CN111762808A - Solar cell copper-tin-sulfur thin film absorption layer, preparation method thereof and solar cell - Google Patents
Solar cell copper-tin-sulfur thin film absorption layer, preparation method thereof and solar cell Download PDFInfo
- Publication number
- CN111762808A CN111762808A CN201910244593.9A CN201910244593A CN111762808A CN 111762808 A CN111762808 A CN 111762808A CN 201910244593 A CN201910244593 A CN 201910244593A CN 111762808 A CN111762808 A CN 111762808A
- Authority
- CN
- China
- Prior art keywords
- solar cell
- copper
- preparation
- absorption layer
- tin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 42
- SEAVSGQBBULBCJ-UHFFFAOYSA-N [Sn]=S.[Cu] Chemical compound [Sn]=S.[Cu] SEAVSGQBBULBCJ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 34
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000010408 film Substances 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000002243 precursor Substances 0.000 claims abstract description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 45
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 37
- 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 abstract description 33
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 33
- 238000000137 annealing Methods 0.000 claims abstract description 33
- 239000001119 stannous chloride Substances 0.000 claims abstract description 33
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 32
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005118 spray pyrolysis Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000000151 deposition Methods 0.000 claims description 15
- 238000005507 spraying Methods 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000012159 carrier gas Substances 0.000 claims description 10
- 238000005137 deposition process Methods 0.000 claims description 8
- 239000006096 absorbing agent Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 abstract description 6
- 230000008025 crystallization Effects 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 238000000889 atomisation Methods 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 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 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical group OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000002207 thermal evaporation Methods 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 238000003764 ultrasonic spray pyrolysis Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- -1 CTS Chemical class 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- IZSFVWCXDBEUQK-UHFFFAOYSA-N propan-2-ol;zinc Chemical compound [Zn].CC(C)O.CC(C)O IZSFVWCXDBEUQK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical class [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/006—Compounds containing, besides tin, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- 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
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3441—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising carbon, a carbide or oxycarbide
-
- 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
- C03C17/3644—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 metal being silver
-
- 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
- C03C17/3649—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
-
- 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
-
- 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 at least one potential-jump barrier or surface barrier
- H01L31/068—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 at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to the technical field of solar cells, in particular to a copper-tin-sulfur thin film absorption layer of a solar cell, a preparation method of the absorption layer and the solar cell. The preparation method of the copper tin sulfur film absorption layer provided by the invention is characterized in that a precursor liquid containing copper acetate, stannous chloride and thiourea and taking methanol and ethanol as solvents is used as a raw material, the precursor liquid is atomized, sprayed and deposited on the surface of a substrate by adopting a high-pressure gas spray pyrolysis method, and then the copper tin sulfur film absorption layer is prepared by annealing treatment. The method provided by the invention successfully prepares the copper-tin-sulfur film which has the advantages of good crystallization property, proper crystal grain size, smooth surface, high uniformity, excellent optical property and electrical property and capability of meeting the performance requirement of the absorption layer of the solar cell, has the advantages of cheap and easily obtained raw materials, high utilization rate, safety, environmental friendliness, no need of a vacuum preparation process, suitability for large-area film preparation and suitability for industrial production of the solar cell.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a method for preparing a copper-tin-sulfur film absorption layer of a solar cell by high-pressure gas spray pyrolysis.
Background
Copper zinc tin sulfide (Cu)2ZnSnS4CZTS) is considered as a new thin film solar cell material with great development potential, and has large light absorption coefficient and forbidden bandwidth of about 1.45eV, which forms better match with the solar spectrum. In recent years, CZTS thin film solar cells have been widely studied and have made great progress. However, as quaternary compound semiconductors, CZTS readily produces secondary phases such as Cu during fabrication2S、SnS2And Cu2SnS3Etc., adversely affecting the optical and electrical properties of the film. In contrast, ternary copper tin sulfide (Cu)2SnS3CTS) compound has few element types, the component proportion is easier to control, and the CTS is also a direct band gap semiconductor with the band gap value of about 1.0eV, has large light absorption coefficient and P-type conductivity, and is suitable for being used as an absorption layer material of a thin film solar cell. The theoretical conversion efficiency of a CTS thin film solar cell is about 30%.
