CN103956406A - Non-vacuum manufacturing method of copper-zinc-tin-sulfur solar battery of superstrate structure - Google Patents
Non-vacuum manufacturing method of copper-zinc-tin-sulfur solar battery of superstrate structure Download PDFInfo
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- CN103956406A CN103956406A CN201410152965.2A CN201410152965A CN103956406A CN 103956406 A CN103956406 A CN 103956406A CN 201410152965 A CN201410152965 A CN 201410152965A CN 103956406 A CN103956406 A CN 103956406A
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- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 238000000137 annealing Methods 0.000 claims abstract description 54
- 239000000758 substrate Substances 0.000 claims abstract description 54
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 34
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 16
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 16
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 14
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011787 zinc oxide Substances 0.000 claims abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052709 silver Inorganic materials 0.000 claims abstract description 10
- 239000004332 silver Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000007650 screen-printing Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 4
- 239000010439 graphite Substances 0.000 claims abstract description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 116
- 239000002243 precursor Substances 0.000 claims description 96
- 239000007789 gas Substances 0.000 claims description 91
- 239000007864 aqueous solution Substances 0.000 claims description 86
- 238000002360 preparation method Methods 0.000 claims description 82
- 238000000151 deposition Methods 0.000 claims description 75
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- 239000010408 film Substances 0.000 claims description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- 239000011248 coating agent Substances 0.000 claims description 51
- 238000000576 coating method Methods 0.000 claims description 51
- 230000008021 deposition Effects 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 46
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 45
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 29
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 28
- 239000012153 distilled water Substances 0.000 claims description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- 235000014121 butter Nutrition 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 25
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 238000004062 sedimentation Methods 0.000 claims description 24
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 24
- 239000010409 thin film Substances 0.000 claims description 23
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 21
- 229910052786 argon Inorganic materials 0.000 claims description 20
- 239000012159 carrier gas Substances 0.000 claims description 20
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 18
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 17
- 239000004246 zinc acetate Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- 235000019270 ammonium chloride Nutrition 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 12
- 238000000889 atomisation Methods 0.000 claims description 12
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 239000011733 molybdenum Substances 0.000 claims description 12
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 12
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 11
- 238000002207 thermal evaporation Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- CETDWAHZEGNBOI-UHFFFAOYSA-N antimony;sulfanylideneindium Chemical compound [Sb].[In]=S CETDWAHZEGNBOI-UHFFFAOYSA-N 0.000 claims description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- YOXKVLXOLWOQBK-UHFFFAOYSA-N sulfur monoxide zinc Chemical compound [Zn].S=O YOXKVLXOLWOQBK-UHFFFAOYSA-N 0.000 claims description 10
- 239000011592 zinc chloride Substances 0.000 claims description 10
- 235000005074 zinc chloride Nutrition 0.000 claims description 10
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 8
- 238000000197 pyrolysis Methods 0.000 claims description 8
- 239000001119 stannous chloride Substances 0.000 claims description 8
- 235000011150 stannous chloride Nutrition 0.000 claims description 8
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 claims description 8
- 239000003570 air Substances 0.000 claims description 7
- 239000005357 flat glass Substances 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000005566 electron beam evaporation Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229960001296 zinc oxide Drugs 0.000 claims description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 4
- 238000003854 Surface Print Methods 0.000 claims description 4
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- PFGAZGKYFFFSEA-UHFFFAOYSA-I aluminum zinc pentaacetate Chemical compound [Al+3].[Zn++].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O PFGAZGKYFFFSEA-UHFFFAOYSA-I 0.000 claims description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 4
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 3
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical group OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 2
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000002985 plastic film Substances 0.000 claims description 2
- 229940045105 silver iodide Drugs 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 238000002061 vacuum sublimation Methods 0.000 claims description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 230000003139 buffering effect Effects 0.000 abstract 2
- GOANPZZEFWNNRK-UHFFFAOYSA-N O.[S-2].S.[Zn+2] Chemical compound O.[S-2].S.[Zn+2] GOANPZZEFWNNRK-UHFFFAOYSA-N 0.000 abstract 1
- 239000004408 titanium dioxide Substances 0.000 abstract 1
- 229910052793 cadmium Inorganic materials 0.000 description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical group [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- WDLZKULLPVDKJZ-UHFFFAOYSA-L C(C)(=O)[O-].[Zn+2].C(C)(=O)[O-].[Al+3] Chemical compound C(C)(=O)[O-].[Zn+2].C(C)(=O)[O-].[Al+3] WDLZKULLPVDKJZ-UHFFFAOYSA-L 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- PCRGAMCZHDYVOL-UHFFFAOYSA-N copper selanylidenetin zinc Chemical compound [Cu].[Zn].[Sn]=[Se] PCRGAMCZHDYVOL-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002002 slurry 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
- H01L31/18—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
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
-
- 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
Abstract
A non-vacuum manufacturing method of a copper-zinc-tin-sulfur solar battery of a superstrate structure comprises the steps that a, a substrate is provided; b, a conducting layer is prepared, and a fluorine-mixed stannic oxide film or an antimony-mixed stannic oxide film or an aluminum-mixed zinc oxide is atomized, pyrolyzed and deposited on the surface of the substrate; c, a compact layer is prepared, and a titanium dioxide or a zinc oxide film is atomized, pyrolyzed and deposited on the surface of the compact layer; d, a buffering layer is prepared, and a cadmium sulfide film or a zinc sulfide film or an antimony-mixed indium sulfide film or an oxyhydrogen indium sulfide film or an oxygen zinc sulfide film is prepared on the surface of the compact layer in an atomized and pyrolyzed mode or a chemical bath mode; e, an absorbing layer is prepared, a copper-zinc-tin-sulfur film is atomized, pyrolyzed and deposited on the surface of the buffering layer, and annealing treatment is performed; f, an upper electrode is manufactured, graphite paste or silver paste is printed on the surface of the absorbing layer in a silk-screen printing mode, and annealing treatment is performed. The method has the advantages of being low in production cost, easy to operate, environmentally friendly, and suitable for industrialization production of solar batteries.
Description
Technical field
The invention belongs to solar cell preparation and application, particularly a kind of antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell.
Background technology
The film preparation of thin film solar cell is relevant with this body structure of battery, thin film solar cell mainly contains two kinds of structures: substrate structure and superstrate structure, wherein CIGS solar cell is the representative in substrate structure, and cadmium-Te solar battery is the representative in superstrate structure.Superstrate structure is relatively simple, easily encapsulation, and this is one of reason of the extensive industrialization of cadmium telluride battery energy, in addition, is also conducive to use on laminated cell.And substrate structure relative complex is main relevant with battery design and preparation technology.
Cadmium telluride (CdTe) battery and Copper Indium Gallium Selenide (CuIn
xga
1-xse
2) the battery marketization, but there is expensive even poisonous problem, therefore the solar cell of researching and developing low-cost high-efficiency is the core content of theCourse of PV Industry, and find cheapness, environmental protection, semi-conducting material that photovoltaic conversion efficiency is high is the key that develops solar cell technology.Novel quaternary semiconductor: as copper-zinc-tin-sulfur (Cu
2znSnS
4be called for short CZTS) and copper-zinc-tin-selenium (Cu
2znSnSe
4be called for short CZTSe), they possess the advantages such as light absorption is strong, component reserves are abundant, nontoxic, are expected to replace cadmium telluride and copper indium gallium selenide cell, become efficient, cheap films solar cell of future generation, and realize large-area applications.
