CN102637755B - Nanometer structure copper zinc tin sulfide (CZTS) film photovoltaic cell and preparation method of nanometer structure CZTS film photovoltaic cell - Google Patents
Nanometer structure copper zinc tin sulfide (CZTS) film photovoltaic cell and preparation method of nanometer structure CZTS film photovoltaic cell Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 28
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 73
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000004065 semiconductor Substances 0.000 claims abstract description 28
- 230000008021 deposition Effects 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 229910052718 tin Inorganic materials 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 12
- 239000010931 gold Chemical group 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052737 gold Chemical group 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 239000004332 silver Substances 0.000 claims abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011669 selenium Substances 0.000 claims abstract description 6
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 4
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 3
- 239000000956 alloy Substances 0.000 claims abstract description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002086 nanomaterial Substances 0.000 claims description 52
- 239000010949 copper Substances 0.000 claims description 51
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 36
- 229910052802 copper Inorganic materials 0.000 claims description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 32
- 238000000151 deposition Methods 0.000 claims description 28
- 241000446313 Lamella Species 0.000 claims description 21
- 239000004020 conductor Substances 0.000 claims description 21
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 claims description 21
- 239000002071 nanotube Substances 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims description 20
- 239000002070 nanowire Substances 0.000 claims description 20
- 239000011787 zinc oxide Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- 210000001142 back Anatomy 0.000 claims description 12
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 11
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 11
- 239000011135 tin Substances 0.000 claims description 11
- 238000004070 electrodeposition Methods 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 9
- 238000004544 sputter deposition Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005864 Sulphur Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000002207 thermal evaporation Methods 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 claims description 5
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005083 Zinc sulfide Substances 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 4
- AKUCEXGLFUSJCD-UHFFFAOYSA-N indium(3+);selenium(2-) Chemical compound [Se-2].[Se-2].[Se-2].[In+3].[In+3] AKUCEXGLFUSJCD-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 238000005240 physical vapour deposition Methods 0.000 claims description 4
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005987 sulfurization reaction Methods 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 238000007740 vapor deposition Methods 0.000 claims description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- 239000002238 carbon nanotube film Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 claims description 3
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 claims description 2
- PDYXSJSAMVACOH-UHFFFAOYSA-N [Cu].[Zn].[Sn] Chemical compound [Cu].[Zn].[Sn] PDYXSJSAMVACOH-UHFFFAOYSA-N 0.000 claims description 2
- ZYQNKFKPTUYGMQ-UHFFFAOYSA-N [In]=[Se].[Zn] Chemical compound [In]=[Se].[Zn] ZYQNKFKPTUYGMQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005234 chemical deposition Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000001764 infiltration Methods 0.000 claims description 2
- 230000008595 infiltration Effects 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
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- 239000004615 ingredient Substances 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 81
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 16
- 239000010409 thin film Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000002835 absorbance Methods 0.000 description 12
- 239000002800 charge carrier Substances 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000005566 electron beam evaporation Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910001092 metal group alloy Inorganic materials 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 5
- 238000001755 magnetron sputter deposition Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 4
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 4
- 239000003595 mist Substances 0.000 description 4
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000011260 aqueous acid Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- 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
- 230000008859 change Effects 0.000 description 2
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
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- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 description 1
- FGOFFSMOHZYBNA-UHFFFAOYSA-N [S].[Sn].[Zn].[In].[Cu] Chemical compound [S].[Sn].[Zn].[In].[Cu] FGOFFSMOHZYBNA-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 1
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
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- 230000031700 light absorption Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
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Images
Classifications
-
- 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
-
- 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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- Photovoltaic Devices (AREA)
Abstract
The invention discloses a nanometer structure copper zinc tin sulfide (CZTS) film photovoltaic cell, which sequentially consists of a substrate, a back electrode, a p type semiconductor nanometer wire array, an n type semiconductor thin layer, a window layer and a metal grid electrode, wherein the p type semiconductor nanometer wire array consists of semiconductor alloy (CuxB<1-x>)2Cy(DzS<1-z>), wherein x is greater than 0 but is smaller than or equal to 1, y is greater than or equal to 0 but smaller than or equal to 2, z is greater than or equal to 0 but smaller than 1, B is silver and/or gold, C is more than one kind of materials of aluminum, zinc or tin, D is selenium and/or tellurium. Through the subsequent processes of controlling the deposition element types, the deposition element sequence, the heat treatment mode and the like, the ingredients, the phase structure and the energy band structure of the absorption layer nanometer wire array are regulated, so the solar photovoltaic cells with different structures and performance can be prepared. The nanometer structure CZTS film photovoltaic cell provided by the invention has the advantages that the light reflection is reduced, good light capture capability is realized, the band gap regulation is improved, and the great improvement of the photoelectric conversion efficiency is finally realized.
Description
Technical field
The invention belongs to solar-energy photo-voltaic cell technical field, be specifically related to a kind of nanostructure CZTS film photovoltaic cell and preparation method thereof and application.
Background technology
The mankind's survival and development be unable to do without the energy and environment.Along with the develop rapidly of World Economics, it is increasingly serious that energy crisis and environmental problem are just becoming, and becomes one of 21 century mankind significant problem in the urgent need to address.Therefore, exploitation importance clean, regenerative resource seems and becomes increasingly conspicuous.Solar energy is inexhaustible, nexhaustible clean energy resource, and sunlight is very wide at the coverage rate of the whole earth, as long as there is the place of the sun, we just can utilize solar energy to generate electricity.