The preparation method of the thin film material of the thin film solar cell material mainly comprises a Metal Organic Chemical Vapor Deposition (MOCVD) method, a spray pyrolysis method and the like. The MOCVD film has low deposition temperature, high deposition rate, and uniform film, and is compatible with semiconductor process, so that the MOCVD film can be widely used for preparing semiconductor materials. However, the metal organic source (MO source) used in the MOCVD method is a gas or liquid having a high vapor pressure, so that the preparation and purification are difficult, and the present species are limited, and the use and transportation are inconvenient, thereby limiting the development of MOCVD to a certain extent. In order to overcome the defects of the MOCVD method, researchers are developing a new MO source on one hand, and searching a method which has the characteristics of a Chemical Vapor Deposition (CVD) method and does not need the MO source on the other hand. The Spray Pyrolysis method (SP method) was followed. The spray pyrolysis method combines the advantages of the liquid phase method and the gas phase method film preparation technology to a certain extent, the preparation process does not need vacuum conditions, the raw materials are nontoxic, the crust reserves are rich, and the method has a wide application prospect. The spray pyrolysis method comprises an ultrasonic spray pyrolysis method and a high-pressure gas spray pyrolysis method, the ultrasonic spray pyrolysis method adopts expensive ultrasonic atomization equipment, and precursor liquid is atomized by utilizing ultrasonic waves, so that the uniformity of a prepared film can be well ensured, but the preparation cost is high, and the method is not suitable for wide popularization and application. The high-pressure gas spray pyrolysis method (carrier gas flow spray pyrolysis method) utilizes high-pressure carrier flow to atomize the precursor liquid to form aerosol, and the preparation cost is far lower than that of the ultrasonic spray pyrolysis method. However, when the high-pressure gas spray pyrolysis method is used for preparing a thin film of a multicomponent compound such as CTS, the uniformity of the grain size and the uniformity of the surface of the thin film are low, and the light absorption rate and the photoelectric conversion efficiency of the thin film absorption layer are affected. Therefore, there is a need to develop a more efficient method for preparing a CTS film absorbing layer by high pressure gas spray pyrolysis with excellent film properties.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention aims to provide a method for preparing a copper-tin-sulfur thin film absorption layer of a solar cell by high-pressure gas spray pyrolysis.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a preparation method of a copper-tin-sulfur film absorption layer of a solar cell, which takes a precursor liquid containing copper acetate, stannous chloride and thiourea as a raw material and adopts a high-pressure gas spray pyrolysis method for preparation; the precursor solution takes methanol and ethanol as solvents.
The invention discovers that when the high-pressure gas spray pyrolysis method is adopted to prepare the copper-tin-sulfur film absorbing layer, copper acetate, stannous chloride and thiourea are taken as raw materials, and a mixture of methanol and ethanol is taken as a solvent, so that the low-temperature stable solubility of the raw materials of metal salt and thiourea in the solvent, the atomization efficiency of the precursor liquid sprayed by high-pressure gas, the reaction rate of the metal salt and thiourea in the deposition process and the crystallization film forming efficiency can be obviously improved, the pollution of impurities such as chloride ions and carbon atoms to the film is reduced, other impure phases are reduced, the uniformity of the formed crystal grain size and the surface flatness and uniformity of the copper-tin-sulfur film are improved, and the optical and electrical properties of the solar cell absorbing layer are effectively improved.
Preferably, in the precursor liquid, the molar ratio of copper acetate to stannous chloride is (1-5): 1. the molar ratio of the metal salts can better ensure the interaction between the metal salts in the crystallization and nucleation processes, and further improve the crystallization performance of the film.
More preferably, the molar ratio of the copper acetate to the stannous chloride is (1-3): 1.
preferably, the molar concentration of the copper acetate in the precursor solution is 0.25-1.5 mol/L; the molar concentration of the stannous chloride is 0.25-1.5 mol/L; the molar concentration of the thiourea is 0.5-5 mol/L.
More preferably, the molar concentration of the copper acetate in the precursor solution is 0.25-0.75 mol/L; the molar concentration of the stannous chloride is 0.25-0.5 mol/L; the molar concentration of the thiourea is 0.5-1.5 mol/L.
Preferably, in the precursor liquid, the volume ratio of methanol to ethanol is 11: 1-2: 1; more preferably 11: 1-5: 1. by adopting the proportion of the methanol and the ethanol, the stable dissolution of the metal salt can be more effectively realized, the atomization efficiency of high-pressure gas spraying can be improved, and the reaction rate of the metal salt and the thiourea in the deposition process can be increased.
The preparation method of the high-pressure gas spray pyrolysis method comprises the following steps: and atomizing the precursor liquid by adopting high-pressure gas, spraying and depositing the precursor liquid on the surface of the high-temperature substrate, and annealing the substrate.
Preferably, the temperature of the substrate is 100-400 ℃ in the deposition process. By adopting the substrate temperature, the crystallization and nucleation speeds of decomposed substances can be effectively controlled while the full decomposition reaction of copper acetate and stannous chloride is ensured, and uniform film formation is promoted.
Further preferably, in the deposition process, the temperature of the substrate is 100-300 ℃.
Preferably, in the spraying deposition process, the distance from the nozzle to the substrate is 5-15 cm.
Preferably, in the spraying deposition process, nitrogen or argon is used as a carrier gas, and the flow rate of the carrier gas is 5-45 mL/min.
