CN105140319A - Film solar cell and preparation method thereof - Google Patents
Film solar cell and preparation method thereof Download PDFInfo
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- CN105140319A CN105140319A CN201510351099.4A CN201510351099A CN105140319A CN 105140319 A CN105140319 A CN 105140319A CN 201510351099 A CN201510351099 A CN 201510351099A CN 105140319 A CN105140319 A CN 105140319A
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- film solar
- rectification
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- tunnelling
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010410 layer Substances 0.000 claims abstract description 313
- 239000004065 semiconductor Substances 0.000 claims abstract description 44
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910001512 metal fluoride Inorganic materials 0.000 claims abstract description 7
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 7
- 150000004767 nitrides Chemical class 0.000 claims abstract description 7
- 239000010409 thin film Substances 0.000 claims description 95
- 238000000034 method Methods 0.000 claims description 43
- 210000001142 back Anatomy 0.000 claims description 33
- 239000010949 copper Substances 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 239000010408 film Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 238000004528 spin coating Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 238000005240 physical vapour deposition Methods 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 6
- 229960004643 cupric oxide Drugs 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- BTCDLVPEVFCYEU-UHFFFAOYSA-N cadmium;sulfanylidenecopper Chemical compound [Cd].[Cu]=S BTCDLVPEVFCYEU-UHFFFAOYSA-N 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 4
- 229940112669 cuprous oxide Drugs 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 4
- MTRXSNADWVEBGQ-UHFFFAOYSA-N [S].[Se].[Zn].[Cu] Chemical compound [S].[Se].[Zn].[Cu] MTRXSNADWVEBGQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Inorganic materials [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910017083 AlN Inorganic materials 0.000 claims description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- GQCYCMFGFVGYJT-UHFFFAOYSA-N [AlH3].[S] Chemical compound [AlH3].[S] GQCYCMFGFVGYJT-UHFFFAOYSA-N 0.000 claims description 2
- PIOQMRWHQXFDKN-UHFFFAOYSA-N [Cu]S[Cd][Zn] Chemical compound [Cu]S[Cd][Zn] PIOQMRWHQXFDKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004549 pulsed laser deposition Methods 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
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 230000005641 tunneling Effects 0.000 abstract description 7
- 239000002356 single layer Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 58
- 229910004613 CdTe Inorganic materials 0.000 description 25
- 239000002800 charge carrier Substances 0.000 description 25
- 238000000151 deposition Methods 0.000 description 24
- 230000008021 deposition Effects 0.000 description 21
- 239000007789 gas Substances 0.000 description 19
- 239000000758 substrate Substances 0.000 description 19
- 239000012159 carrier gas Substances 0.000 description 16
- 239000011521 glass Substances 0.000 description 15
- 238000004544 sputter deposition Methods 0.000 description 15
- 230000007704 transition Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 230000031700 light absorption Effects 0.000 description 14
- 238000000137 annealing Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 230000006798 recombination Effects 0.000 description 13
- 238000005215 recombination Methods 0.000 description 13
- GKPXMGUNTQSFGA-UHFFFAOYSA-N but-2-ynyl 1-methyl-3,6-dihydro-2h-pyridine-5-carboxylate;4-methylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1.CC#CCOC(=O)C1=CCCN(C)C1 GKPXMGUNTQSFGA-UHFFFAOYSA-N 0.000 description 11
- 238000005286 illumination Methods 0.000 description 11
- 238000004088 simulation Methods 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- 239000011701 zinc Substances 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000005245 sintering Methods 0.000 description 7
- 238000011010 flushing procedure Methods 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 238000007738 vacuum evaporation Methods 0.000 description 6
- 238000007740 vapor deposition Methods 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- VXAPDXVBDZRZKP-UHFFFAOYSA-N nitric acid phosphoric acid Chemical compound O[N+]([O-])=O.OP(O)(O)=O VXAPDXVBDZRZKP-UHFFFAOYSA-N 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- 230000005684 electric field Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- -1 argon ion Chemical class 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005566 electron beam evaporation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 238000000637 aluminium metallisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
Classifications
-
- 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
- H01L31/0352—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035209—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
-
- 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
- Y02E10/543—Solar cells from Group II-VI materials
-
- 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
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a film solar cell and a preparation method thereof. The film solar cell comprises a front electrode layer, a semiconductor layer, a back electrode layer and a tunneling rectification layer. The tunneling rectification layer of a single-layer or multi-layer structure is arranged between the front electrode layer and the semiconductor layer and/or between the semiconductor layer and the back electrode layer, and is made of at least one selected from metal oxide, metal nitride, metal sulfide and metal fluoride. The surface(s) of the front and/or back electrode layer are/is provided with the tunneling rectification layer, the tunneling rectification layer is used to carry out electron rectification, and thus, carrier combination is effectively avoided, the short-circuit current and open-circuit voltage of the solar cell are improved, and the photoelectric conversion efficiency is further improved.
Description
Technical field
The application relates to field of thin film solar cells, particularly relates to thin-film solar cells of a kind of architecture advances and preparation method thereof.
Background technology
Thin-film solar cells is the main representative of second generation solar cell, take thin film semiconductor material as light-absorption layer, thickness is in micron and sub-micrometer scale, greatly reduce the consumption of material, growth technique is simple, be convenient to make light, flexible device, cost performance is preponderated, and industrialization prospect is fine.But thin film semiconductor material defect is more, surface carrier load is serious, and cell photoelectric transformation efficiency only has 10% ~ 20% at present, lower than traditional crystal silicon solar batteries.
Based on above reason, how to reduce the compound of the surface carrier of thin-film solar cells, improve short circuit current and the open circuit voltage of solar cell, thus improve electricity conversion, being the important directions of thin-film solar cells research, is also the key factor expanding its application further.At present, the main method reducing surface carrier compound is, form the passivation layer that one deck is very thick, usually be all the passivation layer of more than 50nm, then in the process of depositing electrode, passivation layer is burnt, make electrode follow semiconductor layer directly to contact, the requirement that this all will be very high for battery manufacturing process and electrode material, thus improve battery cost.