The solar cell of application is still take monocrystalline silicon/polycrystal silicon cell as main in the market, but thin-film solar cells is acknowledged as the main direction of following solar cell development, and become one of solar battery technology of most study in the world.This is because thin-film solar cells has the outstanding advantages such as materials are few, technique is simple, energy consumption is low, cost is low.Hull cell mainly contains following several: silicon-based film solar cells, Copper Indium Gallium Selenide (CIGS) thin-film solar cells, cadmium telluride (CdTe) thin-film solar cells, DSSC, copper-zinc-tin-sulfur (CZTS) thin-film solar cells etc.
Wherein, the commercialization at present of CdTe and CIGS thin-film solar cells, its laboratory conversion efficiency reaches respectively 16.7%, 20.1%.But Cd belongs to poisonous element, human body and environment are had to very large harm, Te, In element are little at the content on earth's surface, are respectively 0.001,0.05ppm.Therefore, these two kinds of thin-film solar cells cannot meet the growing energy demand of people, and its large-scale production has been subject to serious obstruction.Cu, Zn, Sn are abundanter at the content on earth's surface, are respectively 25,71,5.5ppm, and are environmentally friendly elements.Be similar to CIGS, CZTS belongs to direct gap semiconductor material, and band gap width is 0.8 ~ 1.6eV, absorption coefficient ~ 10
4cm
-1, sunlight is had to good assimilation effect, its theoretical transformation efficiency reaches 32.2%.At present, the high conversion efficiency in the laboratory of CZTS solar cell has reached 9.66%.Thus, CZTS solar cell is the very promising thin-film solar cells of one.
Publication number is the disclosed copper zincium tin sulfur compound semiconductor thin-film solar cell of the Chinese patent application of CN101452969A and preparation method, adopt magnetron sputtering method in the glass substrate that is coated with metal back electrode, deposit one deck CZTS film, then by this film at N
2+ H
2annealing in process in S atmosphere, puts into subsequently deionized water or ethanol or ammoniacal liquor and soaks the metal oxide particle that a period of time removes CZTS film surface, finally obtains the good CZTS solar cell light absorption layer film of photoelectric properties.The method controllability is strong, and film quality is high, good uniformity, and technique is simple, is applicable to suitability for industrialized production.
Publication number is the preparation method of the disclosed a kind of absorbing layer of copper-zinc-tin-sulfur film solar cell of Chinese patent application of CN101800263A, adopt coevaporation method to prepare the metal precursor of copper, zinc and tin, then presoma is vulcanized and obtains copper-zinc-tin-sulfur film in sulphur steam.The advantage of the method is: raw material sources is abundant and non-toxic, and preparation technology is simple, and film performance is easy to control and be suitable for large-scale industrial production etc.
Publication number is the preparation method of the disclosed ormolu sulfur solar energy absorbing layer film of Chinese patent application of CN101651171A, adopt and first copper-zinc-tin-sulfur nano particles is dissolved in organic solvent, ultrasonic dispersion, obtain copper-zinc-tin-sulfur nano particles slurries, then these slurries are coated in substrate, substrate is heat-treated, obtain copper-zinc-tin-sulfur solar battery obsorbing layer film.The method green non-pollution, reaction condition gentleness is simple, with low cost, is suitable for large-scale production.
Publication number is the method for the disclosed a kind of alcohol heat deposition copper-zinc-tin-sulfur film of the Chinese patent application of CN102181847A, use thiocarbamide and slaine to form predecessor, alcohol makees solvent, substrate is immersed in solution, in sealing autoclave, heat, Direct precipitation copper-zinc-tin-sulfur film, the film obtaining can improve crystallinity by high annealing.The method is reasonable in design, simple to operate, and easy control of reaction is reproducible, can the substrate of disposable deposition multi-disc.
Publication number is the preparation method of the disclosed a kind of copper-zinc-tin-sulfur film of Chinese patent application of CN102251235A, adopt continuous ionic layer adsorption reaction method by same substrate priority or be alternately immersed in cation precursor solution and anion precursor solution, preparing Cu
2snS
xfilm and ZnS pellicular cascade preformed layer structure, or Cu
2s film and ZnSnS
xpellicular cascade preformed layer structure, then heat-treats and obtains copper-zinc-tin-sulfur film.The method had both solved metal ingredient problem rambunctious, can stop again copper ion to cause forming sulphur copper phase to film surface migration, and this process is simply applicable, with low cost, is suitable for suitability for industrialized production.
Above-mentioned several method can prepare that quality is high, the CZTS film of good uniformity, but the CZTS thin film solar photovoltaic cell conversion efficiency of preparation is lower, the photoelectric conversion efficiency of the CZTS thin film solar cell 9.66% of not only preparing lower than laboratory, also well below theoretical transformation efficiency.
Summary of the invention
In order to overcome the shortcoming and deficiency of prior art, primary and foremost purpose of the present invention is to provide a kind of nanostructure CZTS film photovoltaic cell.
The preparation method who another object of the present invention is to provide above-mentioned nanostructure CZTS film photovoltaic cell, the advantage such as it is simple that the method has preparation technology, can large area produces, not high to equipment requirement, and cost is lower.