Preferably, the annealing temperature is 300-500 ℃, and the annealing time is 30-60 min. The annealing temperature and the annealing time can better ensure the uniformity of film formation.
Further preferably, the annealing temperature is 300-400 ℃, and the annealing time is 45-60 min.
Preferably, the temperature rise time in the annealing process is 0.5-10min, and the temperature reduction time is 1-60 min.
Further preferably, the temperature rise time in the annealing process is 0.5-5 min, and the temperature drop time is 1-10 min.
Preferably, in the annealing process, nitrogen-hydrogen mixed gas with the hydrogen volume percentage of 0.1-4%, hydrogen sulfide diluted gas with the hydrogen sulfide volume percentage of 0.1-15%, and high-purity nitrogen or argon are used as protective gas.
Preferably, the thickness of the copper-tin-sulfur thin film absorption layer is 1-10 μm.
As a preferred embodiment of the present invention, the method for preparing the copper tin sulfide thin film absorption layer of the solar cell includes the following steps:
(1) preparing a precursor solution: adding copper acetate, stannous chloride and thiourea into methanol and ethanol at a volume ratio of 11: 1-5: 1, the concentration of copper acetate is 0.25-0.75 mol/L, the concentration of stannous chloride is 0.25-0.5 mol/L, and the concentration of thiourea is 0.5-1.5 mol/L;
(2) atomization spraying deposition: atomizing the precursor solution prepared in the step (1) into gas under high pressure, taking nitrogen or argon as a carrier, wherein the carrier gas flow is 5-45 mL/min, the distance from a nozzle to a substrate is 5-15 cm, the substrate temperature is 100-300 ℃, and carrying out atomization spraying deposition on the surface of the substrate;
(3) annealing treatment: and after the deposition is finished, introducing nitrogen-hydrogen mixed gas with the hydrogen volume percentage of 0.1-1% as protective gas, and annealing at 300-400 ℃ for 0.5-5 min, 45-60 min and 1-10 min.
The invention further provides a copper tin sulfur thin film absorption layer of the solar cell prepared by the preparation method.
The invention also provides a solar cell containing the copper-tin-sulfur thin film absorption layer.
As a preferable embodiment of the present invention, the solar cell includes, in order from bottom to top, a substrate, a dense layer, a buffer layer, an absorber layer, and an upper electrode.
Preferably, the substrate is FTO conductive glass as a substrate.
Preferably, the dense layer is a titanium dioxide film or a zinc oxide film.
Further preferably, the thickness of the dense layer is 20nm to 200 nm.
Preferably, the buffer layer is a cadmium sulfide thin film, a zinc oxide thin film, a magnesium oxide thin film, a zinc sulfide thin film or an antimony-doped indium sulfide thin film.
Further preferably, the buffer layer has a thickness of 20nm to 200 nm.
Preferably, the upper electrode is a layered structure prepared from graphite, silver, gold and molybdenum electrodes.
Further preferably, the thickness of the upper electrode is 50nm to 150 nm.
The invention also provides a preparation method of the solar cell, which comprises the following steps:
(1) preparing a substrate: cleaning and drying the FTO conductive glass to be used as a substrate;
(2) preparing a compact layer: titanium isopropoxide solution or zinc isopropoxide solution is used as precursor solution, the precursor solution is atomized into gas under high pressure, compressed air, nitrogen or argon is used as carrier gas, and titanium dioxide film or zinc oxide film with the thickness of 20nm-200nm is formed by spray pyrolysis deposition on the surface of the FTO substrate;
(3) preparing a buffer layer: preparing a cadmium sulfide film, a zinc oxide film, a magnesium oxide film, a zinc sulfide film or an antimony-doped indium sulfide film with the thickness of 20nm-200nm on the surface of the compact layer by adopting spray pyrolysis or chemical bath to serve as a buffer layer;
(4) preparation of an absorption layer: adding copper acetate, stannous chloride and thiourea into methanol and ethanol at a volume ratio of 11: 1-5: 1, so that the concentration of copper acetate is 0.25-0.75 mol/L, the concentration of stannous chloride is 0.25-0.5 mol/L, and the concentration of thiourea is 0.5-1.5 mol/L, thereby obtaining a precursor solution; atomizing the precursor liquid into gas at high pressure, taking nitrogen or argon as a carrier, wherein the flow rate of the carrier is 5-45 mL/min, the distance from a nozzle to a substrate is 5-15 cm, the temperature of the substrate is 100-300 ℃, and carrying out atomization spraying on the surface of the substrate to deposit a copper-tin-sulfur film with the thickness of 1-10 mu m; after deposition is finished, introducing nitrogen-hydrogen mixed gas with the hydrogen volume percentage of 0.1-1% as protective gas, and annealing at 300-400 ℃, wherein the temperature rise time is 0.5-5 min, the annealing time is 45-60 min, and the temperature reduction time is 1-10 min;
(5) preparing an upper electrode: printing graphite slurry or silver slurry on the surface of the absorption layer by adopting a screen printing method and carrying out annealing treatment, or evaporating silver, gold, molybdenum and molybdenum disulfide on the surface of the absorption layer by adopting a vacuum thermal evaporation method or an electron beam evaporation method to prepare an upper electrode with the thickness of 50nm-150 nm; wherein the current of vacuum thermal evaporation or electron beam evaporation is 80A-120A; during annealing treatment, nitrogen-hydrogen mixed gas with the volume percentage of hydrogen of 0.1-4%, hydrogen sulfide diluent gas with the volume percentage of hydrogen sulfide of 0.1-15%, and high-purity nitrogen or argon are introduced as protective gas, the annealing temperature is 300-600 ℃, the temperature rise time is 0.5-10min, the annealing time is 5-60min, and the temperature reduction time is 1-60 min.