Summary of the invention
The object of the application is to provide thin-film solar cells of a kind of new architecture advances and preparation method thereof.
The application have employed following technical scheme:
The one side of the application discloses a kind of thin-film solar cells, comprise front electrode layer, semiconductor layer, dorsum electrode layer, and tunnelling rectification layer, tunnelling rectification layer is arranged between front electrode layer and semiconductor layer, or tunnelling rectification layer is arranged between semiconductor layer and dorsum electrode layer, or tunnelling rectification layer is arranged between front electrode layer and semiconductor layer simultaneously, and between semiconductor layer and dorsum electrode layer; Tunnelling rectification layer is single or multiple lift structure, and the material of every layer in the single or multiple lift structure of tunnelling rectification layer is at least one in metal oxide, metal nitride, metal sulfide, metal fluoride.
It should be noted that, the key of the application is, on the surface of front electrode layer, and/or the surface of dorsum electrode layer arranges tunnelling rectification layer, tunnelling rectification layer is electrode layer and/or dorsum electrode layer before whole covering, and electronics directly can penetrate this tunnelling rectification layer, reach the object of rectification, thus avoid the compound of charge carrier, improve short circuit current and the open circuit voltage of solar cell, and then improve electricity conversion; In a kind of implementation of the application, transformation efficiency can improve more than 5% than the solar cell not adding tunnelling rectification layer, after optimal conditions, generally can improve more than 10%.In the application, semiconductor layer is made up of N layer and P layer usually, and concrete N layer and P layer can adopt existing material, thus form different thin-film solar cells, are not specifically limited at this.
Also it should be noted that, the tunnelling rectification layer of the application can be individual layer, merely by a kind of single layer structure formed in metal oxide, metal nitride, metal sulfide, metal fluoride; Also can be sandwich construction, such as two-layer, three layers or more layers, wherein the material of every layer can be different, such as, first deposit one deck silica, deposit one deck aluminium oxide again, form the tunnelling rectification layer of double-layer structure thus.The design principle of sandwich construction tunnelling rectification layer mainly considers the interface compatibility of tunnelling rectification layer and front electrode layer or dorsum electrode layer, although some material tunnelling rectification effects are better, but, be difficult to form good interface at front electrode layer or dorsum electrode layer surface, affect the overall performance of solar cell, therefore, need to adopt the good material of interface compatibility to deposit one deck in advance, then deposit the good material of tunnelling rectification effect.For electrode layer or dorsum electrode layer before different, they are different from the compatibility of tunnelling rectification layer material, and therefore, the tunnelling rectification layer of sandwich construction, the material of each layer can adjust as the case may be, is not specifically limited at this.Be appreciated that the key of the application is to add a tunnelling rectification layer, and tunnelling rectification layer must possess tunnelling and rectification two effects; With reference to existing thin-film solar cells, can be not specifically limited at this as electrode layer, semiconductor layer, dorsum electrode layer before other layer.In addition; front electrode layer, semiconductor layer, dorsum electrode layer are the basic structure of thin-film solar cells; be appreciated that; the thin-film solar cells of the application can also comprise other; each layer that existing thin-film solar cells possesses, as long as the tunnelling rectification layer that have employed the application, carries out rectification to thin-film solar cells; all belong to the protection range of the application, be not specifically limited at this.
Also it should be noted that, in the application, tunnelling rectification layer to make electronics directly to penetrate, reach the object of rectification, test confirms, the metal oxide of general conventional use, metal nitride, metal sulfide, metal fluoride can reach this object, are not specifically limited at this; But in the preferred version of the application, in order to reach better effect, be particularly limited to it, this introduces in detail by follow-up scheme.
Preferably, metal oxide is at least one in aluminium oxide, silica, zinc oxide, titanium oxide, nickel oxide, stannous oxide, cuprous oxide, cupric oxide, hafnium oxide, zirconia.
Preferably, metal nitride is aluminium nitride and/or silicon nitride.
Preferably, metal sulfide is at least one in copper sulfide, cuprous sulfide, copper aluminium sulphur, zinc cadmium copper sulphur.
Preferably, metal fluoride is calcirm-fluoride and/or sodium fluoride.
Preferably, the thickness of tunnelling rectification layer is 0.1nm-50nm.
It should be noted that, the tunnelling rectification layer of the application does not need to burn, that is, back electrode or front electrode directly do not contact with semiconductor layer, and therefore, tunnelling rectification layer must possess two functions, i.e. tunnelling and rectification, find after deliberation, need to possess good rectification effect, tunnelling rectification layer must possess certain thickness; But if tunnelling rectification layer is too thick, can affect electron tunneling again, this is a conflicting problem.Through large quantifier elimination and test, finally determine that the thickness of tunnelling rectification layer is 0.1nm-50nm, the effect of rectification can be met, good tunnelling can be had again.
Preferred, the thickness of tunnelling rectification layer is 0.5nm-20nm.
Preferably, thin-film solar cells is at least one in cadmium telluride diaphragm solar battery, copper-indium-galliun-selenium film solar cell, copper zinc selenium sulfur thin-film solar cells, Ca-Ti ore type thin-film solar cells and organic thin film solar cell.
It should be noted that, the tunnelling rectification layer of the application can be applied to various thin-film solar cells, includes but are not limited to cadmium telluride diaphragm solar battery, copper-indium-galliun-selenium film solar cell, copper zinc selenium sulfur thin-film solar cells, Ca-Ti ore type thin-film solar cells and organic thin film solar cell.
The another side of the application discloses the preparation method of the thin-film solar cells of the application, concrete, and tunnelling rectification layer adopts at least one method preparation in ald, physical vapour deposition (PVD), pulsed laser deposition, chemical vapour deposition (CVD) and spin-coating method.
