CN111554760A - 铜锌锡硫薄膜太阳能电池的前驱体溶液及其制备方法与应用 - Google Patents
铜锌锡硫薄膜太阳能电池的前驱体溶液及其制备方法与应用 Download PDFInfo
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- CN111554760A CN111554760A CN202010410931.4A CN202010410931A CN111554760A CN 111554760 A CN111554760 A CN 111554760A CN 202010410931 A CN202010410931 A CN 202010410931A CN 111554760 A CN111554760 A CN 111554760A
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- Prior art keywords
- copper
- tin
- zinc
- solution
- complex
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- 239000002243 precursor Substances 0.000 title claims abstract description 95
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000010409 thin film Substances 0.000 title abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 88
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 72
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 56
- 239000011135 tin Substances 0.000 claims description 53
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 43
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 34
- 229910052718 tin Inorganic materials 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 29
- 150000004699 copper complex Chemical group 0.000 claims description 28
- 239000010949 copper Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 150000001879 copper Chemical class 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- -1 copper halide salt Chemical class 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- 150000003585 thioureas Chemical class 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- MNOILHPDHOHILI-UHFFFAOYSA-N Tetramethylthiourea Chemical compound CN(C)C(=S)N(C)C MNOILHPDHOHILI-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000002207 thermal evaporation Methods 0.000 claims description 3
- 150000003752 zinc compounds Chemical class 0.000 claims description 3
- ZQGWBPQBZHMUFG-UHFFFAOYSA-N 1,1-dimethylthiourea Chemical group CN(C)C(N)=S ZQGWBPQBZHMUFG-UHFFFAOYSA-N 0.000 claims description 2