The invention has the beneficial effects that:
(1) according to the invention, the copper tin sulfur film which has the advantages of good crystallization property, proper crystal grain size, smooth surface, high uniformity, excellent optical property and electrical property (forbidden bandwidth of 0.97eV and conversion efficiency of 1.05%) and can meet the performance requirement of the solar cell absorption layer is successfully prepared by selecting and optimizing the preparation raw materials for preparing the copper tin sulfur film absorption layer by the high-pressure gas spray pyrolysis method and adaptively carrying out the integral optimization of the whole set of preparation process.
(2) The preparation method of the copper tin sulfur film absorption layer provided by the invention has the advantages of cheap and easily-obtained raw materials, high utilization rate, safety, environmental friendliness, no need of a vacuum preparation process and suitability for large-area film preparation, obviously improves the production efficiency of the copper tin sulfur film absorption layer, reduces the production cost and is suitable for industrial production of solar film batteries.
Drawings
FIG. 1 is a graph showing the results of X-ray diffraction (XRD) analysis of a CTS thin film in Experimental example 1 of the present invention.
FIG. 2 is a Raman spectrum of a CTS film in Experimental example 1 of the present invention.
FIG. 3 is a surface topography of a CTS film in Experimental example 2 of the present invention.
FIG. 4 is a CTS film (α h v) in Experimental example 3 of the present invention2And h ν.
Fig. 5 is a graph showing J-V characteristics of a CTS thin film solar cell in experimental example 4 of the present invention.
Fig. 6 is a schematic structural diagram of a CTS thin film solar cell in embodiment 7 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The embodiment provides a preparation method of a copper-tin-sulfur thin film absorption layer of a solar cell, which comprises the following specific steps:
(1) preparing a precursor solution: adding copper acetate, stannous chloride and thiourea into methanol and ethanol at a volume ratio of 11: 1, preparing a precursor solution with the concentration of copper acetate of 0.25mol/L, the concentration of stannous chloride of 0.25mol/L and the concentration of thiourea of 0.5 mol/L;
(2) atomization spraying deposition: atomizing the precursor liquid prepared in the step (1) into gas at high pressure, wherein the gas source for high-pressure atomization is air, and the pressure is 0.1 MPa; carrying out atomization spraying on the surface of a substrate at the temperature of 300 ℃ by taking nitrogen as a carrier, wherein the flow rate of the carrier is 15mL/min, the distance from a nozzle to the substrate is 5cm, and a copper-tin-sulfur film with the thickness of 1 micrometer is deposited;
(3) annealing treatment: and after the deposition is finished, introducing nitrogen-hydrogen mixed gas with the hydrogen volume percentage content of 0.1% as protective gas, and annealing at 300 ℃ for 0.5min, 60min and 1min to obtain the coating.
Example 2
The embodiment provides a method for preparing a copper-tin-sulfur thin film absorber layer of a solar cell, which is different from the embodiment 1 only in the step (1), and specifically comprises the following steps:
preparing a precursor solution: adding copper acetate, stannous chloride and thiourea into methanol and ethanol at a volume ratio of 11: 1, preparing a precursor solution with the concentration of copper acetate of 0.6mol/L, the concentration of stannous chloride of 0.3mol/L and the concentration of thiourea of 1 mol/L.
Example 3
The embodiment provides a method for preparing a copper-tin-sulfur thin film absorber layer of a solar cell, which is different from the embodiment 1 only in the step (1), and specifically comprises the following steps:
preparing a precursor solution: adding copper acetate, stannous chloride and thiourea into methanol and ethanol at a volume ratio of 11: 1, preparing a precursor solution with the concentration of copper acetate of 0.75mol/L, the concentration of stannous chloride of 0.25mol/L and the concentration of thiourea of 1.5 mol/L.