A further object of the present invention is to provide the purposes of above-mentioned nanostructure CZTS film photovoltaic cell.
Object of the present invention is achieved through the following technical solutions:
A kind of nanostructure CZTS film photovoltaic cell, is comprised of substrate, back electrode, p-type conductor nano tube/linear array, N-shaped semiconductor lamella, Window layer and metal grate electrode successively;
Described substrate is pottery, mica, high molecule plastic, metal, silicon chip, glass or stainless steel substrates;
Described back electrode is molybdenum, aluminium, gold, copper, ito glass, silver, tungsten, nickel or titanium, and the thickness of dorsum electrode layer is 50nm～50 μ m;
Described p-type conductor nano tube/linear array is by semiconducting alloy (Cu
xb
1-x)
2c
y(D
zs
1-z)
4composition, wherein 0 < x≤1,0≤y≤2,0≤z < 1, B is silver and/or golden, and C is more than one in aluminium, zinc or tin, and D is selenium and/or tellurium;
Nanowire diameter in described p-type conductor nano tube/linear array is 10-500nm, and length is 100nm～500 μ m;
Described N-shaped semiconductor lamella is more than one in cadmium sulfide, zinc sulphide, zinc selenide, magnesium oxide, zinc oxide, indium selenide, indium sulfide, indium zinc selenium, tin oxide or artificial gold, and the thickness of N-shaped semiconductor lamella is 1-200nm;
Described Window layer is Al-Doped ZnO, ito thin film, graphene film or carbon nano-tube film, and the thickness of Window layer is 1nm～10 μ m;
Described metal grate electrode is molybdenum, aluminium, gold, copper, tungsten-titanium alloy, ito glass, silver, tungsten, nickel or titanium.
The preparation method of above-mentioned nanostructure CZTS film photovoltaic cell, to adopt gas-solid reaction method to prepare cuprous sulfide or copper sulphide nano linear array, in conjunction with physical vaporous deposition and heat treatment method, change above-mentioned nano-wire array into copper-zinc-tin-sulfur (CZTS) nano-wire array again, finally obtain nanostructure CZTS film photovoltaic cell;
The preparation method of above-mentioned nanostructure CZTS film photovoltaic cell, specifically comprises the following steps:
(1) by physical vaporous deposition or electrochemical deposition method, on substrate, deposit successively dorsum electrode layer, copper film, obtained depositing the substrate of copper film;
(2) substrate that has deposited copper film is mixed with hydrogen sulfide/oxygen mixed gas, at 10-200 ℃, react 1-500h, by gas-solid reaction, copper film is converted to cuprous sulfide or copper sulphide nano linear array; The surface oxide layer of cuprous sulfide or copper sulphide nano linear array is removed, then by physical vaporous deposition, depositing copper-zinc-tin element sulphur in cuprous sulfide or copper sulphide nano linear array, obtains p-type conductor nano tube/linear array after heat treatment;
(3), at p-type conductor nano tube/linear array surface deposition N-shaped semiconductor lamella, obtain having the core/shell type nano-wire array of p-n junction;
(4) by physical vaporous deposition, deposit successively Window layer and metal grate electrode on the core/shell type nano-wire array with p-n junction, metal alloyization forms metal ohmic contact, obtains nanostructure CZTS film photovoltaic cell;
The described physical vaporous deposition in step (1) and (4) is sputtering method, thermal evaporation, electron-beam vapor deposition method, laser beam evaporation method or sulfuration method;
The described electrochemical deposition method of step (1) is coating by pulse electrochemical deposition, constant voltage electrochemical deposition or Constant Electric Current chemical deposition;
In hydrogen sulfide/oxygen mixed gas described in step (2), the percent by volume of hydrogen sulfide is 1-100%; Preferably, in mist, the volume of oxygen and hydrogen sulfide is 1:(2-4);
It is cuprous sulfide or copper sulphide nano linear array to be put into aqueous hydrochloric acid solution surface oxide layer is dissolved away that the described surface oxide layer by cuprous sulfide or copper sulphide nano linear array of step (2) is removed; The concentration of described aqueous hydrochloric acid solution is 0.001 ~ 2mol/L;
The described heat treated mode of step (2) is: pass into gas, heat treatment 0.1-50h at 100-1500 ℃; Described gas is Ar, N
2, H
2s or H
2more than one in Se;
The described physical vaporous deposition of step (2) is sputtering method, thermal evaporation, electron-beam vapor deposition method or laser beam evaporation method; Described thermal evaporation is first coevaporation zinc-Xi, then evaporates copper, then coevaporation zinc-Xi; Or first evaporate tin-sulphur, then evaporate zinc-sulphur, finally evaporate copper; Or first evaporate zinc-sulphur, then evaporate tin-sulphur, finally evaporate copper-sulphur; Or first coevaporation zinc-Xi-sulphur, then coevaporation copper-sulphur; The target adopting in described sputtering method is the target being comprised of more than one elements in copper, zinc, tin or sulphur;
The method of the described deposition N-shaped of step (3) semiconductor lamella is chemical bath, spin coating, infiltration, electrochemical deposition or physical vapour deposition (PVD).
Above-mentioned nanostructure CZTS film photovoltaic cell can be for solar power generation.