At present, copper-zinc-tin-selenium solar cell main flow is to use substrate structure, technology transplant is in CIGS solar cell, although battery efficiency is higher, but the Film preparations such as back electrode, absorbed layer, Window layer, top electrode generally adopt the method for vacuum evaporation or sputter, manufacturing cost is higher, and conventionally will adopt hypertoxic selenizing technique, unfavorable to environment.And the copper-zinc-tin-sulfur solar cell of superstrate structure temporarily has no report.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell, and the method low production cost is simple to operate, environmentally friendly, and the industrialization that is applicable to solar cell is produced.
Technical solution of the present invention is:
An antivacuum preparation method for superstrate structure copper-zinc-tin-sulfur solar cell, its concrete steps are:
A, provide substrate
Select the sheet glass, transparent plastic sheet or the polyimide piece that clean up as substrate;
B, conductive layer preparation
Preparation conductive layer precursor aqueous solution, described conductive layer precursor aqueous solution is ammonium fluoride-butter of tin precursor aqueous solution, trichloride antimony-butter of tin precursor aqueous solution or aluminium salt-zinc acetate precursor aqueous solution, conductive layer precursor aqueous solution becomes gas through ultrasonic atomizatio, and becoming thickness at substrate surface pyrolytic deposition is that fluorine-doped tin dioxide film, antimony-doped stannic oxide film or the Al-Doped ZnO film of 0.5 μ m～1.5 μ m is as conductive layer;
C, compacted zone preparation
Preparation compacted zone precursor aqueous solution, described compacted zone precursor aqueous solution is isopropyl titanate precursor aqueous solution or isopropyl alcohol zinc precursor solution, compacted zone precursor aqueous solution becomes gas through ultrasonic atomizatio, taking compressed air, nitrogen or argon gas as carrier gas, becoming thickness at conductive layer surface pyrolytic deposition is that the titanium deoxid film of 20nm～200nm or zinc-oxide film are as compacted zone;
D, resilient coating preparation
Adopt atomization pyrolysis or chemical bath to prepare the resilient coating that thickness is 20nm～200nm on compacted zone surface, described resilient coating is cadmium sulphide membrane, zinc sulfide film, mix antimony indium sulfide thin film, hydrogen-oxygen indium sulfide thin film or zinc oxysulfide film;
E, absorbed layer preparation
Preparation absorbed layer precursor aqueous solution, becomes gas by absorbed layer precursor aqueous solution through ultrasonic atomizatio, and taking nitrogen or argon gas as carrier gas, preparing thickness at buffer-layer surface is 1 μ m～10 μ m copper-zinc-tin-sulfur film, and carries out annealing in process, obtains copper-zinc-tin-sulfur absorbed layer;
When preparation absorbed layer precursor aqueous solution, by mantoquita, zinc salt, pink salt and thiocarbamide add in solvent, being mixed with mantoquita concentration is 0.2 mol/L～1 mol/L, zinc salt concentration is 0.2 mol/L～1 mol/L, pink salt concentration is 0.2 mol/L～1 mol/L, thiourea concentration is the mixed solution of 0.5mol/L～5 mol/L, described mantoquita is dichloride copper, stannous chloride or cuprous iodide, described zinc salt is zinc dichloride or zinc iodide, described pink salt is stannous chloride, butter of tin or tin tetraiodide, described solvent is N, dinethylformamide (DMF)) and monoethanolamine according to the mixed solution of volume ratio 1:1～1:5 preparation, dimethyl sulfoxide (DMSO) (DMSO), methyl alcohol, ethanol, one in water,
When annealing in process, passing into hydrogen volume percentage composition and be 0.1%～4% nitrogen and hydrogen mixture, hydrogen sulfide volumn concentration is that 0.1%～15% hydrogen sulfide diluent gas, high pure nitrogen or argon gas are protection gas, annealing temperature is 300 DEG C～600 DEG C, heating-up time is 0.5min～10 min, annealing time is 5 min～60 min, and temperature fall time is 1 min～15 min or 30 min～60 min;
F, top electrode preparation
Adopt screen printing mode starch and carry out annealing in process at absorbed layer surface printing black lead wash or silver, or adopt vacuum thermal evaporation mode or electron-beam evaporation mode at absorbed layer surface evaporation silver, gold, molybdenum, molybdenum bisuphide, prepare the top electrode that thickness is 50nm～150nm, electric current when vacuum thermal evaporation or electron beam evaporation is 80 A～120A; When annealing in process; passing into hydrogen volume percentage composition and be 0.1%～4% nitrogen and hydrogen mixture, hydrogen sulfide volumn concentration is that 0.1%～15% hydrogen sulfide diluent gas, high pure nitrogen or argon gas are protection gas; annealing temperature is 300 DEG C～600 DEG C; heating-up time is 0.5min～10 min; annealing time is 5 min～60 min, and temperature fall time is 1 min～15 min or 30 min～60 min.
Prepare conductive layer, compacted zone, resilient coating, absorbed layer, while carrying out atomization pyrolytic deposition, gas flow remains on 5mL/min～30mL/min, and sedimentation time is 1min～30min, depositing temperature is 300 DEG C～600 DEG C, and spout is 0.5cm～15cm to hot platform distance.
In ammonium fluoride-butter of tin precursor aqueous solution of step b, the concentration of ammonium fluoride is that the concentration of 1mol/L～2mol/L, butter of tin is 0.6 mol/L～1 mol/L, and solvent is at least one in distilled water, methyl alcohol, ethanol; In trichloride antimony-butter of tin precursor aqueous solution, concentration 0.6 mol/L～1 mol/L of trichloride antimony, the concentration of butter of tin are 1mol/L～2mol/L, and solvent is methyl alcohol or ethanol; In aluminium salt-zinc acetate precursor aqueous solution, concentration 0.6 mol/L～1 mol/L, the acetic acid zinc concentration of aluminium salt is 1mol/L～2mol/L, and solvent is methyl alcohol or ethanol, and described aluminium salt is silver iodide or aluminium acetate.
When step c preparation isopropyl titanate precursor aqueous solution, isopropyl titanate is mixed according to mol ratio 1:1～1:5 with ethanolic solution; When preparation isopropyl alcohol zinc precursor solution, isopropyl alcohol zinc is mixed according to mol ratio 1:1～1:5 with ethanolic solution.
When resilient coating is prepared in atomization pyrolysis, first prepare resilient coating precursor aqueous solution, resilient coating precursor aqueous solution becomes gas through ultrasonic atomizatio, be deposited as resilient coating in compacted zone surface pyrolysis, cadmium sulphide membrane resilient coating, zinc sulfide film resilient coating, when mixing antimony indium sulfide thin film resilient coating and preparing, pass into nitrogen or argon gas as carrier gas; Time prepared by hydrogen-oxygen indium sulfide thin film resilient coating, zinc oxysulfide film film resilient coating, pass into compressed air as carrier gas.