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical group S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000009987 spinning Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 81
- 239000010408 film Substances 0.000 description 49
- 239000010410 layer Substances 0.000 description 26
- 238000010521 absorption reaction Methods 0.000 description 14
- 239000012535 impurity Substances 0.000 description 10
- 238000004528 spin coating Methods 0.000 description 10
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 description 9
- 239000011669 selenium Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 238000001237 Raman spectrum Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 5
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000002245 particle 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
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 229940045803 cuprous chloride Drugs 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910017987 Cu—Zn—Sn—S—Se Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000224 chemical solution deposition Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- 239000012691 Cu precursor Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- PCRGAMCZHDYVOL-UHFFFAOYSA-N copper selanylidenetin zinc Chemical compound [Cu].[Zn].[Sn]=[Se] PCRGAMCZHDYVOL-UHFFFAOYSA-N 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3628—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a sulfide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3607—Coatings of the type glass/inorganic compound/metal
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3631—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a selenide or telluride
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- C—CHEMISTRY; METALLURGY
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- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
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- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3668—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties
- C03C17/3671—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties specially adapted for use as electrodes
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- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3668—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties
- C03C17/3678—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties specially adapted for use in solar cells
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- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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Abstract
本发明公开了一种铜锌锡硫薄膜太阳能电池的前驱体溶液及其制备方法与应用，本发明公开了两类可配制优质前驱体溶液的简单金属配合物，通过使用金属配合物作为前驱体化合物，配制的前驱体溶液稳定性好，可用来制备结晶质量高，薄膜形貌好，无杂质相的铜锌锡硫薄膜吸光材料，以此制备的铜锌锡硫薄膜太阳能电池光电转化效率高。金属配合物的使用，简化了前驱体溶液配制流程，提升了前驱体溶液质量，提高了光伏器件能量转换效率，具有极大的工业应用潜力。
Description
技术领域
本发明属于新能源光伏发电技术领域，具体涉及一种铜锌锡硫薄膜太阳能电池的前驱体溶液及其制备方法与应用，具体是用于光伏器件的制备与应用。
背景技术
能源短缺问题是制约人类未来发展的关键问题，可再生能源的开发和利用是解决该问题的优质方案，光伏发电技术是可再生能源中最具前景的发展方向。过去几十年，以单晶硅和多晶硅为代表的硅基太阳能电池和以碲化镉(CdTe)和铜铟镓硒(CIGS)为代表的多元化合物半导体薄膜太阳能电池在能量效率方面取得了长足的进步，已成功实现商业化生产。目前单晶硅电池实验室获得的最高光电转换效率达到26.7％，CIGS和CdTe薄膜太阳能电池在实验室获得的最高光电转换效率也分别达到23.35％和22.1％。但由于硅半导体的低吸光系数，低缺陷耐受性差，Cd元素潜在的环境毒害性，In、Ga、Te元素的地壳资源稀缺性等因素，导致这些光伏器件的制作成本居高不下，难以与传统能源进行市场竞争。铜锌锡硫(CZTS)材料与铜铟镓硒(CIGS)材料具有相似的晶体结构和光学带隙，可见光范围吸光系数＞104/cm，带隙在1.0～1.5eV范围可调，与太阳能电池材料的最佳光学带隙区间相匹配，具有较高的理论转化效率(32.3％)，同时它的组成元素地球储藏极其丰富，价格低廉，安全无毒，是有望取代铜铟镓硒的新型低成本光伏材料。铜锌锡硫膜层材料的制备方法主要分为真空法和溶液法两大类。传统的真空制备法以高真空环境为基础，其材料制备过程能耗高，材料利用率较低。溶液法以化学溶液为基础，无需真空环境，其能耗较低，可用于大面积成膜，还具备提高材料利用率和低温加工等优点。
分子前驱体溶液法因工艺简单，制备的电池转换效率较高，在近些年颇受研究者关注。2013年IBM公司报道了基于肼溶剂的前驱体溶液法制备得到能量转化效率为12.6％的铜锌锡硫硒太阳能电池。但是由于肼的易爆性和高毒害性限制了该方法的应用。美国华盛顿大学Hillhouse课题组提出了低危害性的基于二甲基亚砜溶剂的前驱体溶液方案，但由于溶液中阳离子氧化还原反应的存在，限制了所制备的太阳能电池效率的提高。鉴于此，通过对溶液化学的研究，本发明公开一种简单、新颖、稳定、绿色环保的前驱体溶液配制方案，该方案被成功应用于铜锌锡硫膜硒膜层材料和铜锌锡硫硒太阳能电池的制备，制备得到的铜锌锡硫硒材料结晶质量高，形貌好，无杂相，其光伏器件能量转化效率超过10％，表明该发明显著的先进性。