In recent years, the research of nanowire solar cells is all hot issue in field of scientific study or in engineering research field.Obviously, we need high efficiency, solar cell cheaply.In any step of light transfer process, with respect to traditional Thin film cell or hull cell, the solar cell of nano thread structure has many potential advantages: light reflection reduces, fabulous light capture ability, radially p-n junction separate that exciton, band gap adjustment improve, strain relaxation preferably, the tolerance increase to defect etc.Although the conversion efficiency of nanowire solar cells can not exceed the theoretical transformation efficiency of material itself, but they can reduce and reach this limit to the quality of material own and quantitative requirement, thereby fundamentally reduce the cost of solar cell.In addition, utilize nano thread structure complicated single crystal semiconductor device directly can be assemblied in to some cheaply on substrate and electrode, such as: aluminium foil, stainless steel substrates, electro-conductive glass etc., this has solved again another the large Cost Problems existing in current photovoltaic technology.But, also do not have relevant report that a kind of preparation method of CZTS nano-wire array solar-energy photo-voltaic cell light absorbing zone is provided at present.
The present invention has following advantage and effect with respect to prior art:
1, the physical gas phase deposition technology that the present invention adopts is the technology of current industrial quarters comparative maturity, can prepare on a large scale high efficiency, CZTS nanowire array structure thin-film solar cells cheaply.
2, the present invention utilizes method large area deposition cuprous sulfide or copper sulphide nano linear array on different substrates of gas-solid reaction, greatly reduces the cost of battery; By controlling the parameters such as reaction temperature, gas ratio, reaction time, regulate the size, pattern of nano wire etc., to grow the cuprous sulfide or the copper sulfide template that are conducive to prepare high efficiency CZTS nano wire solar cell simultaneously.
3, the present invention regulates composition, phase structure and the band structure of absorbed layer nano-wire array by controlling the subsequent processes such as the order of kind, deposition of elements of deposition of elements and heat treated mode, thereby prepares the solar-energy photo-voltaic cell of different structure and performance.
3, nanostructure CZTS film photovoltaic cell light reflection of the present invention reduces, has fabulous light capture ability, band gap adjustment to improve, and has finally realized increasing substantially of photoelectric conversion efficiency.
4, preparation technology of the present invention simple, to equipment requirement is not high, cost is lower, can realize the preparation of large area, nanowire array structure thin film solar photovoltaic cell that photoelectric conversion efficiency is higher.
Accompanying drawing explanation
Fig. 1 is the structural representation of nanostructure CZTS film photovoltaic cell of the present invention; Wherein, 1-substrate, 2-back electrode, 3-p type conductor nano tube/linear array, 4-n type semiconductor lamella, 5-Window layer, 6-metal grate electrode.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
A kind of nanostructure CZTS film photovoltaic cell, is prepared by following steps:
(1) get pottery, with the NaOH solution of 1mol/L, the hydrochloric acid solution of 1mol/L, clean successively, then use successively absolute ethyl alcohol, deionized water ultrasonic cleaning, then sputter one deck ITO in ceramic substrate, the thickness of ITO is that 700nm(also can select ito glass);
(2) on the substrate after sputtering sedimentation ITO, (also can select ito glass), the copper film that sputter a layer thickness is 1um;
(3) by sputter the substrate of copper film mix with hydrogen sulfide/oxygen mixed gas (both volume ratio 1:4), at 18 ℃, vulcanize 18h, generate cuprous sulfide nano-wire array;
(4) aqueous hydrochloric acid solution of the substrate that has generated cuprous sulfide nano-wire array being put into 0.5mol/L dissolves surface oxide layer;
(5) product of step (4) is first infiltrated to 20s in the cadmium sulfate of 50mM, with after deionized water rinsing, then infiltrate 20s in the vulcanized sodium of 50mM, then use deionized water rinsing, infiltrate successively multiple circulations, obtain the cadmium sulfide layer that thickness is 60nm;
(6) 20g zinc nitrate is dissolved in 40mL absolute alcohol, adds monoethanolamine as stabilizer, 60 ℃ of stirred in water bath 2.5h, the then quiet 72h of putting at room temperature, makes colloidal sol;
(7) sample pivoted frame rotating speed being set is 3000r/min; The colloidal sol of step (6) is dropped in to substrate (being the product of step (5)) under pivoted frame low speed rotation upper, then under High Rotation Speed, carry out spin coating, then at 150 ℃, toast 5min, naturally cooling, repeat spin coating 7 times; Surface is processed to 10min with the substrate of colloidal sol at 250 ℃, then at 450 ℃, carry out the annealing in process of 2h, obtain the zinc oxide film that thickness is 60nm;
(8) by the product of step (7) sputtering sedimentation Al-Doped ZnO layer in substrate frame, deposit thickness is 450nm, a last sputter W fork formula electrode;
(9) by the product heating of step (8), after metal alloy, form ohmic contact, make cuprous sulfide nano-array solar-energy photo-voltaic cell.
The nanostructure CZTS film photovoltaic cell of the present embodiment, substrate 1 is pottery, is ITO dorsum electrode layer 2 on substrate successively, Cu
2s conductor nano tube/linear array 3, CdS, ZnO N-shaped semiconductor lamella 4, Al-Doped ZnO Window layer 5, Mo metal grate electrode 6.
