-shaped light absorbing zone alloy described in any one using claim 9 or 11, by vacuum evaporation, film forming N-shaped light absorbing zone on the light absorbing zone being laminated in substrate.
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| 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 |
| JP2020180376A (en) * | 2020-06-29 | 2020-11-05 | 古河機械金属株式会社 | Metal film, anode for lithium ion battery, lithium ion battery, and manufacturing method of metal film |
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