发明内容
发明目的：为了克服现有技术中存在的不足，本发明提供一种铜锌锡硫(CZTS)薄膜太阳能电池的前驱体溶液及其电池制备方法与应用，以制备高效铜锌锡硫太阳能电池为目的，通过使用铜盐与硫脲形成的铜配合物作为铜的前驱体，锡盐与二甲基亚砜或N,N-二甲基甲酰胺生成的锡配合物作为锡的前驱体，简单锌盐作为锌的前驱体，配制稳定的前驱体溶液，制备高质量、无杂质相的铜锌锡硫吸光材料，制备高光电转化效率的铜锌锡硫薄膜太阳能电池。
技术方案：为实现上述目的，本发明采用的技术方案为：
一种铜锌锡硫太阳能电池的前驱体溶液，以二甲基亚砜DMSO或N,N-二甲基甲酰胺DMF为溶剂，前驱体化合物为溶质配制；所述前驱体化合物由金属配合物、金属化合物和硫脲组成，其中，所述金属配合物为铜盐与硫脲或硫脲衍生物形成的铜配合物、锡盐与DMF或DMSO形成的锡配合物，金属化合物为二价锌盐；将以上前驱体化合物溶解在DMSO或DMF溶剂中得到稳定、澄清透明的前驱体溶液。
进一步的，所述铜配合物为铜盐与硫脲或硫脲的衍生物形成的配合物，包括：卤素铜盐与硫脲形成的配合物Cu(Tu)3X，其中X为包括F、Cl、Br、I在内的卤族元素，所形成的铜配合物包括：Cu(Tu)3Cl，[Cu2(Tu)6]Cl2·2H2O,Cu(Tu)3Br；还包括卤素铜盐与硫脲衍生物形成的配合物：Cu(DMTu)3Br，Cu(TMTu)3Cl，[Cu(ETu)2Br]2，其中DMTu为N,N-二甲基硫脲，TMTU为四甲基硫脲，ETu为乙撑硫脲；还包括硝酸铜盐与硫脲形成的配合物Cu4(Tu)10(NO3)·Tu·3H2O。
进一步的，所述锡配合物选自Sn(X)yCl4，Sn(X)yF4,Sn(X)yBr4,Sn(X)yI4,Sn(X)y(CH3COO)4中的一种或多种，X选自DMSO、DMF、乙醇、N-甲基吡咯烷酮中的一种，y为大于零的自然数。
进一步的，所述锌盐为二价锌的化合物，包括但不限于卤素锌盐、乙酸锌、硝酸锌、硫酸锌。
进一步的，所述前驱体溶液中，硫脲物质的量：铜元素的物质的量为(0～1)：1。
进一步的，所述前驱体化合物中：
铜元素的物质的量：锡元素的物质的量为(1.5～2.5)：1；
锌元素物质的量：锡元素的物质的量为(0.9～1.5)：1；
硫元素物质的量：铜、锡与锌元素物质的量之和为(1.0～6.0)：1。
进一步的，所述前驱体溶液中：
铜元素在溶液中浓度为0.05mol/L～5mol/L；
锡元素在溶液中浓度为0.05mol/L～5mol/L；
锌元素在溶液中浓度为0.05mol/L～5mol/L；
硫元素在溶液中浓度为0.15mol/L～5mol/L。
本发明还公开了上述的铜锌锡硫太阳能电池的前驱体溶液的制备方法，制备前驱体溶液的具体方法为分步制备法：以DMSO或DMF为溶剂，将铜配合物和硫脲溶解在溶剂中制备溶液一，其中硫脲物质的量：铜元素的物质的量不大于1；将锡配合物和锌盐溶解在溶剂中制备溶液二；将溶液一和溶液二混合得到澄清透明的前驱体溶液。
进一步的，铜配合物、锡配合物的制备方法为：
合成铜配合物：将硫脲溶解在去离子水中，待硫脲完全溶解后将铜盐加入溶液中，所加入的硫脲与铜盐的物质的量之比为3:1，反应过程溶液温度为70摄氏度；溶解后，将溶液过滤，静置，缓慢冷却，目标产物铜配合物晶体从溶液中析出，取出上述晶体产物并烘干；
合成锡配合物：取四价锡盐于圆底烧瓶中，密封瓶口，取有机化合物溶剂DMF或DMSO注入瓶中，其中溶剂中有机化合物与锡盐物质的量之比为2～20；锡盐与DMF或DMSO溶剂反应生成大量白色沉淀，用乙醇将沉淀清洗干净，烘干即得相应目标产物锡配合物。
上述的一种高效铜锌锡硫太阳能电池的前驱体溶液制备方法及将其应用于铜锌锡硫太阳能电池的制备，包括以下步骤：
(1)合成铜配合物：将一定量硫脲溶解在去离子水中，待硫脲完全溶解后将铜盐加入溶液中，所加入的硫脲与铜盐的物质的量之比为3:1，反应过程溶液温度为70摄氏度。两种物质基本溶解后，将溶液过滤，静置，缓慢冷却，目标产物铜配合物晶体从溶液中析出。过滤得到上述晶体产物，烘干。
(2)合成锡配合物：取一定量四价锡盐于圆底烧瓶中并密封瓶口，取过量有机化合物DMF或DMSO注入瓶中，反应生成大量白色沉淀，过滤，使用乙醇将沉淀清洗干净，烘干即得目标产物锡配合物。
(3)制备前驱体溶液：以DMSO或DMF为溶剂，将铜配合物、锡配合物、二价锌化合物和硫脲溶解在溶剂中，得到澄清透明的前驱体溶液；