The another side of the application also discloses and adopts the preparation method of the application to prepare, be more preferably the thin-film solar cells in scheme, its tunnelling rectification layer is metal oxide layer prepared by ald, metal oxide layer is specially alumina layer, nickel oxide layer, copper oxide or titanium oxide layer, the thickness of metal oxide layer is 0.1nm-50nm, and preferred thickness is for being 0.5nm-20nm.
The another side of the application also discloses and adopts the preparation method of the application to prepare, be more preferably the thin-film solar cells in scheme, its tunnelling rectification layer is the copper sulfide layer prepared of spin-coating method or sulphur copper cadmium layer, the thickness of copper sulfide layer or sulphur copper cadmium layer is 0.1nm-50nm, and preferred thickness is for being 0.5nm-20nm.
The beneficial effect of the application is:
The thin-film solar cells of the application, on the surface of front electrode layer and/or dorsum electrode layer, tunnelling rectification layer is set, tunnelling rectification layer is utilized to carry out rectification to electronics, thus effectively avoid the compound of charge carrier, improve short circuit current and the open circuit voltage of solar cell, and then improve electricity conversion.
Accompanying drawing explanation
Fig. 1 is film solar battery structure schematic diagram in the embodiment of the present application, and (a) is the structural representation only arranging tunnelling rectification layer between front electrode layer and semiconductor layer; B () is simultaneously between front electrode layer and semiconductor layer, arrange the structural representation of tunnelling rectification layer between semiconductor layer and dorsum electrode layer;
Fig. 2 is the CdTe solar cell SEM photo being provided with tunnelling rectification layer in the embodiment of the present application, and wherein, a is profile, and b is surface topography map;
Fig. 3 is that in the embodiment of the present application, CdTe thin film solar cell is provided with tunnelling rectification layer and does not arrange the effect schematic diagram of tunnelling rectification layer, and a is the situation not arranging tunnelling rectification layer, and b is the situation arranging tunnelling rectification layer;
Fig. 4 is the IV curve under the rectification of CdTe thin film solar cell in the embodiment of the present application and tunnelling effect;
Fig. 5 is photovoltage curve under the rectification of CdTe thin film solar cell in the embodiment of the present application and tunnelling effect and external quantum efficiency curve, and a is photovoltage curve chart, and b is external quantum efficiency curve chart;
Fig. 6 is preparation method's flow chart of thin-film solar cells in the embodiment of the present application.
Embodiment
The thin-film solar cells of the application, as shown in Figure 1, arranges tunnelling rectification layer on the surface of front electrode layer and/or dorsum electrode layer, take into account rectification and tunneling effect, namely, while minimizing Carrier recombination, ensure that transporting of electric charge by tunnelling current, as shown in Figure 3.The tunnelling rectification layer added in the thin-film solar cells of the application, electronics can directly penetrate, and does not need to burn tunnelling rectification layer, and compared with existing passivation layer, rectification effect is better; Further, due to without the need to burning step, preparation technology is more simple, and production cost also decreases.
Below by specific embodiment, the application is described in further detail.Following examples are only further described the application, should not be construed as the restriction to the application.
Embodiment one
This example adopts cadmium telluride diaphragm solar battery to test, and utilizes ald to form Al on CdTe surface
2o
3layer, i.e. the tunnelling rectification layer of this example, tunnelling rectification layer is arranged between semiconductor layer and dorsum electrode layer.
As shown in Figure 6, use sputtering method to prepare transparent front electrode layer FTO on the glass substrate successively, thickness can be 300nm ~ 1 μm to basic preparation flow, and this example specifically prepares the transparent electrode layer of thickness 500nm; Then sputter N-shaped transition zone CdS, thickness can be 100-200nm, and this example has specifically prepared the N-shaped transition zone of thickness 145nm, uses vacuum evaporation deposition CSS to prepare p-type light-absorption layer CdTe thin film, after carry out CdCl successively
2the steps such as annealing in process, nitric acid phosphoric acid NP etching and copper Cu doping, obtain the film that surface has dangling bonds, i.e. the semiconductor layer of this example; Then ald is being utilized to form Al in semiconductor layer surface
2o
3layer, i.e. the tunnelling rectification layer of this example, ald temperature is 120 DEG C, and background vacuum pressure is 300mTorr.Four step continuous print processes form a complete deposition cycle below: the trimethyl aluminium TMA of (1) gas phase is carried by high-purity carrier gas and enters reative cell, saturated adsorption reaction is there is, Ar or N that the high-purity carrier gas of this example adopts purity to be greater than 99.99% on CdTe surface
2, flow is 30sccm; (2) carrier gas purge, take unnecessary TMA and reaction residual gas out of reative cell, flushing times is 25s; (3) the water H of gas phase
2o is carried by high-purity carrier gas and enters reative cell, and chemical reaction occurs the TMA adsorbed with step (1), generates Al
2o
3layer; (4) carrier gas purge, by unnecessary H
2o and reaction residual gas take reative cell out of, and flushing times is 25s.So move in circles, until deposit the Al that thickness is 0.5nm
2o
3layer, namely obtains the tunnelling rectification layer of this example; At the Au electrode that tunnelling rectification layer surface vapor deposition 40nm is thick, i.e. dorsum electrode layer, after this carry out 200 DEG C of annealing sintering; Obtain the thin-film solar cells of this example.
Adopt electron-microscope scanning to observe thin-film solar cells prepared by this example, as shown in Figure 2, its profile is as shown in a in Fig. 2, and prepared CdTe crystal grain is larger, and each interface is compact and complete for result; Surface topography is as shown in b in Fig. 2, and result shows, at CdTe layer surface uniform deposition one deck Al
2o
3layer, does not affect surface topography.The current-voltage test result of Fig. 4 illustrates the object that can realize ballast and tunnelling through transpassivation rectification layer.