The specific area of the nanostructure CZTS film photovoltaic cell of the present embodiment increases more with respect to other type solar cells, make the absorption area of light become large, and in p-type layer prepared by the present embodiment method, cuprous sulfide is mono-crystalline structures, less to reflection of light than polycrystalline and amorphous solar cell, through being tested, its p-type layer finds that its absorbance in whole visible region has all reached more than 1.5, than the p-type layer structure of film, its absorbance has increased nearly 70%.In addition, the motion that the core/shell structure of the nanostructure CZTS film photovoltaic cell of the present embodiment makes charge carrier radially, can reduce the compound of charge carrier, thereby improves nano-structured solar power conversion efficiency (pce).
A kind of nanostructure CZTS film photovoltaic cell, is prepared by following steps:
(1) get silicon chip, with the NaOH solution of 1mol/L, the hydrochloric acid solution of 1mol/L, clean successively, then use successively absolute ethyl alcohol, deionized water ultrasonic cleaning, then sputter one deck Al in silicon chip substrate, the thickness of Al is 800nm;
(2) depositing sputter a layer thickness on the substrate after Al and be about the copper film of 1um;
(3) by sputter the substrate of copper film mix with hydrogen sulfide/oxygen mixed gas (both volume ratio 1:2), at 20 ℃, vulcanize 14h, generate the sub-nano-array of sulfuration;
(4) substrate that has generated copper sulphide nano linear array being put into 1mol/L aqueous hydrochloric acid solution dissolves surface oxide layer;
(5) product of step (4) is placed on magnetic control sputtering device rotary substrate frame, cosputtering Sn, Zn and S, then, under the protection of Ar gas, obtain p-type conductor nano tube/linear array after 500 ℃ of heat treatment 12h;
(6) after sputter finishes, 50mM cadmium nitrate is dropped on absorbed layer after spin coating, then the vulcanized sodium of 50mM is dropped in to spin coating on absorbed layer, repeat successively multiple circulations, the thickness that finally deposits cadmium sulfide shell is 60nm;
(7) on the product after spin coating, evaporate Al-Doped ZnO layer, deposit thickness is 500nm; A last sputter Cu fork formula electrode;
(8) by the product heating of step (7), after metal alloy, form ohmic contact, make copper indium zinc-tin sulfur nano structure solar-energy photo-voltaic cell.
The nanostructure CZTS film photovoltaic cell of the present embodiment, substrate 1 is silicon chip, is Al dorsum electrode layer 2, Cu on substrate successively
2znSnS
4conductor nano tube/linear array 3, CdS N-shaped semiconductor lamella 4, Al-Doped ZnO Window layer 5, Cu metal grate electrode 6.
The specific area of the nanostructure CZTS film photovoltaic cell of the present embodiment increases more with respect to other type solar cells, make the absorption area of light become large, simultaneously, in p-type layer prepared by the present embodiment method, copper sulfide is mono-crystalline structures, deposit again other element, less to reflection of light than polycrystalline and amorphous solar cell, through being tested, its p-type layer finds that its absorbance in whole visible region has all reached more than 1.4, than the p-type layer structure of plane, its absorbance has increased nearly 60%.In addition, the motion that the core/shell structure of the nanostructure CZTS film photovoltaic cell of the present embodiment makes charge carrier radially, can reduce the compound of charge carrier, thereby improves nano-structured solar power conversion efficiency (pce).
A kind of nanostructure CZTS film photovoltaic cell, is prepared by following steps:
(1) electron beam evaporation one deck W on the mica sheet substrate of newly cutting open, the thickness of W is 800nm;
(2), on the substrate after electron beam evaporation W, evaporation a layer thickness is about the copper film of 1um;
(3) substrate that has evaporated copper film is mixed with hydrogen sulfide/oxygen mixed gas (both volume ratio 1:2), at 22 ℃, vulcanize 12h, generate copper sulphide nano linear array;
(4) aqueous hydrochloric acid solution of the substrate that has generated copper sulphide nano linear array being put into 1mol/L dissolves surface oxide layer;
(5) product of step (4) is placed on rotary substrate frame, layered evaporator Zn, Sn, S, then at N
2under gas protection, after 600 ℃ of heat treatment 15h, obtain p-type conductor nano tube/linear array;
(6) after evaporation finishes, by the product of step (5), at zinc sulfate, thiocarbamide, carries out chemical bath in the mixed solution of ammoniacal liquor and hydrazine hydrate, deposition zinc sulphide shell, and thickness is 60nm;
(7) product after chemical bath is placed in substrate frame and evaporates Al-Doped ZnO layer, deposit thickness is 500nm, finally deposits a Ni fork formula electrode;
(8) by the product heating of step (7), after metal alloy, form ohmic contact, make copper-zinc-tin-sulfur nano-structured solar photovoltaic cell.
The nanostructure CZTS film photovoltaic cell of the present embodiment, substrate 1 is mica, is W dorsum electrode layer 2, Cu on substrate successively
2zn
1.1sn
0.9s
4conductor nano tube/linear array 3, ZnS N-shaped semiconductor lamella 4, Al-Doped ZnO Window layer 5, Ni metal grate electrode 6.