Example 4
The embodiment provides a method for preparing a copper-tin-sulfur thin film absorber layer of a solar cell, which is different from the embodiment 1 only in the step (1), and specifically comprises the following steps:
preparing a precursor solution: adding copper acetate, stannous chloride and thiourea into methanol and ethanol at a volume ratio of 5: 1, preparing a precursor solution with the concentration of copper acetate of 0.25mol/L, the concentration of stannous chloride of 0.25mol/L and the concentration of thiourea of 0.5 mol/L.
Example 5
This example provides a method for preparing a copper-tin-sulfur thin film absorber layer of a solar cell, which is different from example 1 only in that the substrate temperature of the spray deposition in step (2) is 250 ℃.
Example 6
This example provides a method for preparing a copper-tin-sulfur thin film absorber layer of a solar cell, which is different from example 1 only in that the annealing temperature in step (3) is 400 ℃ and the annealing time is 60 min.
Example 7
The embodiment provides a method for preparing a solar cell with a copper-tin-sulfur film as an absorption layer, which comprises the following specific steps:
(1) preparing a substrate: the method comprises the following steps of taking FTO conductive glass as a substrate, putting the substrate into a beaker, firstly, ultrasonically cleaning for 0.5h by using a washing powder solution, then ultrasonically cleaning for 15min by using a saturated sodium hydroxide-ethanol solution, then ultrasonically cleaning until no alkali liquor residue exists on the surface by using tap water, then ultrasonically cleaning by using deionized water, and finally drying by using nitrogen for later use.
(2) Preparing a compact layer: titanium isopropoxide and ethanol are mixed according to a molar ratio of 1: 1, uniformly mixing to prepare a titanium isopropoxide solution, spraying, pyrolyzing and depositing on the surface of the FTO conductive glass substrate by taking compressed air as a carrier gas to form a titanium dioxide film with the thickness of 20nm, wherein the deposition temperature is 400 ℃, and the distance from a nozzle to a hot platform is 5 cm;
(3) preparing a buffer layer: adding cadmium acetate and thiourea into distilled water to prepare a precursor solution, wherein the concentration of the cadmium acetate is 0.05mol/L, the concentration of the thiourea is 0.2mol/L, spraying and pyrolyzing on the surface of the compact layer by taking nitrogen as carrier gas to prepare a cadmium sulfide thin film buffer layer with the thickness of 20nm, the deposition temperature is 300 ℃, and the distance from a nozzle to a hot platform is 5 cm;
(4) preparation of an absorption layer: adding copper acetate, stannous chloride and thiourea into methanol and ethanol at a volume ratio of 11: 1, preparing a precursor solution with the concentration of copper acetate of 0.25mol/L, the concentration of stannous chloride of 0.25mol/L and the concentration of thiourea of 0.5 mol/L; atomizing the prepared precursor liquid into gas at high pressure, taking nitrogen as a carrier, controlling the flow rate of the carrier gas to be 15mL/min, controlling the distance from a nozzle to a hot table to be 5cm, controlling the temperature of a substrate to be 300 ℃, and carrying out atomization spraying on the surface of the substrate to deposit a copper-tin-sulfur film with the thickness of 1 mu m; and after the deposition is finished, introducing nitrogen-hydrogen mixed gas with the hydrogen volume percentage of 0.1% as protective gas, and annealing at 300 ℃ for 0.5min, 60min and 1 min.
(5) Preparing an upper electrode: and (2) performing gold evaporation plating on the surface of the absorption layer by using gold (Au) with the purity of 99.99% as a raw material by adopting a vacuum thermal evaporation method, and then performing annealing treatment to obtain an upper electrode with the thickness of 100nm, wherein high-purity nitrogen is introduced as a protective gas during the annealing treatment, the annealing temperature is 400 ℃, the temperature rise time is 5min, the annealing time is 30min, and the temperature reduction time is 15 min.
The embodiment also provides a solar cell prepared by the method, and the structural schematic diagram of the solar cell is shown in fig. 6.
Comparative example 1
The comparative example provides a preparation method of a copper-tin-sulfur thin film absorption layer of a solar cell, which is different from the method of example 1 only in the step (1) and specifically comprises the following steps:
preparing a precursor solution: adding copper chloride, stannous chloride and thiourea into the mixture according to the volume ratio of 11: 1, preparing a precursor solution with the concentration of copper chloride of 0.25mol/L, stannous chloride of 0.25mol/L and thiourea of 0.5 mol/L.
Comparative example 2
The comparative example provides a preparation method of a copper-tin-sulfur thin film absorption layer of a solar cell, which is different from the method of example 1 only in the step (1) and specifically comprises the following steps:
preparing a precursor solution: adding copper sulfate, tin chloride and thiourea into the mixture according to the volume ratio of 11: 1, preparing a precursor solution with copper sulfate concentration of 0.25mol/L, tin chloride concentration of 0.25mol/L and thiourea concentration of 0.5 mol/L.