By the test of intensity modulated photovoltaic spectrum (IMVS), contrast increases rectification tunnel layer and the sample do not increased, determine battery minority carrier lifetime contrast raising more than 10%, the raising of minority carrier lifetime illustrates that the surface recombination of charge carrier reduces, thus improve battery efficiency, illustrate that this technique effectively reduces the surface recombination of device charge carrier.Under the solar light irradiation of simulation AM1.5, the test of illumination voltage-to-current is carried out to the thin-film solar cells of this example, light source is the Sun3000 model solar simulator that ABET company produces, voltage-current curve is shown test by the 2602A type figure source of Keithley company and is drawn, test result as shown in Figure 5, Fig. 5 (a) indicates battery efficiency result, the reason that the battery efficiency that illustrates Fig. 5 (b) improves, good passivation effect is described, result shows, the battery efficiency of this example, than the sample do not increased, improves 10%.Battery efficiency improves the raising being mainly derived from open circuit voltage (Voc) and fill factor, curve factor (FF), and this result illustrates that increase is then worn rectification layer and effectively improve transporting and reception of charge carrier.
Embodiment two
This example adopt cadmium telluride diaphragm solar battery test, with embodiment one unlike, this example is by tunnelling rectification layer Al
2o
3layer is arranged between semiconductor layer and front electrode layer.
Use sputtering method to prepare transparent electrode layer FTO on the glass substrate successively, this routine thickness can be 300nm ~ 1 μm, and this example specifically prepares the transparent electrode layer of thickness 500nm; Then ald is utilized to form Al at front electrode surface
2o
3layer, i.e. the tunnelling rectification layer of this example, concrete tunnel layer preparation technology can refer to the detailed process of embodiment one, and tunneling layer thickness is 1nm; Then at sputtering N-shaped transition zone CdS, thickness can be 100-200nm, and this example has specifically prepared the N-shaped transition zone of thickness 145nm, uses vacuum evaporation deposition CSS to prepare p-type light-absorption layer CdTe thin film, after carry out CdCl successively
2the steps such as annealing in process, nitric acid phosphoric acid NP etching and copper Cu doping, and the Au electrode that vapor deposition 40nm is thick, i.e. dorsum electrode layer, after this carry out 200 DEG C of annealing sintering; Obtain the thin-film solar cells of this example.
Adopt electron-microscope scanning to observe thin-film solar cells prepared by this example, result shows, and has one deck Al at transparent electrode layer FTO surface uniform deposition
2o
3layer.
By the test of intensity modulated photovoltaic spectrum (IMVS), determine that battery minority carrier lifetime improves more than 10%, illustrate that this technique effectively reduces the surface recombination of device charge carrier.Under the solar light irradiation of simulation AM1.5, the test of illumination voltage-to-current is carried out to the thin-film solar cells of this example, light source is the Sun3000 model solar simulator that ABET company produces, voltage-current curve is shown test by the 2602A type figure source of Keithley company and is drawn, test result shows, and the battery efficiency of this example improves 5%.Battery efficiency improves the raising being mainly derived from open circuit voltage (Voc) and fill factor, curve factor (FF), and this result illustrates that increase is then worn rectification layer and effectively improve transporting and reception of charge carrier.
Embodiment three
This example adopts copper-indium-galliun-selenium film solar cell to test, on the back electrode molybdenum Mo of CIGS thin-film solar, mainly use physical gas-phase deposite method to form cuprous oxide Cu
2o layer, i.e. the tunnelling rectification layer of this example; Tunnelling rectification layer is arranged between semiconductor layer and dorsum electrode layer.
Substrate of glass sputters and uses sputtering method to prepare metallic back electrode layer Mo on the glass substrate successively, this routine thickness can be 500nm ~ 1 μm, and this example specifically prepares the metal electrode layer of thickness 1 μm; Tunnel layer depositing temperature is 200 DEG C, and background vacuum pressure is 1.0 × 10
-3below Pa, pass into argon Ar as sputter gas, a small amount of oxygen is as reacting gas, (1) substrate and semiconductive thin film and target are under the effect of the alternating electric field added by radio-frequency power supply, middle electronics oscillate, and increase the collision probability of electronics and gas molecule and ionize and produce argon ion Ar
+and oxonium ion O
2+; (2) Ar is ionized
+under electric field action, bombard target material surface and make Cu atom with certain energy to substrate motion, with O in motion process
2+in conjunction with, and finally deposit on substrate, and form Cu
2o film, time expand, is until deposit the Cu that thickness is 5nm
2o layer, namely obtains the tunnelling rectification layer of this example, i.e. the tunnelling rectification layer of this example; Then at sputtering p-type light-absorption layer Copper Indium Gallium Selenide CIGS, thickness can be 1-2um, and this example has specifically prepared the p-type light-absorption layer of thickness 1.5um; Then at sputtering N-shaped transition zone CdS, this routine thickness is 100-200nm, and this example specifically prepares the N-shaped transition zone of thickness 200nm; Then electrode layer before electrode intrinsic blocking layer native oxide zinc i-ZnO layer and Al-Doped ZnO AZO before sputtering respectively, thickness is respectively 100nm and 500nm, after this carries out 300 DEG C of annealing sintering; Obtain the thin-film solar cells of this example.
Adopt electron-microscope scanning to observe thin-film solar cells prepared by this example, result shows, and has one deck cuprous oxide Cu at back electrode molybdenum Mo surface uniform deposition
2o layer.
By the test of intensity modulated photovoltaic spectrum (IMVS), determine that battery minority carrier lifetime improves more than 10%, illustrate that this technique effectively reduces the surface recombination of device charge carrier.Under the solar light irradiation of simulation AM1.5, the test of illumination voltage-to-current is carried out to the thin-film solar cells of this example, light source is the Sun3000 model solar simulator that ABET company produces, voltage-current curve is shown test by the 2602A type figure source of Keithley company and is drawn, test result shows, and the battery efficiency of this example improves 10%.Battery efficiency improves the raising being mainly derived from open circuit voltage (Voc) and fill factor, curve factor (FF), and this result illustrates that increase is then worn rectification layer and effectively improve transporting and reception of charge carrier.