The specific area of the nanostructure CZTS film photovoltaic cell of the present embodiment increases more with respect to other type solar cells, make the absorption area of light become large, simultaneously, in p-type layer prepared by the present embodiment method, copper sulfide is mono-crystalline structures, deposit again other element, less to reflection of light than polycrystalline and amorphous solar cell, through being tested, its p-type layer finds that its absorbance in whole visible region has all reached more than 1.2, than the p-type layer structure of plane, its absorbance has increased nearly 40%.In addition, the motion that the core/shell structure of the nanostructure CZTS film photovoltaic cell of the present embodiment makes charge carrier radially, can reduce the compound of charge carrier, thereby improves nano-structured solar power conversion efficiency (pce).
A kind of nanostructure CZTS film photovoltaic cell, is prepared by following steps:
(1) get stainless steel substrates, use successively absolute ethyl alcohol, deionized water ultrasonic cleaning, then electron beam evaporation layer of Ni on stainless steel substrates substrate, the thickness of Ni is 800nm;
(2) on the substrate after electron beam evaporation Ni, evaporate the copper film that a layer thickness is about 5um;
(3) substrate that has evaporated copper film is mixed with hydrogen sulfide/oxygen mixed gas (both volume ratio 1:2), at 24 ℃, vulcanize 12h, generate cuprous sulfide nano-array;
(4) aqueous hydrochloric acid solution of the substrate that has generated cuprous sulfide nano-wire array being put into 1mol/L dissolves surface oxide layer;
(5) product of step (4) is placed on rotary substrate frame, evaporation Zn, Sn element, then at Ar/H
2se mist (H
2se percent by volume is 20%) in, heat treatment 20h at 300 ℃, obtains p-type conductor nano tube/linear array;
(6) after sulfuration finishes, the product of step (5) is carried out to chemical bath in the mixed solution of zinc sulfate, thiocarbamide, ammoniacal liquor and hydrazine hydrate, deposition zinc sulphide shell, thickness is 60nm;
(7) sample after chemical bath is placed in substrate frame and evaporates Al-Doped ZnO layer, deposit thickness is 500nm, finally deposits a Cu fork formula electrode;
(8) by the product heating of step (7), after metal alloy, form ohmic contact, make copper-zinc-tin-sulfur (selenium) nano-structured solar photovoltaic cell.
The nanostructure CZTS film photovoltaic cell of the present embodiment, substrate 1 is stainless steel substrates, is Ni dorsum electrode layer 2, Cu on substrate successively
2znSn (S, Se)
4conductor nano tube/linear array 3, ZnS N-shaped semiconductor lamella 4, Al-Doped ZnO Window layer 5, Cu metal grate electrode 6.
The specific area of the nanostructure CZTS film photovoltaic cell of the present embodiment increases more with respect to other type solar cells, make the absorption area of light become large, simultaneously, in p-type layer prepared by the present embodiment method, cuprous sulfide is mono-crystalline structures, deposit again other element, less to reflection of light than polycrystalline and amorphous solar cell, through being tested, its p-type layer finds that its absorbance in whole visible region has all reached more than 1.3, than the p-type layer structure of plane, its absorbance has increased nearly 50%.In addition, the motion that the core/shell structure of the nanostructure CZTS film photovoltaic cell of the present embodiment makes charge carrier radially, can reduce the compound of charge carrier, thereby improves nano-structured solar power conversion efficiency (pce).
A kind of nanostructure CZTS film photovoltaic cell, is prepared by following steps:
(1) get polystyrene plastics, use successively absolute ethyl alcohol, deionized water ultrasonic cleaning, then electron beam evaporation one deck Ag on polystyrene plastics substrate, the thickness of Ag is 700nm;
(2) on the substrate after electron beam evaporation Ag, evaporate the copper film that a layer thickness is about 1um;
(3) substrate that has evaporated copper film is mixed with hydrogen sulfide/oxygen mixed gas (both volume ratio 1:2.5), at 26 ℃, vulcanize 12h, generate copper sulphide nano linear array;
(4) aqueous hydrochloric acid solution of the substrate that has generated copper sulphide nano linear array being put into 0.7mol/L dissolves surface oxide layer;
(5) product of step (4) is placed on rotary substrate frame, layered evaporator Zn, Sn, then at Ar/H
2s mist (H
2s percent by volume is 20%) in, after heat treatment 20h, obtain p-type conductor nano tube/linear array at 400 ℃;
(6) after evaporation finishes, utilize magnesium oxide target, magnetron sputtering one deck magnesium oxide layer on the product of step (5), thickness is 70nm;
(7) product after magnetron sputtering is placed in substrate frame and evaporates Al-Doped ZnO layer, deposit thickness is 600nm, finally deposits a Cu fork formula electrode;
(8) by the product heating of step (7), after metal alloy, form ohmic contact, make copper-zinc-tin-sulfur nano-structured solar photovoltaic cell.
The nanostructure CZTS film photovoltaic cell of the present embodiment, substrate 1 is polystyrene plastics, is Ag dorsum electrode layer 2, Cu on substrate successively
2zn
1.2sn
0.8s
4conductor nano tube/linear array 3, MgO N-shaped semiconductor lamella 4, Al-Doped ZnO Window layer 5, Cu metal grate electrode 6.