(4)将步骤1中获得的前驱体溶液旋涂在钼玻璃上，加热退火生成铜锌锡硫前驱体薄膜；
(5)将步骤2中生成的铜锌锡硫前驱体薄膜在Se的气氛中加热反应，以Se原子部分或者全部取代S原子生成铜锌锡硫薄膜材料；
(6)将硒化反应后的铜锌锡硫Se膜取出，用超纯水浸泡后置于含有氨水、硫酸镉和硫脲溶液的水夹套烧杯中，在加热情况下进行反应，在铜锌锡硫Se膜表面沉积一层CdS；(7)通过磁控溅射技术在步骤4的样品表面依次溅射50nm本征氧化锌(i-ZnO)以及250nm铟锡氧化物(ITO)作为窗口层；
(8)通过热蒸镀方法在步骤5获得的样品表面依次蒸镀50nm金属Ni和1μm Al的栅形电极。
进一步的，步骤4中旋涂与退火的反应条件为：旋涂转速为500～8000rpm，时间为10～600s，退火温度为200～500℃，加热时间为20～120s，重复旋涂退火3～15次。
进一步的，步骤5硒化反应的具体步骤如下：
(5-1)将铜锌锡硫薄膜与0.2～0.5g的硒粒置于石墨盒中，然后将石墨盒水平缓慢放入石英管中，石英管两端法兰连有气体管路，气体管路上连有压力表与气体阀门；
(5-2)用机械泵将石英管中的气体抽至3×10-2Torr以下，然后充入氩气至管中气压为常压；
(5-3)启动管式炉加热程序，目标温度为500℃～600℃，升温速率为0.2℃～10℃/s，在目标温度下退火5～30分钟。
(5-4)退火程序终止后，自然冷却至室温。
有益效果：本发明提供的一种铜锌锡硫薄膜太阳能电池的前驱体溶液制备方法，与现有技术相比，具有以下优势：
1.本发明公开了两类简单的金属配合物的合成方法并用来配制稳定的前驱体溶液，金属配合物的使用保持了金属前驱体的初始价态，避免了一价铜离子与四价锡离子发生氧化还原反应，得到的前驱体溶液质量优，稳定性好，重复性好。
2.本发明制备的前驱体溶液可制备高质量、无杂质相的铜锌锡硫吸光材料，制备的铜锌锡硫薄膜太阳能电池的光电转化效率高。
3.金属配合物的使用，简化了溶液配制流程，大幅缩短溶液配制时间，利于工业化生产。
附图说明
图1、实施例中氯化亚铜与硫脲的生成的铜配合物Cu(Tu)3Cl的实物图。
图2、实施例三中四氯化锡与N,N-二甲基甲酰胺生成的锡配合物Sn(DMF)2Cl4的实物图。
图3、实施例一中的DMSO前驱体溶液实物图。
图4、实施例三中的DMF前驱体溶液实物图。
图5、实施例一中前驱体薄膜的X射线衍射图谱。
图6、实施例三中的前驱体薄膜的X射线衍射图谱。
图7、实施例一中的吸收层薄膜的X射线衍射图谱。
图8、实施例三中的吸收层薄膜的X射线衍射图谱。
图9、实施例一中的前驱体薄膜的拉曼光谱。
图10、实施例三中的前驱体薄膜的拉曼光谱。
图11、实施例一中的吸收层薄膜的拉曼光谱。
图12、实施例三中的吸收层薄膜的拉曼光谱。
图13、实施例一中的吸收层薄膜的扫描电镜图(膜层横截面)。
图14、实施例三中的吸收层薄膜的扫描电镜图(膜层横截面)。
图15、实施例一中的吸收层薄膜的扫描电镜图(膜层表面)。
图16、实施例三中的吸收层薄膜的扫描电镜图(膜层表面)。
图17、实施例一中的铜锌锡硫硒太阳能电池器件在AM1.5G标准太阳光强下的电压-电流特性曲线。
图18、实施例三中铜锌锡硫硒太阳能电池器件在AM1.5G标准太阳光强下的电压-电流特性曲线。
具体实施方式
本发明公开了一种高效铜锌锡硫太阳能电池的前驱体溶液的制备方法及其光伏器件的制备与应用。本发明公开了两类配制稳定性能优异的前驱体溶液的简单金属配合物，通过使用金属配合物作为前驱体化合物配制的前驱体溶液稳定性和重复性好，可用来制备结晶质量高，薄膜形貌好，无杂质相的铜锌锡硫薄膜吸光材料，以此制备的铜锌锡硫薄膜太阳能电池光电转化效率高。金属配合物的使用，简化了前驱体溶液配制流程，提升了前驱体溶液质量，提高了光伏器件能量转换效率，具有极大的工业应用潜力。
下面对本发明的实施例作详细说明，本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实例。
根据下述实施例，可以更好的理解本发明。然而，本领域的技术人员容易理解，实施例所描述的具体的物料配比、工艺条件及其结果仅用于说明本发明，而不应当也不会限制权利要求书中所详细描述的本发明。
实施示例一：
步骤一：铜配合物的制备。
称取45.67g(0.6mol)硫脲溶解于100ml去离子水中，加热搅拌保持溶液温度为70℃，待硫脲完全溶解，称取19.8g(0.2mol)氯化亚铜加入其中，反应30分钟后，大部分氯化亚铜溶解，将溶液热过滤，将滤液静置，自然冷却。一段时间后滤液中析出无色透明晶体即为目标产物铜配合物Cu(Tu)3Cl，过滤，烘干。
步骤二：锡配合物的制备。
称取12.53克四氯化锡至圆底烧瓶中，将瓶口密封，取50ml DMSO通过注射器注射至瓶中，两种物质接触后反应剧烈，生成大量白色沉淀。反应完成后。反应完成后，过滤反应液得白色沉淀，并用乙醇洗涤多次，烘干，得目标产物Sn(DMSO)4Cl4。
步骤三：前驱体溶液的制备。
量取8mL DMSO至试剂瓶中，称取2.0g(6.12mmol)步骤一中制备的铜配合物，1.667g(4mmol)步骤二中制备的锡配合物Sn(DMSO)4Cl4，0.734g(4mmol)乙酸锌和0.2g硫脲加入试剂瓶中并在室温下搅拌至完全溶解。
步骤四：铜锌锡硫(铜锌锡硫)前驱体薄膜的制备。
将镀钼玻璃在丙酮和异丙醇中各超声清洗10分钟后吹干。在手套箱中对步骤三制备的前驱体溶液进行旋涂，旋涂参数为旋涂速度1500转/分，旋涂时间60s。旋涂结束后，将样品放到420℃的热台上退火2min。重复以上旋涂-加热过程7次，得到铜锌锡硫前驱体薄膜。
步骤五：铜锌锡硫硒(铜锌锡硫Se)薄膜的制备。
将步骤四制备的两片前驱体薄膜样品(2.45cm×2.45cm)置于石墨盒中，称量约0.35g的Se粒对称放入石墨盒中，将阀门关紧，抽真空使管内真空度达到3×10-2Torr后往管内通入氩气，重复以上操作3次以排净管内的空气，确保硒化反应在无水无氧环境下进行。启动管式炉加热程序，目标温度为550℃，升温速率为2℃/s，在550℃下退火20分钟。退火结束后样品自然冷却至室温。
步骤六：缓冲层CdS的制备。
硒化反应结束后，将石墨盒中的样品取出置于超纯水中浸泡6min，然后通过化学浴沉积法(CBD)沉积CdS缓冲层。第一步：设置水浴温度为65℃，用量筒分别量取22mL浓度为0.75mol/L的硫脲溶液，22mL浓度为0.015mol/L的硫酸镉溶液以及28mL的氨水。第二步：将量好的氨水和硫酸镉溶液倒入150mL超纯水中混合，将混合溶液倒入水夹套烧杯中，随后将超纯水浸泡的样品放入水夹套烧杯混合溶液中。将65℃的循环水充入水夹套烧杯的夹层加热并开始计时。第三步：一分钟后将预先量取好的硫脲溶液倒入反应溶液中。随着反应的进行，溶液由澄清变为淡黄，最终变为黄色的半透明悬浊液。第四步：溶液反应八分钟后取出样品，用超纯水冲洗样品表面除去表面吸附的CdS颗粒，然后用氮气枪将样品吹干。
步骤七：窗口层(ZnO/ITO)的制备。
通过磁控溅射法在上述样品上沉积本征氧化锌(i-ZnO)和氧化铟锡(ITO)做窗口层材料。磁控溅射仪溅射i-ZnO，溅射功率80W，纯氩气环境，气压为0.5Pa，膜层厚度50nm。溅射ITO的溅射功率为60W，纯氩气环境溅射气压为0.5Pa，膜层厚度200nm。
步骤八：电极(Ni/Al)的制备。
电池的阴极由金属Ni和Al组成，通过热蒸镀法制备。Ni和Al的厚度分别为50nm和500nm。
根据以上工艺制备的铜锌锡硫前驱体膜层和吸收膜层均无杂相，吸收层材料结晶度高，形貌好，制备得到的铜锌锡硫太阳能电池能量转化效率为10.9％。
实施示例二：
步骤一：铜配合物的制备。此步骤操作方法同实施示例一。
步骤二：称取12.53克四氯化锡至圆底烧瓶中，将瓶口密封，取50ml DMF通过注射器注射至瓶中，两种物质接触后反应剧烈，生成大量白色沉淀。反应完成后，过滤反应液得白色沉淀，并用乙醇洗涤多次，烘干，得目标产物Sn(DMF)2Cl4。
步骤三：前驱体溶液的制备。量取8mL DMSO至试剂瓶中，称取2.0g(6.12mmol)步骤一中制备的铜配合物，1.626g(4mmol)步骤二中制备的锡配合物Sn(DMF)2Cl4，0.734g(4mmol)乙酸锌和0.2g硫脲加入试剂瓶中并在室温下搅拌至完全溶解。
步骤四至步骤八：操作方法同实施示例一。
实施示例三：
步骤一：铜配合物的制备。此步骤操作方法同实施示例一。
步骤二：称取12.53克四氯化锡至圆底烧瓶中，将瓶口密封，取50ml DMSO通过注射器注射至瓶中，两种物质接触后反应剧烈，生成大量白色沉淀。反应完成后。反应完成后，过滤反应液得白色沉淀，并用乙醇洗涤多次,烘干，得目标产物Sn(DMSO)4Cl4。
步骤三：前驱体溶液的制备。量取8mL DMF至试剂瓶中，称取2.0g(6.12mmol)步骤一中制备的铜配合物Cu(Tu)3Cl，1.667g(4mmol)步骤二中制备的锡配合物Sn(DMSO)4Cl4，0.734g(4mmol)乙酸锌和0.2g硫脲加入试剂瓶中并在室温下搅拌至完全溶解。
步骤四至步骤八：操作方法同实施示例一。
实施示例四：
步骤一：铜配合物的制备。此步骤操作方法同实施示例一。
步骤二：称取12.53克四氯化锡至圆底烧瓶中，将瓶口密封，取50ml DMF通过注射器注射至瓶中，两种物质接触后反应剧烈，生成大量白色沉淀。反应完成后，过滤反应液得白色沉淀，并用乙醇洗涤多次，烘干，得目标产物锡配合物Sn(DMF)2Cl4。
步骤三：前驱体溶液的制备。量取8mL DMF至试剂瓶中，称取2.0g(6.12mmol)步骤一中制备的铜配合物，1.626g(4mmol)步骤二中制备的锡配合物Sn(DMF)2Cl4，0.734g(4mmol)乙酸锌和0.2g硫脲加入试剂瓶中并在室温下搅拌至完全溶解。
步骤四至步骤八：操作方法同实施示例一。
本发明实施例提供了四种全新的制备高效CZTS太阳能电池的前驱体溶液的制备方法，即通过使用金属配合物作为前驱体化合物配制的前驱体溶液，制备结晶质量高，薄膜形貌好，无杂质相的铜锌锡硫薄膜吸光材料，制备出高效率的铜锌锡硫太阳能电池。图1和图2分别为铜配合物和锡配合物的实物照片，经元素分析仪分析其化学组分分别为Cu(Tu)3Cl和Sn(DMF)2Cl。
图3、图4分别为基于以上两种金属配合物在DMSO和DMF溶剂中配制的前驱体溶液的实物照片，可以观察到两种溶液均澄清透明无沉淀和杂质产生，且稳定性好，表明其溶液质量高。
图5和图6为两种前驱体溶液经旋涂退火形成的前驱体薄膜的X射线衍射图谱，两个前驱体薄膜在衍射角2-Theta＝28.5，47.3，56.1度处均出现微弱的衍射峰，这些衍射峰分别对应铜锌锡硫相(CZTS)的(112)，(220)，(312)晶面(PDF#26-0575)，表明两组前驱体膜中均有CZTS相生成。图9和图10为前驱体薄膜的拉曼图谱，两个前驱体薄膜在拉曼位移为337cm-1处均出现明显的拉曼振动峰，对应于CZTS相。这两种表征手段都表明了前驱体薄膜中仅存在单一的铜锌锡硫物相，无其他杂质相，这有利于薄膜的后续生长和结晶。图7和图8为为两种前驱体薄膜硒化反应形成的铜锌锡硫硒吸收层薄膜的X射线衍射图谱，从图中可以看出两个铜锌锡硫硒吸收层薄膜在2-Theta＝27.1，45.0，53.4处均出现强衍射峰，这些衍射峰分别对应铜锌锡硒相(CZTSe)的(112)，(204)，(312)晶面，表明硒化后的吸收层薄膜均为CZTSe相，无其他杂相可观测到。
图11和图12为铜锌锡硫硒吸收层薄膜的拉曼图谱，从图中可以看出，两个前驱体薄膜在拉曼位移为172，193，231cm-1处均出现明显的拉曼振动峰，对应于铜锌锡硒相(CZTSe)，无其他杂质相的拉曼振动峰可观察到。这表明了制备的吸收层薄膜为高质量的铜锌锡硫硒薄膜。结合图13，14，15和16中观察到的的结晶度高，平整致密，无杂相的吸收层薄膜的扫描电镜照片，进一步表明实例制备的吸收层薄膜质量高。将两组吸光膜层制备成太阳能电池器件并对其进行光伏性能测试，它们的电压-电流特性曲线如图17，18所示，两个器件的光电转换效率均超过10％，达到国际先进水平。
综上，本发明的技术方案制备了稳定澄清透明的高质量前驱体溶液，并将其应用于铜锌锡硫硒薄膜材料和光伏器件制备，最终，得到了结晶质量高，形貌好，无杂相的铜锌锡硫硒薄膜材料和能量转化效率超过10％的光伏器件，表明该发明显著的先进性。
以上所述仅是本发明的优选实施方式，应当指出：对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种铜锌锡硫太阳能电池的前驱体溶液，其特征在于：以二甲基亚砜DMSO或N,N-二甲基甲酰胺DMF为溶剂，前驱体化合物为溶质配制；所述前驱体化合物由金属配合物、金属盐和硫脲组成，其中，所述金属配合物为铜盐与硫脲或硫脲衍生物形成的铜配合物、锡盐与DMF或DMSO形成的锡配合物，金属盐为二价锌盐；将以上前驱体化合物溶解在DMSO或DMF溶剂中得到稳定、澄清透明的前驱体溶液。
2.根据权利要求1所述的铜锌锡硫太阳能电池的前驱体溶液，其特征在于：所述铜配合物为铜盐与硫脲或硫脲的衍生物形成的配合物，包括：卤素铜盐与硫脲形成的配合物Cu(Tu)3X，其中X为包括F、Cl、Br、I在内的卤族元素，所形成的铜配合物，包括：Cu(Tu)3Cl，[Cu2(Tu)6]Cl2·2H2O,Cu(Tu)3Br；还包括卤素铜盐与硫脲衍生物形成的配合物：Cu(DMTu)3Br，Cu(TMTu)3Cl，[Cu(ETu)2Br]2，其中DMTu为N,N-二甲基硫脲，TMTU为四甲基硫脲，ETu为乙撑硫脲；还包括硝酸铜盐与硫脲形成的配合物Cu4(Tu)10(NO3)·Tu·3H2O。