While preparing cadmium sulphide membrane, the concentration of first preparing cadmium acetate is that the concentration of 0.05 mol/L～0.5 mol/L, thiocarbamide is the resilient coating precursor aqueous solution of 0.2 mol/L～1 mol/L, and wherein solvent is distilled water, methyl alcohol or ethanol; While preparing zinc sulfide film, the concentration of first preparing acetic acid zinc concentration and be 0.05 mol/L～0.5 mol/L, thiocarbamide is the resilient coating precursor aqueous solution of 0.2 mol/L～1 mol/L, and wherein solvent is distilled water, methyl alcohol or ethanol; When antimony indium sulfide thin film is mixed in preparation, first the concentration of preparing indium trichloride is that the concentration of 0.1mol/L～0.6mol/L, trichloride antimony is that the concentration of 0.05 mol/L～0.5 mol/L, thiocarbamide is the resilient coating precursor aqueous solution of 0.2 mol/L～1 mol/L, and wherein solvent is methyl alcohol or ethanol; While preparing hydrogen-oxygen indium sulfide thin film, first preparing indium trichloride concentration is that 0.1mol/L～0.6mol/L, thiourea concentration are the resilient coating precursor aqueous solution of 0.2 mol/L～1 mol/L, and wherein solvent is distilled water, methyl alcohol or ethanol; While preparing zinc oxysulfide film, first preparing zinc acetate concentration is that 0.1mol/L～0.6mol/L, thiourea concentration are the resilient coating precursor aqueous solution of 0.2 mol/L～1 mol/L, and wherein solvent is distilled water, methyl alcohol or ethanol.
Adopt chemical bath to prepare resilient coating, time prepared by cadmium sulphide membrane, cadmium acetate, ammonium chloride, thiocarbamide and ammoniacal liquor are equipped with in the beaker of distilled water, being mixed with cadmium acetate concentration is that 0.05 mol/L～0.5 mol/L, ammonium chloride concentration are that 0.2 mol/L～1 mol/L, thiourea concentration are that 0.2 mol/L～1 mol/L, ammonia concn are the mixed solution of 0.2 mol/L～1 mol/L; The substrate for preparing conductive layer and compacted zone is put into beaker, at-10 DEG C～90 DEG C, react 10min～100min, form cadmium sulphide membrane on compacted zone surface;
Time prepared by zinc sulfide film, zinc acetate, ammonium chloride, thiocarbamide and ammoniacal liquor are added in the beaker that distilled water is housed, and being mixed with zinc acetate concentration is that 0.05 mol/L～0.5 mol/L, ammonium chloride concentration are that 0.2 mol/L～1 mol/L, thiourea concentration are that 0.2 mol/L～1 mol/L, ammonia concn are the mixed solution of 0.2 mol/L～1 mol/L; The substrate for preparing conductive layer and compacted zone is put into beaker, at-10 DEG C～90 DEG C, react 10min～100min, form zinc sulfide film on compacted zone surface;
When mixing antimony indium sulfide thin film and preparing, indium trichloride, trichloride antimony, thiocarbamide and ammoniacal liquor are added in the beaker that distilled water is housed, and being mixed with indium trichloride concentration is that 0.1 mol/L～0.6 mol/L, trichloride antimony concentration are that 0.05 mol/L～0.5 mol/L, thiourea concentration are that 0.2mol/L～1 mol/L and ammonia concn are the mixed solution of 0.1mol/L～0.5 mol/L; The substrate for preparing conductive layer and compacted zone is put into beaker, at-10 DEG C～90 DEG C, react 10min～100min, form and mix antimony indium sulfide thin film on compacted zone surface;
Time prepared by hydrogen-oxygen indium sulfide thin film, indium trichloride, thiocarbamide and ammoniacal liquor are added in the beaker that distilled water is housed, and being mixed with indium trichloride concentration is that 0.1 mol/L～0.6 mol/L, thiourea concentration are the mixed solution of 0.2mol/L～1 mol/L, ammonia concn 0.2-1 mole every liter; The substrate for preparing conductive layer and compacted zone is put into beaker, at-10 DEG C～90 DEG C, react 10min～100min, form hydrogen-oxygen indium sulfide thin film on compacted zone surface;
When zinc oxysulfide film preparation, zinc acetate, thiocarbamide and ammoniacal liquor are added in the beaker that distilled water is housed, and being mixed with zinc acetate concentration is that 0.05mol/L～0.6 mol/L, thiourea concentration are that 0.2 mol/L～1 mol/L, ammonia concn are 0.2 mol/L～1 mol/L; The substrate for preparing conductive layer and compacted zone is put into beaker, at-10 DEG C～90 DEG C, react 10min～100min, form zinc oxysulfide film on compacted zone surface.
Described black lead wash is that electrically conductive graphite and cellulose, terpinol are mixed according to mass ratio 10:3～10:2,10:2～10:1 respectively, and the purity of Vacuum sublimation or electron beam evaporation material silver, gold, molybdenum or molybdenum bisuphide used is 99.9%～99.99%.
While cleaning substrate, substrate is put in beaker, poured into acetone, ultrasonic cleaning 5min～8min, then use alcohol ultrasonic cleaning 5min～8min, then use saturated NaOH alcohol solution dipping ultrasonic cleaning 20min～25min, finally use deionized water rinsing, natural drying.
Beneficial effect of the present invention:
(1) in preparation process, except preparing top electrode, all retes carry out completely under non-vacuum condition, preparing thin-film process mainly adopts atomization pyrolysis or chemical bath to carry out, use raw material is cheap inorganic salts, raw material availability is high, has advantages of low production cost compared with conventional vacuum evaporation or sputter and selenizing technique.
(2) adopt the mode of atomization pyrolysis to be applicable to the preparation of large-area solar cell, be conducive to the industrialization of solar cell.
(3) advantages of nontoxic raw materials using in battery preparation process, has avoided poisonous selenization process, and safety non-pollution is environmentally friendly.
Brief description of the drawings
Fig. 1 is the XRD figure of fluorine-doped tin dioxide conductive layer of the present invention;
Fig. 2 is the XRD figure of cadmium sulfide resilient coating of the present invention;
Fig. 3 is the XRD figure of copper-zinc-tin-sulfur absorbed layer of the present invention;
Fig. 4 is the Raman spectrogram of copper-zinc-tin-sulfur absorbed layer of the present invention;
Fig. 5 is the scanning electron microscope (SEM) photograph of copper-zinc-tin-sulfur absorbed layer of the present invention;
Fig. 6 is the XRD figure of antimony-doped stannic oxide conductive layer of the present invention;
Fig. 7 is the XRD figure of zinc sulphide resilient coating of the present invention;
Fig. 8 is the XRD figure of Al-Doped ZnO conductive layer of the present invention.