Embodiment four
This example adopts copper-zinc-tin-sulfur CZTS thin-film solar cells to test, and utilizes electron-beam evaporation method to form nickel oxide NiO on CZTS surface
xlayer, i.e. the tunnelling rectification layer of this example, tunnelling rectification layer is arranged between semiconductor layer and dorsum electrode layer.
Substrate of glass sputters and uses sputtering method to prepare metallic back electrode layer Mo on the glass substrate successively, this routine thickness can be 500nm ~ 1 μm, and this example specifically prepares the metal electrode layer of thickness 1 μm; Then use electron beam evaporation method at metal electrode layer growth oxidation nickel O
xlayer, being the tunnelling rectification layer of this example, specifically making deposited by electron beam evaporation NiO powder, is 1 × 10 in vacuum degree
-3below Pa, passing into purity is that the oxygen of 4mol/L makes air pressure be increased to 2 × 10
-2pa, is adjusted to required evaporation power by electron beam current, evaporation rate is 0.1nm/s, and time expand is until deposit the NiO that thickness is 5nm
xlayer; Then grown p-type light-absorption layer copper-zinc-tin-sulfur CZTS layer: (1) is coated with in the substrate of ZnO by Co-evaporated Deposition above-mentioned Cu, Zn and Sn; (2) sulphur steam is passed in deposition process by a valve; (3) by system CZTS film to anneal in air atmosphere at 570 DEG C of temperature 5min, thickness can be 1-2 μm, and this example has specifically prepared the p-type light-absorption layer of thickness 1.5 μm; Then electrode layer before electrode intrinsic blocking layer native oxide zinc i-ZnO layer and Al-Doped ZnO AZO before sputtering respectively, thickness is respectively 100nm and 500nm, obtains the thin-film solar cells of this example.
Adopt electron-microscope scanning to observe thin-film solar cells prepared by this example, result shows, and has one deck nickel oxide NiO at dorsum electrode layer Mo surface uniform deposition
xlayer.
By the test of intensity modulated photovoltaic spectrum (IMVS), determine that battery minority carrier lifetime improves more than 10%, illustrate that this technique effectively reduces the surface recombination of device charge carrier.Under the solar light irradiation of simulation AM1.5, the test of illumination voltage-to-current is carried out to the thin-film solar cells of this example, light source is the Sun3000 model solar simulator that ABET company produces, voltage-current curve is shown test by the 2602A type figure source of Keithley company and is drawn, test result shows, and the battery efficiency of this example improves 10%.Battery efficiency improves the raising being mainly derived from open circuit voltage (Voc) and fill factor, curve factor (FF), and this result illustrates that increase is then worn rectification layer and effectively improve transporting and reception of charge carrier.
Embodiment five
This example adopts organic thin film solar cell to test, utilize metal-organic chemical vapor deposition equipment MOCVD method to form zinc oxide ZnO layer on organic film light-absorption layer surface, the i.e. tunnelling rectification layer of this example, tunnelling rectification layer is arranged between semiconductor layer and dorsum electrode layer.
Use sputtering method to prepare transparent electrode layer ITO on the glass substrate successively, this routine thickness can be 300nm ~ 1 μm, and this example specifically prepares the transparent electrode layer of thickness 500nm; Then rotating coating is used to prepare transparent p-type transition zone PEDOT:PSS respectively, and P3HT and PCBM mixed solution obtains light-absorption layer, thickness is respectively 50nm and 200nm, and the 20min that anneals under 150 DEG C of conditions, obtain the film that surface has organic substance dangling bonds, i.e. the semiconductor layer of this example; Then use metal-organic chemical vapor deposition equipment system in metal electrode layer growth native oxide zinc layers, be the tunnelling rectification layer of this example, concrete use electron level zinc source DEZn, oxidant is H
2o, argon gas (Ar) is carrier gas, flow control device 10sccm and 50sccm respectively of zinc source and oxidant, and in deposition process, gas pressure in vacuum is stabilized in 3.0torr, underlayer temperature controls at 160 DEG C, and time expand is until deposit the ZnO layer that thickness is 5nm; Then use metal fever evaporation coating method AM aluminum metallization Al electrode, thickness is 100nm, obtains the thin-film solar cells of this example.
Adopt electron-microscope scanning to observe thin-film solar cells prepared by this example, result shows, and between semiconductor layer and dorsum electrode layer, uniform deposition has layer of ZnO layer.
By the test of intensity modulated photovoltaic spectrum (IMVS), determine that battery minority carrier lifetime improves more than 10%, illustrate that this technique effectively reduces the surface recombination of device charge carrier.Under the solar light irradiation of simulation AM1.5, the test of illumination voltage-to-current is carried out to the thin-film solar cells of this example, light source is the Sun3000 model solar simulator that ABET company produces, voltage-current curve is shown test by the 2602A type figure source of Keithley company and is drawn, test result shows, and the battery efficiency of this example improves 10%.Battery efficiency improves the raising being mainly derived from open circuit voltage (Voc) and fill factor, curve factor (FF), and this result illustrates that increase is then worn rectification layer and effectively improve transporting and reception of charge carrier.
Embodiment six
This example adopts perovskite thin film solar cell to test, and utilizes ald to form aluminium oxide Al
2o
3and silicon oxide sio
2composite bed, i.e. the tunnelling rectification layer of this example, tunnelling rectification layer is arranged between semiconductor layer and dorsum electrode layer.