3.根据权利要求1所述的铜锌锡硫太阳能电池的前驱体溶液，其特征在于：所述锡配合物选自Sn(X)yCl4，Sn(X)yF4,Sn(X)yBr4,Sn(X)yI4,Sn(X)y(CH3COO)4中的一种或多种，X选自DMSO、DMF、乙醇、N-甲基吡咯烷酮中的一种，y为大于零的自然数。
4.根据权利要求1所述的铜锌锡硫太阳能电池的前驱体溶液，其特征在于：所述锌盐为二价锌的化合物，包括但不限于卤素锌盐、乙酸锌、硝酸锌、硫酸锌。
5.根据权利要求1所述的铜锌锡硫太阳能电池的前驱体溶液，其特征在于：所述前驱体溶液中，硫脲物质的量：铜元素的物质的量不大于1。
6.根据权利要求1所述的铜锌锡硫太阳能电池的前驱体溶液，其特征在于：所述前驱体化合物中：
铜元素的物质的量：锡元素的物质的量为(1.5～2.5)：1；
锌元素物质的量：锡元素的物质的量为(0.9～1.5)：1；
硫元素物质的量：铜、锡与锌元素物质的量之和为(1.0～6.0)：1。
7.根据权利要求1所述的铜锌锡硫太阳能电池的前驱体溶液，其特征在于：所述前驱体溶液中：
铜元素在溶液中浓度为0.05mol/L～5mol/L；
锡元素在溶液中浓度为0.05mol/L～5mol/L；
锌元素在溶液中浓度为0.05mol/L～5mol/L；
硫元素在溶液中浓度为0.15mol/L～5mol/L。
8.根据权利要求1-7任一所述的铜锌锡硫太阳能电池的前驱体溶液的制备方法，其特征在于：制备前驱体溶液的具体方法为分步制备法：以DMSO或DMF为溶剂，将铜配合物和硫脲溶解在溶剂中制备溶液一；将锡配合物和锌盐溶解在溶剂中制备溶液二；将溶液一和溶液二混合得到澄清透明的前驱体溶液。
9.根据权利要求8所述的铜锌锡硫太阳能电池的前驱体溶液的制备方法，其特征在于：铜配合物、锡配合物的制备方法为：
合成铜配合物：将硫脲溶解在去离子水中，待硫脲完全溶解后将铜盐加入溶液中，所加入的硫脲与铜盐的物质的量之比为3:1，反应过程溶液温度为70摄氏度；溶解后，将溶液过滤，静置，缓慢冷却，目标产物铜配合物晶体从溶液中析出，取出上述晶体产物并烘干；
合成锡配合物：取四价锡盐于圆底烧瓶中，密封瓶口，取有机化合物溶剂DMF或DMSO注入瓶中，其中溶剂中有机化合物与锡盐物质的量之比为2～20；锡盐与DMF或DMSO溶剂反应生成大量白色沉淀，用乙醇将沉淀清洗干净，烘干即得相应目标产物锡配合物。
10.根据权利要求1-7任一所述的一种铜锌锡硫太阳能电池的前驱体溶液应用于制备铜锌锡硫太阳能电池，其特征在于：铜锌锡硫太阳能电池的制备方法包括以下步骤：
(1)将制备获得的前驱体溶液旋涂在钼玻璃上，加热退火生成铜锌锡硫前驱体薄膜；
(2)将所述前驱体薄膜在Se的气氛中加热进行硒化反应，以Se原子部分或者全部取代S原子生成铜锌锡硫Se薄膜材料；
(3)将硒化反应后的铜锌锡硫Se膜取出并用超纯水浸泡后置于含有氨水、硫酸镉和硫脲溶液的水夹套烧杯中，在加热情况下进行反应，在铜锌锡硫Se膜表面沉积一层CdS；
(4)通过磁控溅射技术在步骤(3)的样品表面依次溅射ZnO和ITO作为窗口层；
(5)通过热蒸镀方法在步骤(4)获得的样品表面蒸镀金属Ni和Al作为阴极。
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| CN112397598A (zh) * | 2020-11-17 | 2021-02-23 | 南京邮电大学 | 前驱体溶液及其制备银铜锌锡硫薄膜太阳能电池的方法 |
| WO2021227362A1 (zh) * | 2020-05-15 | 2021-11-18 | 南京邮电大学 | 铜锌锡硫薄膜太阳能电池的前驱体溶液及其制备方法与应用 |
| CN114899280A (zh) * | 2022-05-11 | 2022-08-12 | 中南大学 | 一种镉掺杂的铜锌锡硫硒薄膜制备方法及其在太阳能电池中的应用 |
| CN114899279A (zh) * | 2022-05-11 | 2022-08-12 | 中南大学 | 一种改性铜锌锡硫前驱体溶液及薄膜太阳电池的制备方法 |
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| CN114988715B (zh) * | 2022-05-25 | 2023-06-27 | 中南大学 | 一种铜锌锡硫薄膜的制备方法 |
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