Embodiment
Embodiment 1
A, provide substrate
Select sheet glass as substrate, substrate is put in beaker, pour acetone into, ultrasonic cleaning 5min, then use alcohol ultrasonic cleaning 5min, and then use saturated NaOH alcohol solution dipping ultrasonic cleaning 20min, finally use deionized water rinsing, natural drying;
B, conductive layer preparation
It is that the concentration of 1mol/L, butter of tin is ammonium fluoride-butter of tin precursor aqueous solution of 0.6 mol/L that ammonium fluoride and butter of tin are added to the concentration of preparing ammonium fluoride in distilled water, ammonium fluoride-butter of tin precursor aqueous solution becomes gas through ultrasonic atomizatio, becoming thickness at substrate surface pyrolytic deposition is that the fluorine-doped tin dioxide film of 0.5 μ m is as conductive layer, when pyrolytic deposition, gas flow remains on 5mL/min, sedimentation time is 1min, depositing temperature is 300 DEG C, and spout is 0.5cm to hot platform distance;
C, compacted zone preparation
Isopropyl titanate is mixed and is mixed with isopropyl titanate precursor aqueous solution according to mol ratio 1:1 with ethanolic solution, isopropyl titanate precursor aqueous solution becomes gas through ultrasonic atomizatio, taking compressed air as carrier gas, becoming thickness at conductive layer surface pyrolytic deposition is that the titanium deoxid film of 20nm is as compacted zone, when pyrolytic deposition, gas flow remains on 5mL/min, sedimentation time is 1min, and depositing temperature is 300 DEG C, and spout is 0.5cm to hot platform distance;
D, resilient coating preparation
It is that the concentration of 0.05 mol/L, thiocarbamide is cadmium acetate-thiocarbamide precursor aqueous solution of 0.2 mol/L that cadmium acetate and thiocarbamide are added to the concentration that is mixed with cadmium acetate in distilled water, cadmium acetate-thiocarbamide precursor aqueous solution becomes gas through ultrasonic atomizatio, nitrogen buffer gas, preparing thickness on compacted zone surface is the cadmium sulphide membrane resilient coating of 20nm, when pyrolytic deposition, gas flow remains on 5mL/min, sedimentation time is 1min, and depositing temperature is 300 DEG C, and spout is 0.5cm to hot platform distance;
E, absorbed layer preparation
Dichloride copper, zinc dichloride, stannous chloride and thiocarbamide are added in methyl alcohol, being mixed with dichloride copper concentration is that 0.2 mol/L, zinc dichloride concentration are that 0.2 mol/L, stannous chloride concentration are the absorbed layer precursor aqueous solution that 0.2 mol/L, thiourea concentration are 0.5mol/L, absorbed layer precursor aqueous solution is become to gas through ultrasonic atomizatio, nitrogen buffer gas, becoming thickness at buffer-layer surface pyrolytic deposition is 1 μ m copper-zinc-tin-sulfur film, when pyrolytic deposition, gas flow remains on 5mL/min, sedimentation time is that 1min depositing temperature is 100 DEG C, and spout is 0.5cm to hot platform distance; Then carry out annealing in process, when annealing in process, pass into hydrogen volume percentage composition and be 0.1% nitrogen and hydrogen mixture, annealing temperature is 300 DEG C, and the heating-up time is 0.5 min, and annealing time is 60 min, and temperature fall time is 1min, obtains copper-zinc-tin-sulfur absorbed layer;
F, top electrode preparation
Adopt screen printing mode at absorbed layer surface printing black lead wash; described black lead wash is that electrically conductive graphite and cellulose, terpinol are mixed according to mass ratio 10:3:2 respectively; then carry out annealing in process; obtain the top electrode that thickness is 500 nm, when annealing in process, pass into high pure nitrogen for protection gas; annealing temperature is 300 DEG C; heating-up time is 0.5min, and annealing time is 60 min, and temperature fall time is 1min.
Embodiment 2
A, provide substrate
Select sheet glass as substrate, substrate is put in beaker, pour acetone into, ultrasonic cleaning 8min, then use alcohol ultrasonic cleaning 8min, and then use saturated NaOH alcohol solution dipping ultrasonic cleaning 25min, finally use deionized water rinsing, natural drying;
B, conductive layer preparation
It is that the concentration of 2mol/L, butter of tin is ammonium fluoride-butter of tin precursor aqueous solution of 1 mol/L that ammonium fluoride and butter of tin are added to the concentration of preparing ammonium fluoride in ethanol, ammonium fluoride-butter of tin precursor aqueous solution becomes gas through ultrasonic atomizatio, becoming thickness at substrate surface pyrolytic deposition is that the fluorine-doped tin dioxide film of 1.5 μ m is as conductive layer, when pyrolytic deposition, gas flow remains on 30mL/min, sedimentation time is 30min, depositing temperature is 600 DEG C, and spout is 15cm to hot platform distance;
C, compacted zone preparation
Isopropyl titanate is mixed and is mixed with isopropyl titanate precursor aqueous solution according to mol ratio 1:5 with ethanolic solution, isopropyl titanate precursor aqueous solution becomes gas through ultrasonic atomizatio, nitrogen buffer gas, becoming thickness at conductive layer surface pyrolytic deposition is that the titanium deoxid film of 200nm is as compacted zone, when pyrolytic deposition, gas flow remains on 30mL/min, sedimentation time is 30min, and depositing temperature is 600 DEG C, and spout is 15cm to hot platform distance;
D, resilient coating preparation
It is cadmium acetate-thiocarbamide precursor aqueous solution that the concentration of 0.5 mol/L, thiocarbamide is 1mol/L that cadmium acetate and thiocarbamide are added to the concentration that is mixed with cadmium acetate in distilled water, cadmium acetate-thiocarbamide precursor aqueous solution becomes gas through ultrasonic atomizatio, taking argon gas as carrier gas, preparing thickness on compacted zone surface is the cadmium sulphide membrane resilient coating of 200nm, when pyrolytic deposition, gas flow remains on 30mL/min, sedimentation time is 30min, and depositing temperature is 600 DEG C, and spout is 15cm to hot platform distance;
E, absorbed layer preparation
Cuprous iodide, zinc iodide, tin tetraiodide and thiocarbamide are added in ethanol, being mixed with cuprous iodide concentration is that 1mol/L, zinc iodide concentration are that 1 mol/L, tin tetraiodide concentration are the absorbed layer precursor aqueous solution that 1mol/L, thiourea concentration are 5mol/L, absorbed layer precursor aqueous solution is become to gas through ultrasonic atomizatio, taking argon gas as carrier gas, becoming thickness at buffer-layer surface pyrolytic deposition is 10 μ m copper-zinc-tin-sulfur films, when pyrolytic deposition, gas flow remains on 30mL/min, sedimentation time is 30min, depositing temperature is 600 DEG C, and spout is 15cm to hot platform distance; Then carry out annealing in process, when annealing in process, pass into argon gas, annealing temperature is 600 DEG C, and the heating-up time is 10min, and annealing time is 5min, and temperature fall time is 60min, obtains copper-zinc-tin-sulfur absorbed layer;
F, top electrode preparation
Adopt screen printing mode at absorbed layer surface printing silver slurry, then carry out annealing in process, obtain the top electrode that thickness is 150 nm, when annealing in process, pass into argon gas, annealing temperature is 600 DEG C, heating-up time is 10min, and annealing time is 5min, and temperature fall time is 60min.