Use sputtering method to prepare transparent electrode layer FTO on the glass substrate successively, thickness can be 300nm ~ 1 μm, and this example specifically prepares the transparent electrode layer of thickness 500nm; Then N-shaped transition zone titanium oxide TiO is sputtered
2, thickness can be 100-200nm, and this example has specifically prepared the N-shaped transition zone of thickness 150nm, then uses two step method of spin coating spin coating lead iodide PbI respectively
2and methyl amine iodine CH
3nH
3i, obtains the semiconductive thin film that surface has dangling bonds, i.e. the light-absorption layer of this example; Then ald is being utilized to form aluminium oxide Al in semiconductor layer surface
2o
3and silicon oxide sio
2composite bed, i.e. the tunnelling rectification layer of this example, ald temperature is 120 DEG C, and background vacuum pressure is 300mTorr.Four step continuous print processes form a complete deposition cycle below: the trimethyl aluminium TMA of (1) gas phase is carried by high-purity carrier gas and enters reative cell, saturated adsorption reaction is there is, Ar or N that the high-purity carrier gas of this example adopts purity to be greater than 99.99% on CdTe surface
2, flow is 30sccm; (2) carrier gas purge, take unnecessary TMA and reaction residual gas out of reative cell, flushing times is 25s; (3) the water H of gas phase
2o is carried by high-purity carrier gas and enters reative cell, and chemical reaction occurs the TMA adsorbed with step (1), generates Al
2o
3layer; (4) carrier gas purge, by unnecessary H
2o and reaction residual gas take reative cell out of, and flushing times is 25s.So move in circles, until deposit the NiO that thickness is 0.5nm
xlayer, namely obtains the tunnelling rectification layer of this example; At the Au electrode that tunnelling rectification layer surface vapor deposition 40nm is thick, i.e. dorsum electrode layer, after this carry out 200 DEG C of annealing sintering; Obtain the thin-film solar cells of this example.
Adopt electron-microscope scanning to observe thin-film solar cells prepared by this example, result shows, and between semiconductor layer and dorsum electrode layer, uniform deposition has the tunnelling rectification layer of a double-layer structure, i.e. aluminium oxide Al
2o
3layer and silicon oxide sio
2the tunnelling rectification layer of layer compound.
By the test of intensity modulated photovoltaic spectrum (IMVS), determine that battery minority carrier lifetime improves more than 10%, illustrate that this technique effectively reduces the surface recombination of device charge carrier.Under the solar light irradiation of simulation AM1.5, the test of illumination voltage-to-current is carried out to the thin-film solar cells of this example, light source is the Sun3000 model solar simulator that ABET company produces, voltage-current curve is shown test by the 2602A type figure source of Keithley company and is drawn, test result shows, and the battery efficiency of this example improves 10%.Battery efficiency improves the raising being mainly derived from open circuit voltage (Voc) and fill factor, curve factor (FF), and this result illustrates that increase is then worn rectification layer and effectively improve transporting and reception of charge carrier.
Embodiment seven
This example adopts cadmium telluride diaphragm solar battery to test, and utilizes physical vapour deposition (PVD) to form silicon oxide sio on CdTe surface
2layer, i.e. the tunnelling rectification layer of this example, tunnelling rectification layer is arranged between semiconductor layer and dorsum electrode layer.
Use sputtering method to prepare transparent electrode layer FTO on the glass substrate successively, thickness can be 300nm ~ 1 μm, and this example specifically prepares the transparent electrode layer of thickness 500nm; Then sputter N-shaped transition zone CdS, thickness can be 100-200nm, and this example has specifically prepared the N-shaped transition zone of thickness 145nm, uses vacuum evaporation deposition CSS to prepare p-type light-absorption layer CdTe thin film, after carry out CdCl successively
2the steps such as annealing in process, nitric acid phosphoric acid NP etching and copper Cu doping, obtain the film that surface has dangling bonds, i.e. the semiconductor layer of this example; Then physical vapour deposition (PVD) is utilized to form silicon oxide sio at semiconductor
2layer, the tunnelling rectification layer of this example of level, tunnel layer depositing temperature is 200 DEG C, and background vacuum pressure is 1.0 × 10
-3below Pa, pass into argon Ar as sputter gas, (1) substrate and semiconductive thin film and target are under the effect of the alternating electric field added by radio-frequency power supply, middle electronics oscillate, and increase the collision probability of electronics and gas molecule and ionize and produce argon ion Ar
+; (2) Ar is ionized
+under electric field action, bombard target material surface and make SiO
2with certain energy deposition on substrate, and form SiO
2film, time expand, is until deposit the SiO that thickness is 2nm
2layer, namely obtains the tunnelling rectification layer of this example; At the Au electrode that tunnelling rectification layer surface vapor deposition 40nm is thick, i.e. dorsum electrode layer, after this carry out 200 DEG C of annealing sintering; Obtain the thin-film solar cells of this example.
Adopt electron-microscope scanning to observe thin-film solar cells prepared by this example, result shows, and has one deck SiO at the surface uniform deposition of CdTe
2layer.
By the test of intensity modulated photovoltaic spectrum (IMVS), determine that battery minority carrier lifetime improves more than 10%, illustrate that this technique effectively reduces the surface recombination of device charge carrier.Under the solar light irradiation of simulation AM1.5, the test of illumination voltage-to-current is carried out to the thin-film solar cells of this example, light source is the Sun3000 model solar simulator that ABET company produces, voltage-current curve is shown test by the 2602A type figure source of Keithley company and is drawn, test result shows, and the battery efficiency of this example improves 10%.Battery efficiency improves the raising being mainly derived from open circuit voltage (Voc) and fill factor, curve factor (FF), and this result illustrates that increase is then worn rectification layer and effectively improve transporting and reception of charge carrier.
Embodiment eight
This example adopts cadmium telluride diaphragm solar battery to test, and utilizes ald to form cupric oxide CuO on CdTe surface
xlayer, i.e. the tunnelling rectification layer of this example, tunnelling rectification layer is arranged between semiconductor layer and dorsum electrode layer.
Use sputtering method to prepare transparent electrode layer FTO on the glass substrate successively, thickness can be 300nm ~ 1 μm, and this example specifically prepares the transparent electrode layer of thickness 500nm; Then sputter N-shaped transition zone CdS, thickness can be 100-200nm, and this example has specifically prepared the N-shaped transition zone of thickness 145nm, uses vacuum evaporation deposition CSS to prepare p-type light-absorption layer CdTe thin film, after carry out CdCl successively
2the steps such as annealing in process, nitric acid phosphoric acid NP etching and copper Cu doping, obtain the film that surface has dangling bonds, i.e. the semiconductor layer of this example; Then ald is being utilized to form CuO in semiconductor layer surface
xlayer, i.e. the tunnelling rectification layer of this example, ald temperature is 120 DEG C, and background vacuum pressure is 300mTorr.Four step continuous print processes form a complete deposition cycle below: (1) gas phase [Cu (
ipr-Me-AMD)]
2carried by high-purity carrier gas and enter reative cell, on CdTe surface, saturated adsorption reaction occurs, Ar or N that the high-purity carrier gas of this example adopts purity to be greater than 99.99%
2, flow is 30sccm; (2) carrier gas purge, by unnecessary [Cu (
ipr-Me-AMD)]
2take reative cell out of with reaction residual gas, flushing times is 25s; (3) the water H of gas phase
2o is carried by high-purity carrier gas and enters reative cell, with step (1) adsorb [Cu (
ipr-Me-AMD)]
2there is chemical reaction, generate CuO
xlayer; (4) carrier gas purge, by unnecessary H
2o and reaction residual gas take reative cell out of, and flushing times is 25s.So move in circles, until deposit the CuO that thickness is 0.5nm
xlayer, namely obtains the tunnelling rectification layer of this example; At the Au electrode that tunnelling rectification layer surface vapor deposition 40nm is thick, i.e. dorsum electrode layer, after this carry out 200 DEG C of annealing sintering; Obtain the thin-film solar cells of this example.
Adopt electron-microscope scanning to observe thin-film solar cells prepared by this example, result shows, and has one deck cupric oxide CuO at the surface uniform deposition of CdTe
xlayer.
By the test of intensity modulated photovoltaic spectrum (IMVS), determine that battery minority carrier lifetime improves more than 10%, illustrate that this technique effectively reduces the surface recombination of device charge carrier.Under the solar light irradiation of simulation AM1.5, the test of illumination voltage-to-current is carried out to the thin-film solar cells of this example, light source is the Sun3000 model solar simulator that ABET company produces, voltage-current curve is shown test by the 2602A type figure source of Keithley company and is drawn, test result shows, and the battery efficiency of this example improves 10%.Battery efficiency improves the raising being mainly derived from open circuit voltage (Voc) and fill factor, curve factor (FF), and this result illustrates that increase is then worn rectification layer and effectively improve transporting and reception of charge carrier.
Embodiment nine
This example adopts cadmium telluride diaphragm solar battery to test, and utilizes spin-coating method to form Cu on CdTe surface
xs layer, i.e. the tunnelling rectification layer of this example, tunnelling rectification layer is arranged between semiconductor layer and dorsum electrode layer.
Sputtering method is used to prepare the transparent electrode layer of thickness 500nm on the glass substrate successively; Then sputter N-shaped transition zone CdS, thickness can be 100-200nm, and this example has specifically prepared the N-shaped transition zone of thickness 145nm, uses vacuum evaporation deposition CSS to prepare p-type light-absorption layer CdTe thin film, carries out CdCl
2annealing in process obtains the semiconductor layer of this example; By the CuCl of special ratios
2be dissolved in configuration precursor liquid in the solvent (DMF or DMSO) of specified quantitative with sulphur source (thiocarbamide or thioacetamide), adopt spin-coating method and hot plate process to obtain Cu
xs layer, i.e. the tunnelling rectification layer of this example, spin coating rotating speed is 3000rpm, and spin-coating time is 30s, and hot plate treatment temperature is 200 DEG C, and the processing time is 5min.At the Au electrode that tunnelling rectification layer surface vapor deposition 40nm is thick, i.e. dorsum electrode layer, after this carry out 200 DEG C of annealing sintering; Obtain the thin-film solar cells of this example.
Adopt electron-microscope scanning to observe thin-film solar cells prepared by this example, result shows, and has one deck Cu at the surface uniform deposition of CdTe
xs layer.
By the test of intensity modulated photovoltaic spectrum (IMVS), determine that battery minority carrier lifetime improves more than 10%, illustrate that this technique effectively reduces the surface recombination of device charge carrier.Under the solar light irradiation of simulation AM1.5, the test of illumination voltage-to-current is carried out to the thin-film solar cells of this example, light source is the Sun3000 model solar simulator that ABET company produces, voltage-current curve is shown test by the 2602A type figure source of Keithley company and is drawn, test result shows, and the battery efficiency of this example improves 10%.Battery efficiency improves the raising being mainly derived from open circuit voltage (Voc) and fill factor, curve factor (FF), and this result illustrates that increase is then worn rectification layer and effectively improve transporting and reception of charge carrier.
Embodiment ten
This example adopts CdTe thin film solar cell to test, and FTO transparent conducting glass deposits Zn with immersion method
1-x-ycd
xcu
ys electrically conducting transparent Window layer, forms heterojunction through subsequent treatment and CdTe and is prepared into the solar cell device with photoelectric conversion efficiency.
First on the FTO through clean, prepare with immersion method the Zn that a layer thickness is 100 ~ 200nm
1-x-ycd
xcu
ys transparency conducting layer, then utilizes into the Space Sublimation method CdTe light-absorption layer that evaporation about 5 μm is thick on previous transparency conducting layer.After carry out CdCl successively
2process, nitric acid-phosphoric acid NP etch and Cu/Au back electrode evaporation, thus obtain the glass/SnO2:F/Zn of this example
1-x-ycd
xcu
ythe thin film solar cell of S/CdTe/Cu-Au back electrode.