Comparative example 3
The comparative example provides a preparation method of a copper-tin-sulfur thin film absorption layer of a solar cell, which is different from the method of example 1 only in the step (1) and specifically comprises the following steps:
preparing a precursor solution: adding copper acetate, stannous chloride and thiourea into methanol to prepare a precursor solution with the concentration of 0.25mol/L of copper acetate, the concentration of 0.25mol/L of stannous chloride and the concentration of 0.5mol/L of thiourea.
Comparative example 4
The comparative example provides a preparation method of a copper-tin-sulfur thin film absorption layer of a solar cell, which is different from the method of example 1 only in the step (1) and specifically comprises the following steps:
preparing a precursor solution: adding copper acetate, stannous chloride and thiourea into the mixture according to the volume ratio of 11: 1, preparing a precursor solution with the concentration of copper acetate of 1.5mol/L, the concentration of stannous chloride of 0.25mol/L and the concentration of thiourea of 1.0 mol/L.
Comparative example 5
The comparative example provides a preparation method of a copper-tin-sulfur thin film absorption layer of a solar cell, which is different from the method of example 1 only in the step (1) and specifically comprises the following steps:
preparing a precursor solution: adding copper sulfate, tin chloride and thiourea into the mixture according to the volume ratio of 1: 1, preparing a precursor solution with the concentration of copper acetate of 0.25mol/L, the concentration of stannous chloride of 0.25mol/L and the concentration of thiourea of 0.5 mol/L.
Experimental example 1 Crystal Structure analysis of film
The X-ray diffractometer is adopted to respectively detect the crystal structures of the CTS films prepared by the methods of examples 1-6 and comparative examples 1-5, and the results show that the CTS films prepared by the examples 1-6 are the CTS films with a Kesterite structure, have no hetero-phase peak and have the grain size of 1 mu m; the X-ray diffraction peak of the CTS films prepared in the comparative examples 1-5 is weak, which indicates that the crystallinity is not good enough; wherein the X-ray diffraction pattern of the CTS thin film prepared in example 1 is shown in fig. 1.
The internal structures of the CTS films prepared by the methods of examples 1-6 and comparative examples 1-5 are analyzed by Raman spectroscopy (Raman), and the results show that the films prepared by examples 1-6 and comparative examples 1-5 are CTS films, but compared with comparative examples 1-5, the Raman spectroscopy peak values of examples 1-6 are stronger, which indicates that the CTS films of the examples have better quality; the raman spectrum result of the CTS film prepared in example 1 is shown in fig. 2.
Experimental example 2 surface morphology analysis of film
The surface appearance of the CTS films prepared by the methods of examples 1-6 and comparative examples 1-5 is observed by using a scanning electron microscope, and the results show that the CTS films of examples 1-6 have compact and flat surfaces, no crack defects and high quality; the films prepared by the methods of comparative examples 1-5 have poor surface compactness, holes and smaller grain size; the results of the CTS film prepared in example 1 are shown in FIG. 3.
Experimental example 3 optical Properties of film
The optical performance of the CTS films prepared by the methods of examples 1-6 and comparative examples 1-5 is analyzed by an ultraviolet-visible spectrometer, and the result shows that the forbidden bandwidth of the CTS films prepared by examples 1-6 is within the range of 0.95-1 eV; the forbidden band width prepared in the comparative examples 1-5 is less than 0.90 eV; the detection result of the ultraviolet-visible spectrometer of the CTS film prepared in example 1 is shown in fig. 4, and the forbidden bandwidth is 0.97 eV.
Experimental example 4 analysis of electrical properties of CTS thin film solar cell
The electrical properties of the CTS thin-film solar cell prepared by the method of example 7 were measured by an IV tester and analyzed, and the current density-voltage (J-V) characteristic curve thereof is shown in fig. 5, and the conversion efficiency thereof was calculated to be 1.05%.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a copper tin sulfur film absorption layer of a solar cell is characterized in that a precursor liquid containing copper acetate, stannous chloride and thiourea is used as a raw material, and a high-pressure gas spray pyrolysis method is adopted for preparation; the precursor solution takes methanol and ethanol as solvents.
2. The preparation method according to claim 1, wherein the molar ratio of copper acetate to stannous chloride in the precursor liquid is (1-5): 1; preferably (1-3): 1.
3. the method according to claim 2, wherein the molar concentration of copper acetate in the precursor solution is 0.25 to 1.5 mol/L; the molar concentration of the stannous chloride is 0.25-1 mol/L; the molar concentration of the thiourea is 0.5-5 mol/L;
preferably, the molar concentration of the copper acetate in the precursor solution is 0.25-0.75 mol/L; the molar concentration of the stannous chloride is 0.25-0.5 mol/L; the molar concentration of the thiourea is 0.5-1.5 mol/L.