Embodiment 3
A, provide substrate
Select polyimide piece as substrate, substrate is put in beaker, pour acetone into, ultrasonic cleaning 6min, then use alcohol ultrasonic cleaning 6min, and then use saturated NaOH alcohol solution dipping ultrasonic cleaning 22min, finally use deionized water rinsing, natural drying;
B, conductive layer preparation
It is that the concentration of 1.5mol/L, butter of tin is ammonium fluoride-butter of tin precursor aqueous solution of 0.8 mol/L that ammonium fluoride and butter of tin are added to the concentration of preparing ammonium fluoride in methyl alcohol, ammonium fluoride-butter of tin precursor aqueous solution becomes gas through ultrasonic atomizatio, becoming thickness at substrate surface pyrolytic deposition is that the fluorine-doped tin dioxide film of 1 μ m is as conductive layer, when pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, depositing temperature is 400 DEG C, and spout is 8cm to hot platform distance; The XRD of fluorine-doped tin dioxide film conductive layer schemes as shown in Figure 1, in figure, a represents commodity fluorine-doped tin dioxide (FTO), b represents the fluorine-doped tin dioxide that in the present invention, atomization pyrolysismethod makes (FTO), as seen from Figure 1, the two spectrogram is substantially identical, shows that the fluorine-doped tin dioxide (FTO) making is pure phase;
C, compacted zone preparation
Isopropyl titanate is mixed and is mixed with isopropyl titanate precursor aqueous solution according to mol ratio 1:2 with ethanolic solution, isopropyl titanate precursor aqueous solution becomes gas through ultrasonic atomizatio, taking argon gas as carrier gas, becoming thickness at conductive layer surface pyrolytic deposition is that the titanium deoxid film of 100nm is as compacted zone, when pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, and depositing temperature is 400 DEG C, and spout is 8cm to hot platform distance;
D, resilient coating preparation
It is that the concentration of 0.2 mol/L, thiocarbamide is cadmium acetate-thiocarbamide precursor aqueous solution of 0.5 mol/L that cadmium acetate and thiocarbamide are added to the concentration that is mixed with cadmium acetate in distilled water, cadmium acetate-thiocarbamide precursor aqueous solution becomes gas through ultrasonic atomizatio, taking argon gas as carrier gas, preparing thickness on compacted zone surface is the cadmium sulphide membrane resilient coating of 100nm, when pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, and depositing temperature is 400 DEG C, and spout is 8cm to hot platform distance; The XRD of cadmium sulfide resilient coating schemes as shown in Figure 2;
E, absorbed layer preparation
Dichloride copper, zinc dichloride, butter of tin and thiocarbamide are added in solvent, being mixed with dichloride copper concentration is that 0.2 mol/L, zinc dichloride concentration are that 0.2 mol/L, butter of tin concentration are the absorbed layer precursor aqueous solution that 0.2 mol/L, thiourea concentration are 0.5mol/L, described solvent is DMF (DMF)) and monoethanolamine according to the mixed solution of volume ratio 1:1 preparation; Absorbed layer precursor aqueous solution is become to gas through ultrasonic atomizatio, and taking argon gas as carrier gas, becoming thickness at buffer-layer surface pyrolytic deposition is 5 μ m copper-zinc-tin-sulfur films, when pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, and depositing temperature is 400 DEG C, and spout is 8cm to hot platform distance; Then carry out annealing in process, when annealing in process, pass into high pure nitrogen for protection gas, annealing temperature is 400 DEG C, and the heating-up time is 5min, and annealing time is 30min, and temperature fall time is 15min, obtains copper-zinc-tin-sulfur absorbed layer; The XRD of copper-zinc-tin-sulfur absorbed layer schemes as shown in Figure 3, and as shown in Figure 4, as shown in Figure 5, copper-zinc-tin-sulfur absorbed layer is evenly distributed the scanning electron microscope (SEM) photograph of copper-zinc-tin-sulfur absorbed layer the Raman spectrogram of copper-zinc-tin-sulfur absorbed layer as seen from Figure 5;
F, top electrode preparation
Adopt vacuum thermal evaporation mode; the gold that is 99.9% by purity (Au) is at absorbed layer surface gold evaporation; then carry out annealing in process; obtain the top electrode that thickness is 100 nm, when annealing in process, pass into high pure nitrogen for protection gas; annealing temperature is 400 DEG C; heating-up time is 5min, and annealing time is 30min, and temperature fall time is 15min.
Embodiment 4
A, provide substrate
Select sheet glass as substrate, substrate is put in beaker, pour acetone into, ultrasonic cleaning 6min, then use alcohol ultrasonic cleaning 6min, and then use saturated NaOH alcohol solution dipping ultrasonic cleaning 22min, finally use deionized water rinsing, natural drying;
B, conductive layer preparation
It is that the concentration of 0.8mol/L, butter of tin is trichloride antimony-butter of tin precursor aqueous solution of 1.5 mol/L that trichloride antimony and butter of tin are added to the concentration of preparing ammonium fluoride in methyl alcohol, trichloride antimony-butter of tin precursor aqueous solution becomes gas through ultrasonic atomizatio, becoming thickness at substrate surface pyrolytic deposition is that the antimony-doped stannic oxide film of 1 μ m is as conductive layer, when pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, depositing temperature is 400 DEG C, and spout is 8cm to hot platform distance; The XRD of antimony-doped stannic oxide film conductive layer schemes as shown in Figure 6; The square resistance that obtains antimony-doped stannic oxide with four probe method test is 10 Ω/;
C, compacted zone preparation
Isopropyl alcohol zinc is mixed and is mixed with isopropyl alcohol zinc precursor solution according to mol ratio 1:2 with ethanolic solution, isopropyl alcohol zinc precursor solution becomes gas through ultrasonic atomizatio, taking compressed air as carrier gas, becoming thickness at conductive layer surface pyrolytic deposition is that the zinc-oxide film of 100nm is as compacted zone, when pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, and depositing temperature is 400 DEG C, and spout is 8cm to hot platform distance;
D, resilient coating preparation
Zinc acetate, ammonium chloride, thiocarbamide and ammoniacal liquor are added in the beaker that distilled water is housed, and being mixed with zinc acetate concentration is that 0.05 mol/L, ammonium chloride concentration are that 0.2 mol/L, thiourea concentration are that 0.2 mol/L, ammonia concn are the mixed solution of 0.2 mol/L; The substrate for preparing conductive layer and compacted zone is put into beaker, at-10 DEG C, react 10min, form on compacted zone surface the zinc sulfide film that thickness is 100nm; The XRD of zinc sulphide resilient coating schemes as shown in Figure 7;
E, absorbed layer preparation
Stannous chloride, zinc iodide, butter of tin and thiocarbamide are added in ethanol, being mixed with stannous chloride concentration is that 0.5mol/L, zinc iodide concentration are that 0.5 mol/L, butter of tin concentration are the absorbed layer precursor aqueous solution that 0.5mol/L, thiourea concentration are 2mol/L, absorbed layer precursor aqueous solution is become to gas through ultrasonic atomizatio, taking argon gas as carrier gas, becoming thickness at buffer-layer surface pyrolytic deposition is 5 μ m copper-zinc-tin-sulfur films, when pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, depositing temperature is 400 DEG C, and spout is 8cm to hot platform distance; Then carry out annealing in process, when annealing in process, pass into high pure nitrogen for protection gas, annealing temperature is 400 DEG C, and the heating-up time is 5min, and annealing time is 30min, and temperature fall time is 15min, obtains copper-zinc-tin-sulfur absorbed layer;