Adopt electron-microscope scanning to observe thin-film solar cells prepared by this example, result shows, and has one deck Zn at the surface uniform deposition of FTO transparent conducting glass
1-x-ycd
xcu
ys layer.
By the test of intensity modulated photovoltaic spectrum (IMVS), determine that battery minority carrier lifetime improves more than 10%, illustrate that this technique effectively reduces the surface recombination of device charge carrier.Under the solar light irradiation of simulation AM1.5, the test of illumination voltage-to-current is carried out to the thin-film solar cells of this example, light source is the Sun3000 model solar simulator that ABET company produces, voltage-current curve is shown test by the 2602A type figure source of Keithley company and is drawn, test result shows, and the battery efficiency of this example improves 10%.Battery efficiency improves the raising being mainly derived from open circuit voltage (Voc) and fill factor, curve factor (FF), and this result illustrates that increase is then worn rectification layer and effectively improve transporting and reception of charge carrier.
Embodiment 11
This example adopts organic thin film solar cell to test, and utilizes solution spin coating to form titanium dioxide TiO
2layer, i.e. the tunnelling rectification layer of this example, tunnelling rectification layer is arranged between semiconductor layer and FTO electrode layer.
This example of sputtering method is used specifically to prepare the transparent electrode layer of thickness 500nm on the glass substrate successively; Then in FTO substrate, TiO is prepared in spin coating
2layer, thickness can be 0.1-50nm, and this example has specifically prepared 5nm thickness tunnelling rectification layer, uses solution spin-coating method to prepare the film that P3HT:PCBM is active layer material, then vacuum evaporation 10nmMoO successively
3and 120nmAg, carry out 150 DEG C of annealing in process; Obtain the thin-film solar cells of this example.
Adopt electron-microscope scanning to observe thin-film solar cells prepared by this example, result shows, and has layer of titanium dioxide TiO at the surface uniform deposition of FTO electrode layer
2layer.
By the test of intensity modulated photovoltaic spectrum (IMVS), determine that battery minority carrier lifetime improves more than 10%, illustrate that this technique effectively reduces the surface recombination of device charge carrier.Under the solar light irradiation of simulation AM1.5, the test of illumination voltage-to-current is carried out to the thin-film solar cells of this example, light source is the Sun3000 model solar simulator that ABET company produces, voltage-current curve is shown test by the 2602A type figure source of Keithley company and is drawn, test result shows, and the battery efficiency of this example improves 10%.Battery efficiency improves the raising being mainly derived from open circuit voltage (Voc) and fill factor, curve factor (FF), and this result illustrates that increase is then worn rectification layer and effectively improve transporting and reception of charge carrier.
Above content is the further description done the application in conjunction with concrete execution mode, can not assert that the concrete enforcement of the application is confined to these explanations.For the application person of an ordinary skill in the technical field, under the prerequisite not departing from the application's design, some simple deduction or replace can also be made, all should be considered as the protection range belonging to the application.
Claims (10)
1. a thin-film solar cells, comprise front electrode layer, semiconductor layer and dorsum electrode layer, it is characterized in that: also comprise tunnelling rectification layer, described tunnelling rectification layer is arranged between described front electrode layer and semiconductor layer, or tunnelling rectification layer is arranged between described semiconductor layer and dorsum electrode layer, or tunnelling rectification layer is arranged between front electrode layer and semiconductor layer simultaneously, and between semiconductor layer and dorsum electrode layer;
Described tunnelling rectification layer is single or multiple lift structure, and the material of every layer in the single or multiple lift structure of tunnelling rectification layer is at least one in metal oxide, metal nitride, metal sulfide, metal fluoride.
2. thin-film solar cells according to claim 1, is characterized in that: described metal oxide is at least one in aluminium oxide, silica, zinc oxide, titanium oxide, nickel oxide, stannous oxide, cuprous oxide, cupric oxide, hafnium oxide, zirconia.
3. thin-film solar cells according to claim 1, is characterized in that: described metal nitride is at least one in aluminium nitride, silicon nitride.
4. thin-film solar cells according to claim 1, is characterized in that: described metal sulfide is at least one in copper sulfide, cuprous sulfide, copper aluminium sulphur, zinc cadmium copper sulphur.
5. thin-film solar cells according to claim 1, is characterized in that: described metal fluoride is at least one in calcirm-fluoride, sodium fluoride.
6. thin-film solar cells according to claim 1, is characterized in that: the thickness of described tunnelling rectification layer is 0.1nm-50nm, and preferred thickness is 0.5nm-20nm.
7. the thin-film solar cells according to any one of claim 1-6, is characterized in that: described thin-film solar cells is at least one in cadmium telluride diaphragm solar battery, copper-indium-galliun-selenium film solar cell, copper zinc selenium sulfur thin-film solar cells, Ca-Ti ore type thin-film solar cells and organic thin film solar cell.
8. the preparation method of the thin-film solar cells according to any one of claim 1-7, is characterized in that: described tunnelling rectification layer adopts at least one method preparation in ald, physical vapour deposition (PVD), pulsed laser deposition, chemical vapour deposition (CVD) and spin-coating method.
9. the thin-film solar cells prepared of preparation method according to claim 8, it is characterized in that: described tunnelling rectification layer is metal oxide layer prepared by ald, described metal oxide layer is specially alumina layer, nickel oxide layer, copper oxide or titanium oxide layer, and the thickness of described metal oxide layer is 0.1nm-50nm.
10. the thin-film solar cells prepared of preparation method according to claim 8, is characterized in that: described tunnelling rectification layer is the copper sulfide layer prepared of spin-coating method or sulphur copper cadmium layer, and the thickness of described copper sulfide layer or sulphur copper cadmium layer is 0.1nm-50nm.
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