The specific area of the nanostructure CZTS film photovoltaic cell of the present embodiment increases more with respect to other type solar cells, make the absorption area of light become large, simultaneously, in p-type layer prepared by the present embodiment method, copper sulfide is mono-crystalline structures, deposit again other element, less to reflection of light than polycrystalline and amorphous solar cell, through being tested, its p-type layer finds that its absorbance in whole visible region has all reached more than 1.2, than the p-type layer structure of plane, its absorbance has increased nearly 40%.In addition, the motion that the core/shell structure of the nanostructure CZTS film photovoltaic cell of the present embodiment makes charge carrier radially, can reduce the compound of charge carrier, thereby improves nano-structured solar power conversion efficiency (pce).
A kind of nanostructure CZTS film photovoltaic cell, is prepared by following steps:
(1) get nickel sheet, use successively absolute ethyl alcohol, deionized water ultrasonic cleaning, then electron beam evaporation one deck Ag on nickel sheet, the thickness of Ag is 700nm;
(2) on the substrate after electron beam evaporation Ag, evaporate the copper film that a layer thickness is about 1um;
(3) substrate that has evaporated copper film is mixed with hydrogen sulfide/oxygen mixed gas (both volume ratio 1:2.5), at 28 ℃, vulcanize 12h, generate cuprous sulfide nano-wire array;
(4) aqueous hydrochloric acid solution of the substrate that has generated cuprous sulfide nano-wire array being put into 0.7mol/L dissolves surface oxide layer;
(5) product of step (4) is placed on rotary substrate frame, layered evaporator Zn, Sn, S, then at N
2/ H
2s mist (H
2s percent by volume is 15%) in, after heat treatment 24h, obtain p-type conductor nano tube/linear array at 500 ℃;
(6) after evaporation finishes, utilize indium selenide target, magnetron sputtering one deck indium selenide layer on the product of step (5), thickness is 70nm;
(7) product after magnetron sputtering is placed in substrate frame and evaporates Al-Doped ZnO layer, deposit thickness is 600nm, finally deposits a Cu fork formula electrode;
(8) by the product heating of step (7), after metal alloy, form ohmic contact, make copper-zinc-tin-sulfur nano-structured solar photovoltaic cell.
The nanostructure CZTS film photovoltaic cell of the present embodiment, substrate 1 is nickel sheet, is Ag dorsum electrode layer 2, Cu on substrate successively
2zn
1.3sn
0.7s
4conductor nano tube/linear array 3, InSe N-shaped semiconductor lamella 4, Al-Doped ZnO Window layer 5, Cu metal grate electrode 6.
The specific area of the nanostructure CZTS film photovoltaic cell of the present embodiment increases more with respect to other type solar cells, make the absorption area of light become large, simultaneously, in p-type layer prepared by the present embodiment method, cuprous sulfide is mono-crystalline structures, deposit again other element, less to reflection of light than polycrystalline and amorphous solar cell, through being tested, its p-type layer finds that its absorbance in whole visible region has all reached more than 1.2, than the p-type layer structure of plane, its absorbance has increased nearly 40%.In addition, the motion that the core/shell structure of the nanostructure CZTS film photovoltaic cell of the present embodiment makes charge carrier radially, can reduce the compound of charge carrier, thereby improves nano-structured solar power conversion efficiency (pce).
Embodiment 7
A kind of nanostructure CZTS film photovoltaic cell, its raw materials, preparation method and performance characteristic are with embodiment 6.Difference is: back electrode 2 is Au, and thickness is 50nm; N-shaped semiconductor lamella 4 is In2S, and thickness is 1nm; The gas-solid reaction time is 1h, and watery hydrochloric acid concentration used is 0.001mol/L.
Embodiment 8
A kind of nanostructure CZTS film photovoltaic cell, its raw materials, preparation method and performance characteristic are with embodiment 7.Difference is: metal grate electrode 6 is Au; N-shaped semiconductor lamella 4 is InZnSe, and thickness is 200nm; Window layer 5 is carbon nano-tube film; Back electrode 2 layer thicknesses are 50um; The gas-solid reaction time is 500h, and used salt aqueous acid concentration is 5mol/L.
Embodiment 9
A kind of nanostructure CZTS film photovoltaic cell, its raw materials, preparation method and performance characteristic are with embodiment 8.Difference is: N-shaped semiconductor lamella 4 is SnO
2, thickness is 100nm; Window layer 5 is graphene film; Dorsum electrode layer thickness is 25um, and the gas-solid reaction time is 30h, and used salt aqueous acid concentration is 3mol/L.
Embodiment 10
A kind of nanostructure CZTS film photovoltaic cell, its raw materials, preparation method and performance characteristic are with embodiment 9.Difference is: metal grate electrode 6 is tungsten-titanium alloy; N-shaped semiconductor lamella 4 is SnS
2, thickness is 80nm; Window layer 5 is ito thin film; Dorsum electrode layer thickness is 20um, and the gas-solid reaction time is 25h, and used salt aqueous acid concentration is 2mol/L.