F, top electrode preparation
The silver (Ag) that employing vacuum thermal evaporation mode is 99.9% by purity, at absorbed layer surface evaporation silver, obtains the top electrode that thickness is 100 nm, and electric current when vacuum thermal evaporation is 80A;
Embodiment 5
A, provide substrate
Select sheet glass as substrate, substrate is put in beaker, pour acetone into, ultrasonic cleaning 6min, then use alcohol ultrasonic cleaning 6min, and then use saturated NaOH alcohol solution dipping ultrasonic cleaning 22min, finally use deionized water rinsing, natural drying;
B, conductive layer preparation
It is that the concentration of 0.6mol/L, butter of tin is trichloride antimony-butter of tin precursor aqueous solution of 1 mol/L that trichloride antimony and butter of tin are added to the water to the concentration of preparing ammonium fluoride, trichloride antimony-butter of tin precursor aqueous solution becomes gas through ultrasonic atomizatio, becoming thickness at substrate surface pyrolytic deposition is that the antimony-doped stannic oxide film of 1 μ m is as conductive layer, when pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, depositing temperature is 400 DEG C, and spout is 8cm to hot platform distance;
C, compacted zone preparation
Isopropyl alcohol zinc is mixed and is mixed with isopropyl alcohol zinc precursor solution according to mol ratio 1:2 with ethanolic solution, isopropyl alcohol zinc precursor solution becomes gas through ultrasonic atomizatio, taking compressed air as carrier gas, becoming thickness at conductive layer surface pyrolytic deposition is that the zinc-oxide film of 100nm is as compacted zone, when pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, and depositing temperature is 400 DEG C, and spout is 8cm to hot platform distance;
D, resilient coating preparation
Zinc acetate, ammonium chloride, thiocarbamide and ammoniacal liquor are added in the beaker that distilled water is housed, and being mixed with zinc acetate concentration is that 0.05 mol/L, ammonium chloride concentration are that 0.2 mol/L, thiourea concentration are that 1 mol/L, ammonia concn are the mixed solution of 1 mol/L; The substrate for preparing conductive layer and compacted zone is put into beaker, at 90 DEG C, react 100min, form on compacted zone surface the zinc sulfide film that thickness is 100nm;
E, absorbed layer preparation
Dichloride copper, zinc dichloride, butter of tin and thiocarbamide are added in solvent, being mixed with dichloride copper concentration is that 1 mol/L, zinc dichloride concentration are that 1 mol/L, butter of tin concentration are that 1 mol/L, thiourea concentration are the absorbed layer precursor aqueous solution of 5 mol/L, described solvent is DMF (DMF)) and monoethanolamine according to the mixed solution of volume ratio 1:5 preparation; Absorbed layer precursor aqueous solution is become to gas through ultrasonic atomizatio, and taking argon gas as carrier gas, becoming thickness at buffer-layer surface pyrolytic deposition is 5 μ m copper-zinc-tin-sulfur films, when pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, and depositing temperature is 400 DEG C, and spout is 8cm to hot platform distance; Then carry out annealing in process, when annealing in process, pass into high pure nitrogen for protection gas, annealing temperature is 400 DEG C, and the heating-up time is 5min, and annealing time is 30min, and temperature fall time is 15min, obtains copper-zinc-tin-sulfur absorbed layer;
F, top electrode preparation
Adopt the molybdenum bisuphide (MoS that vacuum thermal evaporation mode is 99.9% by purity
2) at absorbed layer surface evaporation molybdenum bisuphide, obtaining the top electrode that thickness is 100 nm, electric current when vacuum thermal evaporation is 120A;
Embodiment 6
A, provide substrate
Select sheet glass as substrate, substrate is put in beaker, pour acetone into, ultrasonic cleaning 6min, then use alcohol ultrasonic cleaning 6min, and then use saturated NaOH alcohol solution dipping ultrasonic cleaning 22min, finally use deionized water rinsing, natural drying;
B, conductive layer preparation
It is trichloride antimony-butter of tin precursor aqueous solution that the concentration of 4mol/L, butter of tin is 2mol/L that trichloride antimony and butter of tin are added to the water to the concentration of preparing ammonium fluoride, trichloride antimony-butter of tin precursor aqueous solution becomes gas through ultrasonic atomizatio, becoming thickness at substrate surface pyrolytic deposition is that the antimony-doped stannic oxide film of 1 μ m is as conductive layer, when pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, depositing temperature is 400 DEG C, and spout is 8cm to hot platform distance;
C, compacted zone preparation
Isopropyl alcohol zinc is mixed and is mixed with isopropyl alcohol zinc precursor solution according to mol ratio 1:2 with ethanolic solution, isopropyl alcohol zinc precursor solution becomes gas through ultrasonic atomizatio, taking compressed air as carrier gas, becoming thickness at conductive layer surface pyrolytic deposition is that the zinc-oxide film of 100nm is as compacted zone, when pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, and depositing temperature is 400 DEG C, and spout is 8cm to hot platform distance;
D, resilient coating preparation
Zinc acetate, ammonium chloride, thiocarbamide and ammoniacal liquor are added in the beaker that distilled water is housed, and being mixed with zinc acetate concentration is that 0.2mol/L, ammonium chloride concentration are that 0.5 mol/L, thiourea concentration are the mixed solution that 0.5mol/L, ammonia concn are 0.5mol/L; The substrate for preparing conductive layer and compacted zone is put into beaker, at 50 DEG C, react 50min, form on compacted zone surface the zinc sulfide film that thickness is 100nm;
E, absorbed layer preparation
Dichloride copper, zinc dichloride, butter of tin and thiocarbamide are added in solvent, being mixed with dichloride copper concentration is that 0.5mol/L, zinc dichloride concentration are that 0.5mol/L, butter of tin concentration are the absorbed layer precursor aqueous solution that 0.5mol/L, thiourea concentration are 2mol/L, described solvent is DMF (DMF)) and monoethanolamine according to the mixed solution of volume ratio 1:2 preparation; Absorbed layer precursor aqueous solution is become to gas through ultrasonic atomizatio, and taking argon gas as carrier gas, becoming thickness at buffer-layer surface pyrolytic deposition is 5 μ m copper-zinc-tin-sulfur films, when pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, and depositing temperature is 400 DEG C, and spout is 8cm to hot platform distance; Then carry out annealing in process, when annealing in process, pass into high pure nitrogen for protection gas, annealing temperature is 400 DEG C, and the heating-up time is 5min, and annealing time is 30min, and temperature fall time is 15min, obtains copper-zinc-tin-sulfur absorbed layer;
F, top electrode preparation
Adopting purity is 99.9% molybdenum (Mo) vacuum thermal evaporation mode at absorbed layer surface evaporation molybdenum, obtains the top electrode that thickness is 100 nm, and the electric current of vacuum thermal evaporation is 100A.