4. The production method according to any one of claims 1 to 3, wherein the volume ratio of methanol to ethanol in the precursor liquid is 11: 1-2: 1; preferably 11: 1-5: 1.
5. the production method according to any one of claims 1 to 4, characterized in that the high-pressure gas spray pyrolysis production comprises: and atomizing the precursor liquid by adopting high-pressure gas, spraying and depositing the precursor liquid on the surface of a high-temperature substrate, and annealing the substrate.
6. The preparation method according to claim 5, wherein the temperature of the substrate during the deposition is 100-400 ℃; preferably 100 to 300 ℃.
7. The preparation method according to claim 5 or 6, wherein in the spraying deposition process, the distance from the nozzle to the substrate is 5-15 cm;
preferably, in the spraying deposition process, nitrogen or argon is used as a carrier gas, and the flow rate of the carrier gas is 5-45 mL/min.
8. The method according to any one of claims 5 to 7, wherein the annealing temperature is 300 to 500 ℃ and the annealing time is 30 to 60 min;
preferably, the annealing treatment temperature is 300-400 ℃, and the annealing time is 45-60 min.
9. The solar cell copper tin sulfur thin film absorption layer prepared by the preparation method of any one of claims 1 to 8.
10. A solar cell comprising the copper tin sulfide thin film absorber layer of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910244593.9A CN111762808B (en) | 2019-03-28 | 2019-03-28 | Solar cell copper-tin-sulfur thin film absorption layer, preparation method thereof and solar cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910244593.9A CN111762808B (en) | 2019-03-28 | 2019-03-28 | Solar cell copper-tin-sulfur thin film absorption layer, preparation method thereof and solar cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111762808A true CN111762808A (en) | 2020-10-13 |
| CN111762808B CN111762808B (en) | 2023-02-21 |
Family
ID=72717941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910244593.9A Active CN111762808B (en) | 2019-03-28 | 2019-03-28 | Solar cell copper-tin-sulfur thin film absorption layer, preparation method thereof and solar cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111762808B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112563343A (en) * | 2020-12-09 | 2021-03-26 | 电子科技大学 | Based on Zn1-xMgxInorganic solar cell with O buffer layer and preparation method thereof |
| CN113463109A (en) * | 2021-06-16 | 2021-10-01 | 华南师范大学 | Ternary copper-based compound semiconductor photoelectrode, unbiased sunlight water decomposition hydrogen production and oxygen production device and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181847A (en) * | 2011-04-14 | 2011-09-14 | 山东大学 | Method for depositing Cu-Zn-Tin-Sulfur film by ethanol heat |
| CN102593246A (en) * | 2012-02-13 | 2012-07-18 | 南京航空航天大学 | Low cost solution method for preparing solar cell absorption layer material Cu2ZnSnS4 |
| CN103762257A (en) * | 2014-01-17 | 2014-04-30 | 华东师范大学 | Method for manufacturing copper-zinc-tin-sulfide absorbing layer thin film and copper-zinc-tin-sulfide solar cell |
| CN103956406A (en) * | 2014-04-16 | 2014-07-30 | 渤海大学 | Non-vacuum manufacturing method of copper-zinc-tin-sulfur solar battery of superstrate structure |
| CN105185847A (en) * | 2015-08-24 | 2015-12-23 | 扬州大学 | Method for preparing copper-zinc-tin-sulfur film |
| CN105355720A (en) * | 2015-12-03 | 2016-02-24 | 华东师范大学 | Method for preparing copper-tin-sulfur thin film solar cell absorption layer |
| CN106505114A (en) * | 2016-11-03 | 2017-03-15 | 中国科学院兰州化学物理研究所 | A kind of preparation method of copper and tin sulfur light absorbing zone thin-film material |
| CN107394007A (en) * | 2017-07-31 | 2017-11-24 | 渤海大学 | A kind of method suitable for the vulcanization of superstrate structural membranes solar cell or selenizing |
-
2019
- 2019-03-28 CN CN201910244593.9A patent/CN111762808B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181847A (en) * | 2011-04-14 | 2011-09-14 | 山东大学 | Method for depositing Cu-Zn-Tin-Sulfur film by ethanol heat |
| CN102593246A (en) * | 2012-02-13 | 2012-07-18 | 南京航空航天大学 | Low cost solution method for preparing solar cell absorption layer material Cu2ZnSnS4 |
| CN103762257A (en) * | 2014-01-17 | 2014-04-30 | 华东师范大学 | Method for manufacturing copper-zinc-tin-sulfide absorbing layer thin film and copper-zinc-tin-sulfide solar cell |
| CN103956406A (en) * | 2014-04-16 | 2014-07-30 | 渤海大学 | Non-vacuum manufacturing method of copper-zinc-tin-sulfur solar battery of superstrate structure |
| CN105185847A (en) * | 2015-08-24 | 2015-12-23 | 扬州大学 | Method for preparing copper-zinc-tin-sulfur film |