Above-described embodiment is preferably execution mode of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (2)
1. a preparation method for nanostructure CZTS film photovoltaic cell, is characterized in that comprising the following steps:
(1) by physical vaporous deposition or electrochemical deposition method, on substrate, deposit successively dorsum electrode layer, copper film, obtained depositing the substrate of copper film;
(2) substrate that has deposited copper film is mixed with hydrogen sulfide/oxygen mixed gas, at 10-200 ℃, react 1-500h, by gas-solid reaction, copper film is converted to cuprous sulfide or copper sulphide nano linear array; The surface oxide layer of cuprous sulfide or copper sulphide nano linear array is removed, then by physical vaporous deposition, depositing copper-zinc-tin element sulphur in cuprous sulfide or copper sulphide nano linear array, obtains p-type conductor nano tube/linear array after heat treatment;
(3), at p-type conductor nano tube/linear array surface deposition N-shaped semiconductor lamella, obtain having the core/shell type nano-wire array of p-n junction;
(4) by physical vaporous deposition, on the core/shell type nano-wire array with p-n junction, deposit successively Window layer and metal grate electrode, obtain nanostructure CZTS film photovoltaic cell.
2. the preparation method of nanostructure CZTS film photovoltaic cell according to claim 1, is characterized in that:
The described physical vaporous deposition in step (1) and (4) is sputtering method, thermal evaporation, electron-beam vapor deposition method, laser beam evaporation method or sulfuration method;
The described electrochemical deposition method of step (1) is coating by pulse electrochemical deposition, constant voltage electrochemical deposition or Constant Electric Current chemical deposition;
The method of the described deposition N-shaped of step (3) semiconductor lamella is chemical bath, spin coating, infiltration, electrochemical deposition or physical vapour deposition (PVD).
3.the preparation method of nanostructure CZTS film photovoltaic cell according to claim 1, is characterized in that:
The described heat treated mode of step (2) is: pass into gas, heat treatment 0.1-50h at 100-1500 ℃; Described gas is Ar, N
2, H
2s or H
2more than one in Se;
The described physical vaporous deposition of step (2) is sputtering method, thermal evaporation, electron-beam vapor deposition method or laser beam evaporation method.
4.the preparation method of nanostructure CZTS film photovoltaic cell according to claim 3, is characterized in that:
Described thermal evaporation is first coevaporation zinc-Xi, then evaporates copper, then coevaporation zinc-Xi; Or first evaporate tin-sulphur, then evaporate zinc-sulphur, finally evaporate copper; Or first evaporate zinc-sulphur, then evaporate tin-sulphur, finally evaporate copper-sulphur; Or first coevaporation zinc-Xi-sulphur, then coevaporation copper-sulphur;
The target adopting in described sputtering method is the target being comprised of more than one elements in copper, zinc, tin or sulphur.
5.the preparation method of nanostructure CZTS film photovoltaic cell according to claim 1, is characterized in that: described nanostructure CZTS film photovoltaic cell is comprised of substrate, back electrode, p-type conductor nano tube/linear array, N-shaped semiconductor lamella, Window layer and metal grate electrode successively;
Described p-type conductor nano tube/linear array is by semiconducting alloy (Cu
xb
1-x)
2c
y(D
zs
1-z)
4composition, wherein 0 < x≤1,0≤y≤2,0≤z < 1, B is silver and/or golden, and C is more than one in aluminium, zinc or tin, and D is selenium and/or tellurium.
6.the preparation method of nanostructure CZTS film photovoltaic cell according to claim 5, is characterized in that:
Described substrate is pottery, mica, high molecule plastic, metal, silicon chip, glass or stainless steel substrates;
Described back electrode is molybdenum, aluminium, gold, copper, ito glass, silver, tungsten, nickel or titanium, and the thickness of dorsum electrode layer is 50nm～50 μ m.
7.the preparation method of nanostructure CZTS film photovoltaic cell according to claim 5, it is characterized in that: described N-shaped semiconductor lamella is more than one in cadmium sulfide, zinc sulphide, zinc selenide, magnesium oxide, zinc oxide, indium selenide, indium sulfide, indium zinc selenium, tin oxide or artificial gold, and the thickness of N-shaped semiconductor lamella is 1-200 nm.
8.the preparation method of nanostructure CZTS film photovoltaic cell according to claim 5, is characterized in that:
Described Window layer is Al-Doped ZnO, ITO film, graphene film or carbon nano-tube film, and the thickness of Window layer is 1 nm～10 μ m;
Described metal grate electrode is molybdenum, aluminium, gold, copper, tungsten-titanium alloy, ito glass, silver, tungsten, nickel or titanium.
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| CN104465807B (en) * | 2014-12-18 | 2016-06-22 | 商丘师范学院 | A kind of CZTS nano-array thin film solar photovoltaic cell and preparation method thereof |
| CN105615174B (en) * | 2016-03-17 | 2018-02-02 | 杨祖发 | A kind of parasol with charge function |
| CN108486623A (en) * | 2018-03-09 | 2018-09-04 | 湘潭大学 | A kind of method that substep pulse electrodeposition after annealing prepares copper-zinc-tin-sulfur solar battery film material |
| CN110228788A (en) * | 2019-05-22 | 2019-09-13 | 湖北第二师范学院 | A kind of Berzeline nanotube and preparation method thereof, solar battery |
| CN113782622B (en) * | 2021-08-17 | 2024-01-26 | 中国建材国际工程集团有限公司 | Thin film solar cell panel and manufacturing method thereof |
| CN115417445B (en) * | 2022-09-27 | 2023-10-27 | 商丘师范学院 | Copper-zinc-tin-sulfur one-dimensional semiconductor nano-structure array, preparation method and application thereof |
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