Embodiment 7
The preparation of step b conductive layer: add concentration 1 mol/L for preparing aluminium acetate in methyl alcohol, aluminium acetate-zinc acetate precursor aqueous solution aluminium acetate-zinc acetate precursor aqueous solution that acetic acid zinc concentration is 1mol/L to become gas through ultrasonic atomizatio aluminium acetate and zinc acetate, becoming thickness at substrate surface pyrolytic deposition is that the Al-Doped ZnO film of 1 μ m is as conductive layer, when pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, depositing temperature is 400 DEG C, and spout is 8cm to hot platform distance; The XRD of Al-Doped ZnO film schemes as shown in Figure 8; (step a, step c～step f) are with embodiment 3 for other step.
Claims (9)
1. an antivacuum preparation method for superstrate structure copper-zinc-tin-sulfur solar cell, is characterized in that: concrete steps are:
A, provide substrate
Select the sheet glass, transparent plastic sheet or the polyimide piece that clean up as substrate;
B, conductive layer preparation
Preparation conductive layer precursor aqueous solution carries out atomization pyrolytic deposition, described conductive layer precursor aqueous solution is ammonium fluoride-butter of tin precursor aqueous solution, trichloride antimony-butter of tin precursor aqueous solution or aluminium salt-zinc acetate precursor aqueous solution, conductive layer precursor aqueous solution becomes gas through ultrasonic atomizatio, and becoming thickness at substrate surface pyrolytic deposition is that fluorine-doped tin dioxide film, antimony-doped stannic oxide film or the Al-Doped ZnO film of 0.5 μ m～1.5 μ m is as conductive layer;
C, compacted zone preparation
Preparation compacted zone precursor aqueous solution carries out atomization pyrolytic deposition, described compacted zone precursor aqueous solution is isopropyl titanate precursor aqueous solution or isopropyl alcohol zinc precursor solution, compacted zone precursor aqueous solution becomes gas through ultrasonic atomizatio, taking compressed air, nitrogen or argon gas as carrier gas, becoming thickness at conductive layer surface pyrolytic deposition is that the titanium deoxid film of 20nm～200nm or zinc-oxide film are as compacted zone;
D, resilient coating preparation
Adopt atomization pyrolysis or chemical bath to prepare the resilient coating that thickness is 20nm～200nm on compacted zone surface, described resilient coating is cadmium sulphide membrane, zinc sulfide film, mix antimony indium sulfide thin film, hydrogen-oxygen indium sulfide thin film or zinc oxysulfide film;
E, absorbed layer preparation
Preparation absorbed layer precursor aqueous solution carries out atomization pyrolytic deposition, absorbed layer precursor aqueous solution is become to gas through ultrasonic atomizatio, and taking nitrogen or argon gas as carrier gas, becoming thickness at buffer-layer surface pyrolytic deposition is 1 μ m～10 μ m copper-zinc-tin-sulfur film, and carry out annealing in process, obtain copper-zinc-tin-sulfur absorbed layer;
When preparation absorbed layer precursor aqueous solution, by mantoquita, zinc salt, pink salt and thiocarbamide add in solvent, being mixed with mantoquita concentration is 0.2 mol/L～1 mol/L, zinc salt concentration is 0.2 mol/L～1 mol/L, pink salt concentration is 0.2 mol/L～1 mol/L, thiourea concentration is the mixed solution of 0.5mol/L～5 mol/L, described mantoquita is dichloride copper, stannous chloride or cuprous iodide, described zinc salt is zinc dichloride or zinc iodide, described pink salt is stannous chloride, butter of tin or tin tetraiodide, described solvent is N, dinethylformamide and monoethanolamine are according to the mixed solution of volume ratio 1:1～1:5 preparation, dimethyl sulfoxide (DMSO), methyl alcohol, ethanol, one in water,
When annealing in process, passing into hydrogen volume percentage composition and be 0.1%～4% nitrogen and hydrogen mixture, hydrogen sulfide volumn concentration is that 0.1%～15% hydrogen sulfide diluent gas, high pure nitrogen or argon gas are protection gas, annealing temperature is 300 DEG C～600 DEG C, heating-up time is 0.5min～10 min, annealing time is 5 min～60 min, and temperature fall time is 1 min～15 min or 30 min～60 min;
F, top electrode preparation
Adopt screen printing mode starch and carry out annealing in process at absorbed layer surface printing black lead wash or silver, or adopt vacuum thermal evaporation mode or electron-beam evaporation mode at absorbed layer surface evaporation silver, gold, molybdenum, molybdenum bisuphide, prepare the top electrode that thickness is 50nm～150nm, electric current when vacuum thermal evaporation or electron beam evaporation is 80 A～120A; When annealing in process; passing into hydrogen volume percentage composition and be 0.1%～4% nitrogen and hydrogen mixture, hydrogen sulfide volumn concentration is that 0.1%～15% hydrogen sulfide diluent gas, high pure nitrogen or argon gas are protection gas; annealing temperature is 300 DEG C～600 DEG C; heating-up time is 0.5min～10 min; annealing time is 5 min～60 min, and temperature fall time is 1 min～15 min or 30 min～60 min.
2. the antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell according to claim 1, is characterized in that:
Prepare conductive layer, compacted zone, resilient coating, absorbed layer, while carrying out atomization pyrolytic deposition, gas flow remains on 5mL/min～30mL/min, and sedimentation time is 1min～30min, depositing temperature is 300 DEG C～600 DEG C, and spout is 0.5cm～15cm to hot platform distance.
3. the antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell according to claim 1, is characterized in that:
In ammonium fluoride-butter of tin precursor aqueous solution of step b, the concentration of ammonium fluoride is that the concentration of 1mol/L～2mol/L, butter of tin is 0.6 mol/L～1 mol/L, and solvent is at least one in distilled water, methyl alcohol, ethanol; In trichloride antimony-butter of tin precursor aqueous solution, concentration 0.6 mol/L～1 mol/L of trichloride antimony, the concentration of butter of tin are 1mol/L～2mol/L, and solvent is methyl alcohol or ethanol; In aluminium salt-zinc acetate precursor aqueous solution, concentration 0.6 mol/L～1 mol/L, the acetic acid zinc concentration of aluminium salt is 1mol/L～2mol/L, and solvent is methyl alcohol or ethanol, and described aluminium salt is silver iodide or aluminium acetate.
4. the antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell according to claim 1, is characterized in that:
When step c preparation isopropyl titanate precursor aqueous solution, isopropyl titanate is mixed according to mol ratio 1:1～1:5 with ethanolic solution; When preparation isopropyl alcohol zinc precursor solution, isopropyl alcohol zinc is mixed according to mol ratio 1:1～1:5 with ethanolic solution.
5. the antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell according to claim 1, is characterized in that:
When resilient coating is prepared in atomization pyrolysis, first prepare resilient coating precursor aqueous solution, resilient coating precursor aqueous solution becomes gas through ultrasonic atomizatio, be deposited as resilient coating in compacted zone surface pyrolysis, cadmium sulphide membrane resilient coating, zinc sulfide film resilient coating, when mixing antimony indium sulfide thin film resilient coating and preparing, pass into nitrogen or argon gas as carrier gas; Time prepared by hydrogen-oxygen indium sulfide thin film resilient coating, zinc oxysulfide film film resilient coating, pass into compressed air as carrier gas.
6. the antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell according to claim 5, is characterized in that:
While preparing cadmium sulphide membrane, the concentration of first preparing cadmium acetate is that the concentration of 0.05 mol/L～0.5 mol/L, thiocarbamide is the resilient coating precursor aqueous solution of 0.2 mol/L～1 mol/L, and wherein solvent is distilled water, methyl alcohol or ethanol; While preparing zinc sulfide film, the concentration of first preparing acetic acid zinc concentration and be 0.05 mol/L～0.5 mol/L, thiocarbamide is the resilient coating precursor aqueous solution of 0.2 mol/L～1 mol/L, and wherein solvent is distilled water, methyl alcohol or ethanol; When antimony indium sulfide thin film is mixed in preparation, first the concentration of preparing indium trichloride is that the concentration of 0.1mol/L～0.6mol/L, trichloride antimony is that the concentration of 0.05 mol/L～0.5 mol/L, thiocarbamide is the resilient coating precursor aqueous solution of 0.2 mol/L～1 mol/L, and wherein solvent is methyl alcohol or ethanol; While preparing hydrogen-oxygen indium sulfide thin film, first preparing indium trichloride concentration is that 0.1mol/L～0.6mol/L, thiourea concentration are the resilient coating precursor aqueous solution of 0.2 mol/L～1 mol/L, and wherein solvent is distilled water, methyl alcohol or ethanol; While preparing zinc oxysulfide film, first preparing zinc acetate concentration is that 0.1mol/L～0.6mol/L, thiourea concentration are the resilient coating precursor aqueous solution of 0.2 mol/L～1 mol/L, and wherein solvent is distilled water, methyl alcohol or ethanol.
7. the antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell according to claim 1, it is characterized in that: adopt chemical bath to prepare resilient coating, time prepared by cadmium sulphide membrane, cadmium acetate, ammonium chloride, thiocarbamide and ammoniacal liquor are equipped with in the beaker of distilled water, being mixed with cadmium acetate concentration is that 0.05 mol/L～0.5 mol/L, ammonium chloride concentration are that 0.2 mol/L～1 mol/L, thiourea concentration are that 0.2 mol/L～1 mol/L, ammonia concn are the mixed solution of 0.2 mol/L～1 mol/L; The substrate for preparing conductive layer and compacted zone is put into beaker, at-10 DEG C～90 DEG C, react 10min～100min, form cadmium sulphide membrane on compacted zone surface;
Time prepared by zinc sulfide film, zinc acetate, ammonium chloride, thiocarbamide and ammoniacal liquor are added in the beaker that distilled water is housed, and being mixed with zinc acetate concentration is that 0.05 mol/L～0.5 mol/L, ammonium chloride concentration are that 0.2 mol/L～1 mol/L, thiourea concentration are that 0.2 mol/L～1 mol/L, ammonia concn are the mixed solution of 0.2 mol/L～1 mol/L; The substrate for preparing conductive layer and compacted zone is put into beaker, at-10 DEG C～90 DEG C, react 10min～100min, form zinc sulfide film on compacted zone surface;
When mixing antimony indium sulfide thin film and preparing, indium trichloride, trichloride antimony, thiocarbamide and ammoniacal liquor are added in the beaker that distilled water is housed, and being mixed with indium trichloride concentration is that 0.1 mol/L～0.6 mol/L, trichloride antimony concentration are that 0.05 mol/L～0.5 mol/L, thiourea concentration are that 0.2mol/L～1 mol/L and ammonia concn are the mixed solution of 0.1mol/L～0.5 mol/L; The substrate for preparing conductive layer and compacted zone is put into beaker, at-10 DEG C～90 DEG C, react 10min～100min, form and mix antimony indium sulfide thin film on compacted zone surface;
Time prepared by hydrogen-oxygen indium sulfide thin film, indium trichloride, thiocarbamide and ammoniacal liquor are added in the beaker that distilled water is housed, and being mixed with indium trichloride concentration is that 0.1 mol/L～0.6 mol/L, thiourea concentration are the mixed solution of 0.2mol/L～1 mol/L, ammonia concn 0.2-1 mole every liter; The substrate for preparing conductive layer and compacted zone is put into beaker, at-10 DEG C～90 DEG C, react 10min～100min, form hydrogen-oxygen indium sulfide thin film on compacted zone surface;
When zinc oxysulfide film preparation, zinc acetate, thiocarbamide and ammoniacal liquor are added in the beaker that distilled water is housed, and being mixed with zinc acetate concentration is that 0.05mol/L～0.6 mol/L, thiourea concentration are that 0.2 mol/L～1 mol/L, ammonia concn are 0.2 mol/L～1 mol/L; The substrate for preparing conductive layer and compacted zone is put into beaker, at-10 DEG C～90 DEG C, react 10min～100min, form zinc oxysulfide film on compacted zone surface.
8. the antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell according to claim 1, it is characterized in that: described black lead wash is that electrically conductive graphite and cellulose, terpinol are mixed according to mass ratio 10:3～10:2,10:2～10:1 respectively, the purity of Vacuum sublimation or electron beam evaporation material silver, gold, molybdenum or molybdenum bisuphide used is 99.9%～99.99%.
9. the antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell according to claim 1, it is characterized in that: while cleaning substrate, substrate is put in beaker, pour acetone into, ultrasonic cleaning 5min～8min, then use alcohol ultrasonic cleaning 5min～8min, then use saturated NaOH alcohol solution dipping ultrasonic cleaning 20min～25min, finally use deionized water rinsing, natural drying.
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| CN109148625A (en) * | 2018-05-17 | 2019-01-04 | 中国科学院物理研究所 | Copper zinc tin sulfur selenium thin-film solar cells and preparation method thereof |
| CN109560159A (en) * | 2018-11-02 | 2019-04-02 | 云南师范大学 | A kind of copper-zinc-tin-sulfur film solar cell |
| CN111755323A (en) * | 2020-07-07 | 2020-10-09 | 内蒙古大学 | Preparation method of copper-zinc-tin-sulfur solar cell absorption layer film |
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| CN116397200A (en) * | 2023-06-08 | 2023-07-07 | 合肥工业大学 | Single-source thermal evaporation preparation method of molybdenum-copper laminated substrate of copper-antimony-selenium light absorption layer |
| CN116397200B (en) * | 2023-06-08 | 2023-08-08 | 合肥工业大学 | Single-source thermal evaporation preparation method of molybdenum-copper laminated substrate of copper-antimony-selenium light absorption layer |
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