| CN105355720A (en) * | 2015-12-03 | 2016-02-24 | 华东师范大学 | Method for preparing copper-tin-sulfur thin film solar cell absorption layer |
| CN106505114A (en) * | 2016-11-03 | 2017-03-15 | 中国科学院兰州化学物理研究所 | A kind of preparation method of copper and tin sulfur light absorbing zone thin-film material |
| CN107394007A (en) * | 2017-07-31 | 2017-11-24 | 渤海大学 | A kind of method suitable for the vulcanization of superstrate structural membranes solar cell or selenizing |
Non-Patent Citations (1)
| Title |
|---|
| IGNACIO ESTEVEZ ESPINOZA等: "Phase composition of Cu2SnS3thin films prepared by Ultrasonic Spray Pyrolysis as potential photovoltaic material", 《15TH INTERNATIONAL CONFERENCE ON ELECTRICAL ENGINEERING, COMPUTING SCIENCE AND AUTOMATIC CONTROL》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112563343A (en) * | 2020-12-09 | 2021-03-26 | 电子科技大学 | Based on Zn1-xMgxInorganic solar cell with O buffer layer and preparation method thereof |
| CN113463109A (en) * | 2021-06-16 | 2021-10-01 | 华南师范大学 | Ternary copper-based compound semiconductor photoelectrode, unbiased sunlight water decomposition hydrogen production and oxygen production device and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111762808B (en) | 2023-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109621979B (en) | Preparation method of ZnO/zinc indium sulfide nano heterojunction | |
| Luo et al. | Chemical vapor deposition of perovskites for photovoltaic application | |
| Hu et al. | Photostable Cu2O photoelectrodes fabricated by facile Zn-doping electrodeposition | |
| JP2010512647A (en) | Doping technology for IBIIIAVIA group compound layer | |
| US20150087110A1 (en) | Low-Temperature Fabrication of Spray-Coated Metal Oxide Thin Film Transistors | |
| EP1066418A1 (en) | Solution synthesis of mixed-metal chalcogenide nanoparticles and spray deposition of precursor films | |
| KR20090092471A (en) | Fabrication of thin film for solar cells using paste and the thin film fabricated thereby | |
| CN111762808B (en) | Solar cell copper-tin-sulfur thin film absorption layer, preparation method thereof and solar cell | |
| CN107464882A (en) | A kind of organic inorganic hybridization perovskite solar cell and preparation method thereof | |
| CN103956406B (en) | A kind of antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell | |
| CN107180880B (en) | A kind of ultra-thin translucent thin film solar cell and preparation method thereof | |
| CN114373831A (en) | Tunneling oxide layer, N-type double-sided solar crystalline silicon battery and preparation method | |
| Zhang et al. | CuWO4 films grown via seeding-hydrothermal method for photoelectrochemical water oxidation | |
| KR101322681B1 (en) | Czts thin film prepared by electrostatic spray and preparing method of the same | |
| Hishimone et al. | Methods of fabricating thin films for energy materials and devices | |
| CN108689610A (en) | A kind of titania-doped coated glass of niobium and preparation method thereof | |
| KR20240032777A (en) | Method of manufacturing metal oxide electrode, photocathode, and photo-electrochemical cell | |
| Ratnasingham et al. | Novel scalable aerosol-assisted CVD route for perovskite solar cells | |
| CN107240645B (en) | The preparation of perovskite-nanometer germanium particle Organic-inorganic composite solar battery | |
| Li et al. | Solvent evaporation induced preferential crystal orientation BiI3 films for the high efficiency MA3Bi2I9 perovskite solar cells | |
| Hou et al. | In situ Au-catalyzed fabrication of branch-type SnO 2 nanowires by a continuous gas-phase route for dye-sensitized solar cells | |
| CN114772943B (en) | Cs (cell lines) 2 TiBr 6 Preparation method of lead-free double perovskite thin film and solar cell | |
| US20210254225A1 (en) | Photoelectrode for hydrogen generation in solar water splitting and manufacturing method thereof | |
| KR101380142B1 (en) | chemical vapor deposition for mist injection over substrate transport and method for fabricating transparent conducting oxide layer using the same and method for fabricating CIS-based thin film solar battery using the same | |
| Illakkiya et al. | Enhanced optoelectronic and photoelectrochemical characteristics of nebulised spray pyrolysed ‘Cu’rich CuInS2 thin film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210126 Address after: Unit 611, unit 3, 6 / F, building 1, yard 30, Yuzhi East Road, Changping District, Beijing 102208 Applicant after: Zishi Energy Co.,Ltd. Address before: Room a129-1, No. 10, Zhongxing Road, science and Technology Park, Changping District, Beijing Applicant before: DONGTAI HI-TECH EQUIPMENT TECHNOLOGY Co.,Ltd. |
|
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |