CN111029439A - Method for preparing copper indium gallium selenide thin-film solar cell without selenization - Google Patents
Method for preparing copper indium gallium selenide thin-film solar cell without selenization Download PDFInfo
- Publication number
- CN111029439A CN111029439A CN201911264138.1A CN201911264138A CN111029439A CN 111029439 A CN111029439 A CN 111029439A CN 201911264138 A CN201911264138 A CN 201911264138A CN 111029439 A CN111029439 A CN 111029439A
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- Prior art keywords
- layer
- preparing
- alkali metal
- sputtering
- molybdenum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 60
- 239000010409 thin film Substances 0.000 title claims abstract description 33
- 238000004544 sputter deposition Methods 0.000 claims abstract description 100
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 74
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 66
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 44
- 239000011733 molybdenum Substances 0.000 claims abstract description 44
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 238000010521 absorption reaction Methods 0.000 claims abstract description 31
- 230000004888 barrier function Effects 0.000 claims abstract description 23
- 230000001105 regulatory effect Effects 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 238000009792 diffusion process Methods 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 207
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 50
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 44
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 37
- 229910052786 argon Inorganic materials 0.000 claims description 22
- 239000010408 film Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical group [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 10
- QMXBEONRRWKBHZ-UHFFFAOYSA-N [Na][Mo] Chemical compound [Na][Mo] QMXBEONRRWKBHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- -1 alkali metal salt Chemical class 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000011775 sodium fluoride Substances 0.000 claims description 8
- 235000013024 sodium fluoride Nutrition 0.000 claims description 8
- 239000013077 target material Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical group OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 6
- 239000005083 Zinc sulfide Substances 0.000 claims description 6
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 6
- 229920001721 polyimide Polymers 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 6
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012459 cleaning agent Substances 0.000 claims description 5
- 239000005361 soda-lime glass Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- WZGKIRHYWDCEKP-UHFFFAOYSA-N cadmium magnesium Chemical compound [Mg].[Cd] WZGKIRHYWDCEKP-UHFFFAOYSA-N 0.000 claims description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical group [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims 1
- 239000011669 selenium Substances 0.000 abstract description 10
- 239000012298 atmosphere Substances 0.000 abstract description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052711 selenium Inorganic materials 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 239000013589 supplement Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 16
- 238000004140 cleaning Methods 0.000 description 9
- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 description 9
- 239000006096 absorbing agent Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 229910002059 quaternary alloy Inorganic materials 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000010965 430 stainless steel Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003342 selenium Chemical class 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- C—CHEMISTRY; METALLURGY
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/0694—Halides
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/14—Metallic material, boron or silicon
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- 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
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- 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 potential barriers
- 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 potential barriers 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 potential barriers 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
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- 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
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention provides a method for preparing a copper indium gallium selenide thin-film solar cell without selenization, which is characterized in that an alkali metal-molybdenum composite layer is prepared on a substrate deposited with a barrier layer, then an alkali metal regulating layer is introduced, a copper indium gallium selenide absorption layer is sputtered on the high-temperature substrate under the condition of no additional selenium atmosphere supplement, and the diffusion quantity of alkali metal to the absorption layer can be accurately regulated and controlled through the thickness and the processing time of the alkali metal regulating layer, so that the doping concentration in the absorption layer, the preferred orientation of the absorption layer and the grain size are controlled. The absorption layer is formed by one-step sputtering, and the process is simple and has better consistency. The prepared CIGS thin-film solar cell is high in efficiency, good in uniformity and wide in application prospect.
Description
Technical Field
The invention relates to the technical field of thin film solar cell manufacturing, in particular to a method for preparing a copper indium gallium selenide thin film solar cell without selenization.
Background
In the world of today, energy is a common concern all over the world and all over the human, and is also an important material basis for social progress and human activities, which plays a crucial role in the healthy and continuous development of the global economy and the daily life of people. At present, fossil energy such as petroleum and coal is exhausted, and the use of the fossil energy generates a large amount of harmful gas, so that the ecological environment is irreversibly damaged and the survival of human beings is endangered. From the perspective of sustainable development, clean and pollution-free renewable energy sources, such as tidal energy, wind energy, geothermal energy, solar energy, and the like, need to be vigorously developed. With the enhancement of environmental awareness of people, the development of solar cells becomes the key direction in the research field of renewable energy resources at home and abroad.
Photovoltaic power generation is an important development direction for renewable energy utilization, and a Copper Indium Gallium Selenide (CIGS) thin film material is a research hotspot in the field of photovoltaic technology, has the advantages of rich raw materials, low cost, high light absorption coefficient, high theoretical conversion efficiency, adjustable forbidden bandwidth and the like, and the preparation research of the current high-efficiency CIGS solar cell has attracted extensive attention, and the highest conversion efficiency of the current high-efficiency CIGS solar cell is reported to reach 23.4 percent and is 1 percent higher than that of a polysilicon technical cell.
By using vacuum magnetron sputtering technology, which is known for its high deposition rate and good large surface uniformity, many companies have been able to prepare high efficiency modules: MiaSol é 16.5%, 17.5% from Solar Frontier and 18.2% from AVANCIS. The solar Frontier produced CIGS without cadmium in 2019 to a single point world maximum efficiency of 23.3%. Although these companies canCapable of producing a high-efficiency battery module, but inevitably using highly toxic H in the production process thereof2Se gas or Se vapor. Based on H2The high toxicity of Se gas, the high energy consumption of Se steam, the treatment of generated waste and other practical problems, and redundant selenium can be enriched on the inner wall of the vacuum chamber, so that the equipment maintenance cost and the maintenance frequency are increased, and therefore, the research on the method for preparing the copper indium gallium selenide thin-film solar cell without selenization has important practical significance.
Disclosure of Invention
The invention aims to provide a method for preparing a copper indium gallium selenide thin-film solar cell without selenization, and the method is used for solving the problems of high toxicity and high cost of the existing method.
The purpose of the invention is realized by the following technical scheme: a method for preparing a copper indium gallium selenide thin-film solar cell without selenization comprises the following steps:
(a) preparation of a barrier layer: depositing a barrier layer with the thickness of 50-400 nm on the pretreated substrate by adopting a magnetron sputtering method or a plasma enhanced chemical vapor deposition method;
(b) preparing an alkali metal-molybdenum composite layer: depositing a molybdenum layer doped with alkali metal on the barrier layer by adopting a magnetron sputtering method, and then depositing a pure molybdenum layer on the molybdenum layer doped with alkali metal; or
Depositing a molybdenum electrode layer with the thickness of 200-1000 nm on the barrier layer by adopting a magnetron sputtering method, and then preparing an alkali metal salt layer with the thickness of 10-30 nm on the molybdenum electrode layer by adopting an evaporation method;
(c) preparing an alkali metal regulating layer on the pure molybdenum layer or the alkali metal salt layer prepared in the step (b), wherein the alkali metal regulating layer is used for controlling the diffusion amount of alkali metal to the absorption layer;
(d) preparing a copper indium gallium selenide absorption layer: rapidly heating the substrate to 600-700 ℃, and preparing a copper indium gallium selenide absorption layer on the alkali metal regulation and control layer by adopting a magnetron sputtering method;
(e) preparing a buffer layer: preparing a buffer layer with the thickness of 40-200 nm on the copper indium gallium selenide absorption layer by adopting a chemical water bath method or a magnetron sputtering method;
(f) preparing a high-resistance layer: preparing a high-resistance layer with the thickness of 80-200 nm on the buffer layer by adopting a magnetron sputtering method;
(g) preparation of the window layer: preparing a window layer with the thickness of 100-400 nm on the high-resistance layer by adopting a magnetron sputtering method; and obtaining the copper indium gallium selenide thin-film solar cell.
In the step (a), the substrate is a stainless steel sheet with a thickness of 50-300 μm, a soda-lime glass sheet with a thickness of 3.2mm or a polyimide substrate with a thickness of 25-50 μm, and the pretreatment of the substrate is as follows: the substrate is cleaned by a roller brush and a cleaning agent for the first time, then cleaned by high-pressure deionized water under ultrasonic waves, and finally dried by a hot air knife at 80 ℃.
In the step (a), the barrier layer is a single-layer film of one of a silicon oxide film, a titanium oxide film, a silicon nitride film, a titanium metal film and a tungsten-titanium alloy film or a multilayer film formed by alternately depositing more than one film; the air pressure of the barrier layer is 0.2-1 pa when the barrier layer is prepared by magnetron sputtering, and the sputtering power is 0.1-8W/cm2。
In the step (b), the molybdenum layer doped with the alkali metal is a molybdenum sodium layer, and is prepared by adopting a direct-current magnetron sputtering method, wherein the sputtering pressure is 0.2-1 pa, and the sputtering power is 0.2-4W/cm2The target is a molybdenum sodium target mixed with 1-10% of sodium molybdate, the pure molybdenum layer is prepared by a direct-current magnetron sputtering method, the sputtering pressure is 0.1-1 pa, and the sputtering power is 1-10W/cm2The total thickness of the molybdenum sodium layer and the pure molybdenum layer is 200-1000 nm, wherein the thickness of the molybdenum sodium layer is 10% -90% of the total thickness; the alkali metal salt is sodium fluoride, potassium fluoride, rubidium fluoride or cesium fluoride.
In the step (c), when the pure molybdenum layer is adopted, the alkali metal regulating layer is an amorphous copper indium gallium selenide layer deposited on the pure molybdenum layer by adopting a magnetron sputtering method at the temperature of 25-300 ℃; or
The alkali metal regulating layer is a molybdenum oxide layer formed on the surface of the pure molybdenum layer by treating the substrate with ozone or hydrogen peroxide. The amorphous CIGS layer can provide free selenium atoms, and is helpful for the formation of molybdenum selenide.
In the step (c), when the layer is an alkali metal salt layer, the alkali metal regulating layer is an amorphous copper indium gallium selenide layer deposited on the pure molybdenum layer by a magnetron sputtering method at the temperature of 25-300 ℃.
In the step (c), the thickness of the amorphous CIGS layer is 10-100 nm, and the sputtering power during the preparation of the amorphous CIGS layer is 0.1-2 w/cm2The sputtering pressure is 0.2 to 0.5 pa.
In the step (c), the ozone treatment comprises the following steps: carrying out ozone treatment at 25-150 ℃ for 5-30 min by adopting ozone treatment equipment; the hydrogen peroxide treatment comprises the following steps: and (3) treating the mixture for 2-20 min at normal temperature in an air environment by using hydrogen peroxide with the mass concentration of 3-30%.
In the step (d), the CIGS absorbing layer is prepared by adopting a pulse direct current magnetron sputtering method, wherein during sputtering, the pulse delay is 1000-4000 ns, and the sputtering power is 3-5W/cm2The sputtering pressure is 0.2-0.5 pa, and the sputtering thickness is 1000-1500 nm. The purpose of high power sputtering is to provide higher energy to crystallize the CIGS.
In the step (e), the buffer layer is cadmium sulfide or zinc sulfide prepared by a chemical water bath method, wherein the water bath temperature is 60-75 ℃, and the water bath reaction time is 5-15 min; or
The buffer layer is a zinc sulfide, cadmium sulfide or magnesium-doped zinc oxide film prepared by adopting a magnetron sputtering method, a zinc sulfide, cadmium sulfide or magnesium-doped zinc oxide target material is sputtered by adopting a pulse direct-current magnetron sputtering method, and the sputtering power is 0.1-2W/cm2The sputtering frequency is 100KHz, the sputtering time delay is 4000ns, the sputtering pressure is 0.3-0.6 pa, and argon or helium is adopted during sputtering.
According to the invention, a high-efficiency CIGS thin-film solar cell is obtained by directly sputtering under a high-temperature selenium-free atmosphere, the alkali metal regulating layer is innovatively introduced, and the accurate regulation of the diffusion amount of alkali metal to the absorption layer can be realized through the thickness and the processing time of the alkali metal regulating layer, so that the doping concentration in the absorption layer, the preferred orientation and the grain size of the absorption layer are controlled, and the high-efficiency and large-grain CIGS absorption layer is obtained. Because the selenium-free atmosphere annealing is not adopted and the one-time sputtering forming is adopted, the production cost and the equipment maintenance cost are greatly reduced, and the stable and efficient preparation of the CIGS thin-film solar cell is realized.
The CIGS thin-film solar cell prepared by the method has the advantages of high efficiency, good uniformity, simple process, low cost, no need of an additional selenium source and the like.
Drawings
FIG. 1 is an SEM surface picture of the alkali metal control layer prepared in example 1.
Fig. 2 shows XPS test results of sodium for different thickness of the alkali metal control layer.
Fig. 3 is a preferred XRD orientation pattern of the CIGS absorber of example 1 and no alkali metal accommodating layer.
Fig. 4 is a SEM surface (a), cross-section (b) of the CIGS absorber of example 1 compared to a CIGS absorber without an alkali metal modifier layer SEM surface (c), cross-section (d).
FIG. 5 is a graph of CV test results for samples of example 1 and no alkali metal control layer.
FIG. 6 is a graph of IV curves for example 1 and samples without an alkali metal control layer.
FIG. 7 is a graph of the Raman test results of the 80nm low temperature CIGS layer sample and the 80nm600 ℃ sputtered CIGS layer sample after high temperature annealing.
Detailed Description
The following examples are intended to illustrate the present invention in further detail, but the present invention is not limited thereto in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
The manufacturing method of the battery comprises the following steps:
step one, cleaning a substrate: selecting a 430 stainless steel sheet with the thickness of 150 mu m, firstly cleaning by adopting a rolling brush and cleaning agent mode, then cleaning by adopting an ultrasonic wave and high-pressure deionized water mode, and finally drying the substrate by adopting a hot air knife at 80 ℃;
step two, preparing a barrier layer: a titanium nitride barrier layer with the thickness of 100nm is deposited on a substrate by adopting a magnetron sputtering mode of a metallic titanium target under the conditions that the ratio of argon to nitrogen is 10: 1, the sputtering pressure is 0.3pa and the sputtering power is 1600W.
Step three, preparing an alkali metal-molybdenum composite layer: preparing a molybdenum electrode layer with the thickness of 800nm on the barrier layer by adopting a magnetron sputtering molybdenum target material mode under the conditions that the argon flow is 10sccm, the argon pressure is 0.1pa and the sputtering power is 1600W; evaporating a layer of sodium fluoride film with the thickness of 10nm at room temperature by adopting a mode of evaporating sodium fluoride powder by electron beams.
Step four, preparing an alkali metal regulation layer: the CIGS quaternary alloy target is sputtered In a magnetron sputtering mode, the atomic percentage of the target is Cu: In: Ga: Se = 21.961: 19.088: 7.336: 51.615, sputtering is carried out at normal temperature, the flow of argon is 10sccm, the air pressure is 0.4pa, the sputtering power is 200W, and the thickness of the alkali metal regulating layer is 80 nm.
Step five, preparing a high-temperature CIGS absorption layer: heating the substrate with the prepared alkali metal regulation layer in a graphite heater (with the power set to 500W) for 10min, raising the temperature to 630 ℃, preparing a CIGS absorption layer with the thickness of 1.5 mu m on the alkali metal regulation layer by adopting pulse direct-current magnetron sputtering, wherein the sputtering frequency is 100KHz, the sputtering delay is 2500ns, the sputtering gas is argon, the sputtering gas flow is 10sccm, the sputtering power is 1200W, and after the sputtering is finished, closing the heater and reducing the temperature to the room temperature.
Step six, preparing a buffer layer: firstly, dissolving 0.4g of cadmium acetate in 50mL of deionized water, dissolving 0.882g of sodium citrate in 20mL of deionized water, dissolving 1.9g of thiourea in 40mL of deionized water, adopting a magneton to rotate and stir until the powder is completely dissolved, mixing the solution in 10mL of ammonia water, uniformly stirring, putting the mixture into a reaction container, putting the container into a water bath kettle at 75 ℃, reacting for 10min, taking out, adopting deionized water to clean and blow-dry.
Step seven, preparing a high-resistance layer: preparing the high-resistance layer by adopting a magnetron sputtering intrinsic zinc oxide target material mode, wherein the ratio of argon to oxygen is 40: 1, the sputtering pressure is 0.4pa, the sputtering power is 100W, and preparing the high-resistance layer on the cell with the buffer layer, wherein the thickness of the high-resistance layer is 120 nm.
Step eight, preparing a window layer: preparing a window layer by adopting a magnetron sputtering aluminum-doped zinc oxide mode, wherein the sputtering gas is argon, the sputtering pressure is 0.4pa, the sputtering power is 1200W, and preparing the window layer on the battery with the high-resistance layer, wherein the thickness of the window layer is 400 nm.
Examples 2 to 6
The deposition thicknesses of the alkali metal control layers (20 nm, 40nm, 60nm, and 100nm, respectively) were varied, and the other processes were the same as in example 1.
Comparative example 1
Preparing a sample of the alkali-metal-free control layer: the process operation was the same as in example 1 except that the operation of step three was not performed.
FIG. 1 is a SEM surface picture of the alkali metal control layer prepared in example 1; FIG. 2 shows XPS test results of sodium for different thickness alkali metal control layers; fig. 3 is the XRD preferred orientation of the CIGS absorber of example 1 and no alkali metal accommodating layer; fig. 4 is a SEM surface, cross-section, cross-sectional comparison of the CIGS absorber of example 1 with a CIGS absorber SEM surface without an alkali metal modifier. Fig. 5 is a graph showing CV test results of the samples without the alkali metal control layer in example 1, and it is obvious from the results that the width of the depletion layer is reduced by adding the alkali metal control layer. FIG. 6 is a graph of the IV curves of the samples of example 1 and the alkali metal-free control layer, and the results show that without the low temperature alkali metal control layer, the efficiency is very low due to the non-ohmic contact of the interface between the molybdenum and the CIGS absorber layer, and the cell efficiency reaches 16% after the alkali metal control layer is added (Voc 0.562V Jsc 35.3 mA/cm)2FF 80.8 efficiency 16.05%).
Example 7
Step one, cleaning a substrate: selecting a soda-lime glass substrate with the thickness of 3.2mm, firstly cleaning the soda-lime glass substrate by adopting a rolling brush and cleaning agent mode, then cleaning the soda-lime glass substrate by adopting ultrasonic waves and high-pressure deionized water, and finally drying the substrate by adopting a hot air knife at 80 ℃;
step two, preparing a barrier layer: a silicon oxide barrier layer with the thickness of 50nm is deposited on a substrate by adopting a magnetron sputtering silicon target material mode under the conditions that the ratio of argon to oxygen is 10: 2, the sputtering pressure is 0.3pa and the sputtering power is 1200W.
Step three, preparing an alkali metal-molybdenum composite layer: preparing a molybdenum electrode layer with the thickness of 800nm on the barrier layer by adopting a magnetron sputtering molybdenum target material mode under the conditions that the argon flow is 10sccm, the argon pressure is 0.1pa and the sputtering power is 1600W; evaporating a layer of sodium fluoride film with the thickness of 10nm at room temperature by adopting a mode of evaporating sodium fluoride powder by electron beams.
Step four, preparing an alkali metal regulation layer: the method is characterized In that a CIGS quaternary alloy target is sputtered In a magnetron sputtering mode, the atomic percentage of the target is Cu: In: Ga: Se = 21.961: 19.088: 7.336: 51.615, sputtering is carried out at normal temperature, the flow of argon is 10sccm, the air pressure is 0.5pa, the sputtering power is 200W, and the thickness of an alkali metal regulating layer is 80 nm.
Step five, preparing a high-temperature CIGS absorption layer: heating the substrate with the prepared alkali metal regulation layer in a graphite heater (with the power set to 500W) for 10min, raising the temperature to 630 ℃, preparing a CIGS absorption layer with the thickness of 1.5 mu m on the alkali metal regulation layer by adopting pulse direct-current magnetron sputtering, wherein the sputtering frequency is 100KHz, the sputtering delay is 2500ns, the sputtering gas is argon, the sputtering gas flow is 10sccm, the sputtering power is 800W, and after the sputtering is finished, closing the heater and reducing the temperature to the room temperature.
Steps six to eight are the same as in example 1.
Example 8
Step one, cleaning a substrate: selecting a polyimide substrate with the thickness of 50 microns, firstly cleaning the polyimide substrate by adopting a rolling brush and cleaning agent mode, then cleaning the polyimide substrate by adopting ultrasonic waves and high-pressure deionized water, and finally drying the polyimide substrate by adopting a hot air knife at 80 ℃.
Step two, preparing a barrier layer: a titanium nitride barrier layer with the thickness of 100nm is deposited on a substrate by adopting a magnetron sputtering mode of a metallic titanium target under the conditions that the ratio of argon to nitrogen is 10: 1, the sputtering pressure is 0.3pa and the sputtering power is 1600W.
Step three, preparing an alkali metal-molybdenum composite layer: preparing a 800nm molybdenum electrode layer on the barrier layer by adopting a magnetron sputtering molybdenum target material mode under the conditions that the argon flow is 10sccm, the argon pressure is 0.1pa and the sputtering power is 1600W; evaporating a layer of sodium fluoride film with the thickness of 10nm at room temperature by adopting a mode of evaporating sodium fluoride powder by electron beams.
Step four, preparing an alkali metal regulation layer: the CIGS quaternary alloy target is sputtered In a magnetron sputtering mode, the atomic percentage of the target is Cu: In: Ga: Se = 21.961: 19.088: 7.336: 51.615, sputtering is carried out at normal temperature, the flow of argon is 10sccm, the air pressure is 0.4pa, the sputtering power is 200W, and the thickness of the alkali metal regulating layer is 80 nm.
Step five, preparing a high-temperature CIGS absorption layer: heating the substrate with the prepared alkali metal regulation layer in a graphite heater (with the power set to 500W) for 10min, raising the temperature to 630 ℃, preparing a CIGS absorption layer with the thickness of 1.5 mu m on the alkali metal regulation layer by adopting pulse direct-current magnetron sputtering, wherein the sputtering frequency is 100KHz, the sputtering delay is 2500ns, the sputtering gas is argon, the sputtering gas flow is 10sccm, and the sputtering power is 1200W, and closing the heater after the sputtering is finished, and reducing the temperature to the room temperature.
Steps six to eight are the same as in example 1.
Example 9
Step one, step two are the same as example 1.
Step three, preparing an alkali metal-molybdenum composite layer: firstly, a direct current magnetron sputtering mode is adopted to sputter a molybdenum sodium target mixed with 5 percent of sodium molybdate, the sputtering pressure is 0.5pa, and the sputtering power is 1W/cm2Preparing a molybdenum sodium layer with the thickness of 500 nm; then sputtering the molybdenum target material by adopting a direct current magnetron sputtering mode, wherein the sputtering pressure is 0.1pa, and the sputtering power is 5W/cm2And preparing a molybdenum film with the thickness of 500 nm.
Step four, preparing an alkali metal regulation layer: and (3) placing the substrate in a 25% hydrogen peroxide solution, standing for 3min at normal temperature, taking out, washing with deionized water, and drying.
Step five, preparing a high-temperature CIGS absorption layer: heating the substrate with the prepared alkali metal regulation layer in a graphite heater (with the power set to 500W) for 10min, raising the temperature to 630 ℃, preparing a CIGS absorption layer with the thickness of 1.5 mu m on the alkali metal regulation layer by adopting pulse direct-current magnetron sputtering, wherein the sputtering frequency is 100KHz, the sputtering delay is 2500ns, the sputtering gas is argon, the sputtering gas flow is 10sccm, the sputtering power is 800W, and after the sputtering is finished, closing the heater and reducing the temperature to the room temperature.
Steps six to eight are the same as in example 1.
Example 10
Steps one to three are the same as in example 9.
Step four, preparing an alkali metal regulation layer: and (3) placing the substrate in an ozone treatment device, and treating for 10min by adopting ozone under a normal-temperature environment. Taking out and directly placing in vacuum.
Step five, preparing a high-temperature CIGS absorption layer: heating the substrate with the prepared alkali metal regulation layer in a graphite heater (with the power set to 500W) for 10min, raising the temperature to 630 ℃, preparing a CIGS absorption layer with the thickness of 1.5 mu m on the alkali metal regulation layer by adopting pulse direct-current magnetron sputtering, wherein the sputtering frequency is 100KHz, the sputtering delay is 2500ns, the sputtering gas is argon, the sputtering gas flow is 10sccm, the sputtering power is 400W, and after the sputtering is finished, closing the heater and reducing the temperature to the room temperature.
Steps six to eight are the same as in example 1.
Example 11
Steps one to four are the same as in example 1.
Step five, preparing a high-temperature CIGS absorption layer: heating the substrate with the prepared alkali metal regulation layer in a graphite heater (with the power set to 550W) for 10min to 700 ℃, adopting pulse direct current magnetron sputtering, wherein the sputtering frequency is 100KHz, the sputtering delay is 2500ns, the sputtering gas is argon, the sputtering gas flow is 10sccm, the sputtering power is 1200W, preparing a CIGS absorption layer with the thickness of 1.2 mu m on the alkali metal regulation layer, closing the heater after the sputtering is finished, and cooling to the room temperature.
In the CIGS solar cell, the forming of molybdenum selenide can reduce the work function mismatch between Mo and the CIGS absorption layer, and can obviously improve the performance of the device. The fact that molybdenum selenide cannot be formed under the condition of direct sputtering in the selenium-free atmosphere is also a key factor for limiting the process to prepare high-efficiency batteries. The alkali metal regulating layer is prepared on the molybdenum film, the alkali metal regulating layer is beneficial to the formation of molybdenum selenide, and particularly when the alkali metal regulating layer is a CIGS thin film sputtered at a low temperature, the CIGS thin film is in an amorphous state during low-temperature sputtering, and a plurality of free selenium clusters exist, so that the low-temperature CIGS thin film can react with the molybdenum film to form molybdenum diselenide while regulating the alkali metal, the thickness of the molybdenum diselenide is very thin, the current transmission cannot be influenced, and the work function matching between Mo and the CIGS absorbing layer can be regulated. Fig. 7 is a graph showing the results of raman tests performed on 80nm low temperature cigs layer samples and 80nm cigs layer samples sputtered at 600 c after high temperature annealing (other steps refer to example 1). The result shows that the peak position of molybdenum diselenide can be obviously detected after the CIGS sputtered at the low temperature is annealed at the high temperature, and the signal of the molybdenum diselenide is not detected after the CIGS sputtered at the high temperature of 600 ℃, so that the molybdenum diselenide is formed in a direct sputtering method, and the alkali metal regulating layer is a key technical point.
Claims (10)
1. A method for preparing a copper indium gallium selenide thin-film solar cell without selenization is characterized by comprising the following steps:
(a) preparation of a barrier layer: depositing a barrier layer with the thickness of 50-400 nm on the pretreated substrate by adopting a magnetron sputtering method or a plasma enhanced chemical vapor deposition method;
(b) preparing an alkali metal-molybdenum composite layer: depositing a molybdenum layer doped with alkali metal on the barrier layer by adopting a magnetron sputtering method, and then depositing a pure molybdenum layer on the molybdenum layer doped with alkali metal; or
Depositing a molybdenum electrode layer with the thickness of 200-1000 nm on the barrier layer by adopting a magnetron sputtering method, and then preparing an alkali metal salt layer with the thickness of 10-30 nm on the molybdenum electrode layer by adopting an evaporation method;
(c) preparing an alkali metal regulating layer on the pure molybdenum layer or the alkali metal salt layer prepared in the step (b), wherein the alkali metal regulating layer is used for controlling the diffusion amount of alkali metal to the absorption layer;
(d) preparing a copper indium gallium selenide absorption layer: rapidly heating the substrate to 600-700 ℃, and preparing a copper indium gallium selenide absorption layer on the alkali metal regulation and control layer by adopting a magnetron sputtering method;
(e) preparing a buffer layer: preparing a buffer layer with the thickness of 40-200 nm on the copper indium gallium selenide absorption layer by adopting a chemical water bath method or a magnetron sputtering method;
(f) preparing a high-resistance layer: preparing a high-resistance layer with the thickness of 80-200 nm on the buffer layer by adopting a magnetron sputtering method;
(g) preparation of the window layer: preparing a window layer with the thickness of 100-400 nm on the high-resistance layer by adopting a magnetron sputtering method; and obtaining the copper indium gallium selenide thin-film solar cell.
2. The method for preparing the CIGS thin-film solar cell without selenization in claim 1, wherein in the step (a), the substrate is a stainless steel sheet with a thickness of 50-300 μm, a soda-lime glass sheet with a thickness of 3.2mm or a polyimide substrate with a thickness of 25-50 μm, and the pretreatment of the substrate is as follows: the substrate is cleaned by a roller brush and a cleaning agent for the first time, then cleaned by high-pressure deionized water under ultrasonic waves, and finally dried by a hot air knife at 80 ℃.
3. The method for preparing the CIGS thin-film solar cell without selenization, according to claim 1, wherein in the step (a), the blocking layer is a single-layer film of one of a silicon oxide thin film, a titanium oxide thin film, a silicon nitride thin film, a titanium metal film and a tungsten-titanium alloy thin film or a multi-layer film formed by alternately depositing more than one thin film; the air pressure of the barrier layer is 0.2-1 pa when the barrier layer is prepared by magnetron sputtering, and the sputtering power is 0.1-8W/cm2。
4. The method for preparing CIGS thin-film solar cell without selenization in claim 1, wherein, in the step (b), the molybdenum layer doped with alkali metal is a molybdenum sodium layer, and is prepared by a direct current magnetron sputtering method, and sputtering is performedThe jet pressure is 0.2-1 pa, the sputtering power is 0.2-4W/cm2The target is a molybdenum sodium target mixed with 1-10% of sodium molybdate, the pure molybdenum layer is prepared by a direct-current magnetron sputtering method, the sputtering pressure is 0.1-1 pa, and the sputtering power is 1-10W/cm2The total thickness of the molybdenum sodium layer and the pure molybdenum layer is 200-1000 nm, wherein the thickness of the molybdenum sodium layer is 10% -90% of the total thickness; the alkali metal salt is sodium fluoride, potassium fluoride, rubidium fluoride or cesium fluoride.
5. The method for preparing the CIGS thin-film solar cell without selenization, according to claim 1, wherein in the step (c), when the pure molybdenum layer is adopted, the alkali metal control layer is an amorphous CIGS layer deposited on the pure molybdenum layer by a magnetron sputtering method at a temperature of 25-300 ℃; or
The alkali metal regulating layer is a molybdenum oxide layer formed on the surface of the pure molybdenum layer by treating the substrate with ozone or hydrogen peroxide.
6. The method for preparing the CIGS thin-film solar cell without selenization, according to claim 1, wherein in the step (c), when the layer is an alkali metal salt layer, the alkali metal control layer is an amorphous CIGS layer deposited on a pure molybdenum layer by a magnetron sputtering method at a temperature of 25-300 ℃.
7. The method for preparing the CIGS thin-film solar cell without selenization in claim 5 or 6, wherein in the step (c), the thickness of the amorphous CIGS layer is 10-100 nm, and the sputtering power for preparing the amorphous CIGS layer is 0.1-2 w/cm2The sputtering pressure is 0.2 to 0.5 pa.
8. The method for preparing the CIGS thin-film solar cell without selenization in accordance with claim 5, wherein in the step (c), the ozone treatment is: carrying out ozone treatment at 25-150 ℃ for 5-30 min by adopting ozone treatment equipment; the hydrogen peroxide treatment comprises the following steps: and (3) treating the mixture for 2-20 min at normal temperature in an air environment by using hydrogen peroxide with the mass concentration of 3-30%.
9. The method for preparing the CIGS thin-film solar cell without selenization in claim 1, wherein in the step (d), the CIGS absorption layer is prepared by a pulse direct-current magnetron sputtering method, the pulse delay is 1000-4000 ns during sputtering, and the sputtering power is 3-5W/cm2The sputtering pressure is 0.2-0.5 pa, and the sputtering thickness is 1000-1500 nm.
10. The method for preparing the CIGS thin-film solar cell without selenization in claim 1, wherein in the step (e), the buffer layer is cadmium sulfide or zinc sulfide prepared by a chemical water bath method, wherein the water bath temperature is 60-75 ℃, and the water bath reaction time is 5-15 min; or
The buffer layer is a zinc sulfide, cadmium sulfide or magnesium-doped zinc oxide film prepared by adopting a magnetron sputtering method, a zinc sulfide, cadmium sulfide or magnesium-doped zinc oxide target material is sputtered by adopting a pulse direct-current magnetron sputtering method, and the sputtering power is 0.1-2W/cm2The sputtering frequency is 100KHz, the sputtering time delay is 4000ns, the sputtering pressure is 0.3-0.6 pa, and argon or helium is adopted during sputtering.
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