CN105140335A - CZTS film preparation method on transparent conductive substrate through one step - Google Patents
CZTS film preparation method on transparent conductive substrate through one step Download PDFInfo
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- CN105140335A CN105140335A CN201510425337.1A CN201510425337A CN105140335A CN 105140335 A CN105140335 A CN 105140335A CN 201510425337 A CN201510425337 A CN 201510425337A CN 105140335 A CN105140335 A CN 105140335A
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- zinc
- tin
- copper
- sulfur
- electrically conducting
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- 239000000758 substrate Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000000137 annealing Methods 0.000 claims abstract description 28
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 238000004140 cleaning Methods 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000011135 tin Substances 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 239000000344 soap Substances 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 239000011593 sulfur Substances 0.000 claims abstract description 3
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 claims description 76
- 238000000151 deposition Methods 0.000 claims description 18
- 238000004062 sedimentation Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 12
- 235000002906 tartaric acid Nutrition 0.000 claims description 12
- 239000011975 tartaric acid Substances 0.000 claims description 12
- 239000001509 sodium citrate Substances 0.000 claims description 11
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 11
- 229940038773 trisodium citrate Drugs 0.000 claims description 11
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 9
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 9
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 9
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 9
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 9
- 235000011150 stannous chloride Nutrition 0.000 claims description 9
- 239000001119 stannous chloride Substances 0.000 claims description 9
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 9
- 229960001763 zinc sulfate Drugs 0.000 claims description 9
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000002484 cyclic voltammetry Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 238000005137 deposition process Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000002474 experimental method Methods 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- GRPQBOKWXNIQMF-UHFFFAOYSA-N indium(3+) oxygen(2-) tin(4+) Chemical compound [Sn+4].[O-2].[In+3] GRPQBOKWXNIQMF-UHFFFAOYSA-N 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000005987 sulfurization reaction Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 231100000614 poison Toxicity 0.000 abstract description 3
- 230000007096 poisonous effect Effects 0.000 abstract description 3
- 238000004070 electrodeposition Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 49
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 6
- 230000005518 electrochemistry Effects 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229940001474 sodium thiosulfate Drugs 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229940013123 stannous chloride Drugs 0.000 description 2
- 229960001367 tartaric acid Drugs 0.000 description 2
- 235000019263 trisodium citrate Nutrition 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910000928 Yellow copper Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a CZTS film preparation method on a transparent conductive substrate through one step by adopting a three-electrode system. The method comprises the following steps of (1) substrate cleaning: soap liquid ultrasonic cleaning is performed and then ultrasonic cleaning through mixed liquid of hydrogen peroxide and ethanol is performed and cleaning is performed again through deionized water after the substrate is taken out, and the cleaned transparent conductive substrate is immersed in an ethanol solvent for standby application; (2) preparation of electrolyte: electrolyte containing copper, zinc, tin and sulfur substance is prepared; (3) electrochemical deposition: a CZTS preformed layer is deposited by the three-electrode system; (4) cleaning of the preformed layer: direct cleaning is performed through deionized water so as to remove oxide on the surface of the film; and (5) annealing of the preformed layer: annealing is performed under protection of nitrogen so that a CZTS film is obtained. Forbidden bandwidth of a CZTS film solar cell absorption layer prepared by the method is 1.62eV, raw material is non-poisonous and harmless, operation is easy and convenient, sulfuration is not involved in the annealing process, cost is low and thus the method is suitable for industrial scale production.
Description
Technical field
The present invention relates to a kind of copper-zinc-tin-sulfur film obtained in electrically conducting transparent substrate previous step by electrochemistry three-electrode system as the preparation method of the Green Chemistry of solar battery obsorbing layer, belong to photovoltaic material technical field of new energies.
Background technology
Always Environment and energy is the two principal themes of the world today.Solar energy is a kind of inexhaustible, nexhaustible renewable and clean energy resource, and a lot of country starts to develop the new power that solar energy resources seeks economic development.
In the past few decades, cadmium telluride (CdTe) and Copper Indium Gallium Selenide (CIGS) thin-film solar cells are subject to extensive research at photovoltaic art, and the optoelectronic transformation efficiency of copper indium gallium selenide film battery reaches 19.9%, but because cadmium is poisonous, indium and gallium are rare metal, these all limit their large-scale application, and therefore searching one is nontoxic and lower-cost material becomes study hotspot for thin-film solar cells.In recent years, quaternary sulfide copper-zinc-tin-sulfur (CZTS) emerges in thin-film solar cells of future generation, the copper-zinc-tin-sulfur of custerite structure is similar to the Copper Indium Gallium Selenide of yellow copper structure, and the rich content of each element in the earth's crust, therefore with they replace indium, gallium can reduce costs greatly, copper-zinc-tin-sulfur is direct band gap material, and its absorption coefficient of light is higher than 10
-4cm
-1, material requested thickness less (about 3 μm) in battery, energy gap is 1.05 ~ 1.5eV about, matches, be highly suitable for solar cell with the best energy gap 1.5eV required for solar cell.
Current growth depositing copper-zinc-tin sulphur can be divided into the method for physics, chemistry.Such as molecular beam evaporation, mixing sputtering, magnetron sputtering, thermal evaporation, laser pulse evaporation, electron beam evaporation presoma after cure method, sol-gel after cure method, electrochemical process etc.Because copper-zinc-tin-sulfur is that Copper Indium Gallium Selenide develops by copper indium diselenide (CIS).So copper-zinc-tin-sulfur method derives from Copper Indium Gallium Selenide technology of preparing mostly.And there is various problem in physical method preparation, as: equipment is complex and expensive comparatively, produces poisonous accessory substance etc., and much needs to carry out under the high temperature conditions in this several method, often cause the waste of material and the energy, be also unfavorable for the popularization of solar cell.Be just rise for these several years by electrochemically depositing copper-zinc-tin sulphur method, by read documents, we find that the article that electrochemistry prepares copper-zinc-tin-sulfur is mainly published in about 2010.These electrochemical methods are generally the synthetic method and the copper that combine Copper Indium Gallium Selenide, zinc, and tin electroplating technological innovation invents, and generally needs to deposit under acid or alkaline conditions.Certain electrochemical deposition is also divided into three kinds: (1) three kind of Elemental redistribution deposition (copper-zinc-Xi), and final baking prepares copper-zinc-tin-sulfur (CZTS); (2) at room temperature electrochemistry prepares copper-zinc-Xi presoma, sulfuration: presoma and highly purified sulphur are put into tube furnace, heats under nitrogen protection.(3) precursor is prepared, three-electrode system, one-step method deposited copper-zinc-Xi-sulphur.Electrochemical process is that a kind of equipment is simple, and process holds manageable method, does not need high temperature and expensive equipment, has greatly saved cost, more can embody the advantage of green energy resource.More and more to cause extensive concern and the attention of people in recent years.We adopt electrochemistry one-step method to prepare copper-zinc-tin-sulfur film for these reasons.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of with low cost, green, easy to operate and copper-zinc-tin-sulfur film premised on electrochemistry basis, be different from traditional after cure technique and molybdenum does substrate, simplify the preparation flow of copper-zinc-tin-sulfur film, greatly reduce the cost preparing copper-zinc-tin-sulfur film.
The involved in the present invention method preparing copper-zinc-tin-sulfur film in electrically conducting transparent substrate previous step is implemented according to the following steps:
(1) cleaning of electrically conducting transparent substrate: cutting electrically conducting transparent substrate, first ultrasonic cleaning in soap lye, then with washed with de-ionized water until cleaning solution foam washes, in order to remove the grease of surface existence; Use hydrogen peroxide and alcohol mixed solution ultrasonic cleaning again, finally use washed with de-ionized water, to remove the impurity of electrically conducting transparent substrate surface attachment; Be immersed in alcohol solvent for subsequent use after the electrically conducting transparent substrate surface moisture washed is dried up;
(2) prepare deposited electrolyte: the electrolyte of preparation containing copper, zinc, tin, sulfur material, by concentration (mM) of rubbing in the least, in electrolyte, copper sulphate, zinc sulfate concentration are respectively 20 ~ 40,10 ~ 170; Stannous chloride, concentration of sodium thiosulfate are all 10 ~ 20; Trisodium citrate, tartaric acid concentration are respectively 200 ~ 300,100 ~ 200.Add tartaric acid and the pH value of electrolyte is adjusted to 3.6 ~ 4.5, the deionized water of 80 ~ 100ml is as solvent;
(3) electrochemically depositing copper-zinc-tin sulphur preformed layer: adopt three-electrode system and constant potential, first scan by cyclic voltammetry, select suitable potential range.Current potential constant in selection range, and under each constant voltage chosen, select suitable sedimentation time;
(4) by depositing the copper-zinc-tin-sulfur preformed layer washed with de-ionized water obtained, in order to remove impurity; After having cleaned, at once obtained preformed layer is placed heating plate, 110 DEG C of heating 3 ~ 6 minutes, remove the organic solvent in film by volatilization;
(5) annealing region is at 500 ~ 560 DEG C, and pass into nitrogen as protection gas, do not need sulfuration in process, annealing time obtains final copper-zinc-tin-sulfur film after maintaining 60 ~ 90 minutes.
The present invention prepares the method for copper-zinc-tin-sulfur film in electrically conducting transparent substrate previous step, in step (1), and the long 6cm of electrically conducting transparent substrate of cutting, wide 2cm.Before the deposition, conducting resinl is fixed, and makes electrically conducting transparent substrate deposition duration be 3cm, wide for 2cm.Substrate pretreatment first will remove the grease of electrically conducting transparent substrate surface, then removes the impurity of electrically conducting transparent substrate surface attachment.
The present invention prepares the method for copper-zinc-tin-sulfur film in electrically conducting transparent substrate previous step, in step (1), the volume ratio using hydrogen peroxide and ethanol in the hydrogen peroxide alcohol mixeding liquid of impurity is adhered to, hydrogen peroxide: ethanol=3:7 in order to remove electrically conducting transparent substrate surface.
The present invention prepares the method for copper-zinc-tin-sulfur film in electrically conducting transparent substrate previous step, in step (2), preparation electrolyte have employed deionized water as solvent, do not select organic solvent, take trisodium citrate as complexing agent, it makes the growth current potential of each element be close and move to negative pole, take tartaric acid as buffer, play the effect of adjust ph, also serve the effect of reduction simultaneously.
The present invention prepares the method for copper-zinc-tin-sulfur film in electrically conducting transparent substrate previous step, in step (3), is-1.1 ~-1.4V by cyclic voltammetry determination deposition voltage scope, selects sedimentation time to be 15 ~ 25 minutes.
The present invention prepares the method for copper-zinc-tin-sulfur film in electrically conducting transparent substrate previous step, in step (4), the copper-zinc-tin-sulfur film washed with de-ionized water obtained after deposition, and on hot plate 110 DEG C heating 3 ~ 6 minutes, to remove the organic substance in impurity and film.
The present invention prepares the method for copper-zinc-tin-sulfur film in electrically conducting transparent substrate previous step, and in step (5), copper-zinc-tin-sulfur film is put into quartz boat and is pushed into tube furnace zone line, and nitrogen is using the flow of 20 ~ 30sccm as protection gas.Before taking-up copper-zinc-tin-sulfur film, film need treat that in-furnace temperature is down to about 50 DEG C, anti-oxidation.
Beneficial effect:
Method of the present invention is adopted to prepare copper-zinc-tin-sulfur film, solar battery obsorbing layer energy gap is 1.62eV, raw material are nontoxic, easy and simple to handle, annealing process does not relate to sulfuration, with low cost, more difference does substrate with the molybdenum (Mo) of most of bibliographical information, have employed electrically conducting transparent substrate to carry out the advantage such as depositing, be more suitable for industrial-scale production.
Accompanying drawing explanation
Cyclic voltammetry curve figure when Fig. 1 is depositing copper-zinc-tin sulphur film of the present invention.
When Fig. 2 is depositing copper-zinc-tin sulphur film of the present invention, same concentrations, the x-ray diffraction pattern (XRD) under different sedimentation potential, different sedimentation time, different annealing temperature.
When Fig. 3 is depositing copper-zinc-tin sulphur film of the present invention, same concentrations, the Raman figure (Raman) under different sedimentation potential, different sedimentation time, different annealing temperature.
When Fig. 4 is depositing copper-zinc-tin sulphur film of the present invention, same concentrations, the scanning electron microscope (SEM) photograph (SEM) under different sedimentation potential, different sedimentation time, different annealing temperature.
When Fig. 5 is depositing copper-zinc-tin sulphur film of the present invention, same concentrations, the constituent content analysis figure (EDS) under different sedimentation potential, different sedimentation time, different annealing temperature.
Fig. 6 is in example one method, adopts the inventive method when step (4), prepare the scanning electron microscope (SEM) photograph (SEM) of copper-zinc-tin-sulfur.
Fig. 7 is in example one method, adopts the inventive method when step (4), prepare the scanning electron microscope (SEM) photograph (SEM) of copper-zinc-tin-sulfur.
Fig. 8 is in example one method, adopts the inventive method when step (4), prepare (ahv) ~ hv curve chart of copper-zinc-tin-sulfur film.
Embodiment
In conjunction with following specific embodiments and the drawings, the present invention is described in further detail, and protection content of the present invention is not limited to following examples.Be further understood that, upon reading this disclosure, those skilled in that art can do various amendment or corrigendum to the present invention, and the change of these equivalents limits protection range at the application's appended claims equally.
Embodiment 1
One, operating procedure is as follows:
(1) long 6cm is cut, the ito glass sheet of wide 2cm;
(2) the ito glass substrate first ultrasonic cleaning in soap lye first will cut, washed with de-ionized water 3 times, to remove the oily matter on ITO surface; Hydrogen peroxide and ethanol by volume=3:7 mixing ultrasonic cleaning, then use washed with de-ionized water, to remove the impurity of ito glass surface attachment; Be immersed in alcohol solvent for subsequent use after the moisture on ITO surface being dried up with nitrogen, and be fixed as long 3cm with conducting resinl, wide 2cm.
(3) adopt the copper sulphate of AG, zinc sulfate, stannous chloride, sodium thiosulfate, trisodium citrate, tartaric acid as solute, the electrolyte of preparation 80ml.By concentration (mM) of rubbing in the least, in electrolyte, copper sulphate, zinc sulfate concentration are respectively 20,170; Stannous chloride, concentration of sodium thiosulfate are all 10; Trisodium citrate, tartaric acid concentration are respectively 200,100, and magnetic agitation is until solute dissolves completely, and the pH value of electrolyte is 3.6.
(4) using the ito glass sheet that obtains after cleaning in (2) step as work electrode, silver/silver chlorate is as reference electrode, and platinized platinum is as to electrode.Deposit under-1.2V ,-1.3V constant voltage, sedimentation time is 1200 seconds, preliminary obtained copper-zinc-tin-sulfur preformed layer.
(5) by obtained copper-zinc-tin-sulfur film washed with de-ionized water preliminary in (4) step, 110 DEG C are heated 3 ~ 6 minutes on hot plate.
(6) the copper-zinc-tin-sulfur preformed layer obtained in (5) step is put into quartz boat; retell quartz boat and push tube furnace zone line; nitrogen is using the flow of 20 ~ 30sccm as protection gas; annealing temperature is respectively 500 DEG C, 560 DEG C; annealing time is attempted at such a temperature respectively; 60 minutes, 90 minutes, taken out when copper-zinc-tin-sulfur film is cooled to 50 DEG C gradually.
Two, performance characterization:
Fig. 1 is that the present invention is respectively 20,170 mMs in copper sulphate, zinc sulfate concentration; Stannous chloride, concentration of sodium thiosulfate are all 10 mMs; Trisodium citrate, tartaric acid concentration are respectively 200,100 mMs, and the pH of electrolyte is 3.6.Add the current potential of scope from 0Vvs.Ag/AgCl to-1.6Vvs.Ag/AgCl on the working electrode (s, do linear scan with the speed of 50mV/S and the cyclic voltammetry curve recorded, as can be seen from the figure, under this electrolyte, deposition voltage scope is-1.1V ~-1.4V.
Fig. 2 is the present invention with the x-ray diffraction pattern of the copper-zinc-tin-sulfur film sample obtained under said ratio.Abscissa is the angle of diffraction of 2 times, and ordinate is relative intensity, and as can be seen from Fig., sample all defines custerite structure copper-zinc-tin-sulfur film, certainly also there are other phases.The face, peak of corresponding five groups of samples is all respectively (112), (200), (220), (224) face and all matches with the standard diagram (ICDD:00-026-0575CZTS) of custerite structure copper-zinc-tin-sulfur, and five groups of samples are all along (112) face preferential growth.From X-ray diffracting spectrum can find out sample along with annealing time extend and annealing temperature increase preferential growth (112) crystallinity increase.In addition, the intermediate of binary and ternary can be converted at alloyed layer, as copper sulfide, zinc sulphide, stannous sulfide etc. after annealing.
Fig. 3 is the present invention with the Raman spectrogram of the copper-zinc-tin-sulfur film sample obtained under said ratio.As can be seen from the figure, the main Raman peaks position of obtained copper-zinc-tin-sulfur film is at 329 ~ 336cm
-1.With the main peak position of the copper-zinc-tin-sulfur film of bibliographical information at 338cm
-1near match.
Fig. 4 is the present invention with the surface sweeping Electronic Speculum figure of the copper-zinc-tin-sulfur film sample obtained under said ratio.Be-1.2V with constant voltage, sedimentation time is 1200s, and annealing temperature is 560 DEG C, and annealing time is the copper-zinc-tin-sulfur film sample obtained for 60 minutes is example.Multiplication factor: × 10000, as can be seen from the figure, copper-zinc-tin-sulfur film sample topography is homogeneous, compactness and regularity better.
Fig. 5 is the elementary analysis figure of the copper-zinc-tin-sulfur film sample that the present invention obtains under said ratio.Be-1.2V with constant voltage, sedimentation time is 1200s, and annealing temperature is 560 DEG C, and annealing time is the copper-zinc-tin-sulfur film sample obtained for 60 minutes is example.Can find out that both film chemical components after the annealing process and desirable chalcopyrite exist certain error, nonstoichiometry is larger.The component ratio of energy spectrogram display film is: Cu/ (Zn+Sn)=1.05, Zn/Sn=1.87, S/ (Cu+Zn+Sn)=0.56, this demonstrate zinc overdose, and sulphur, selenium is not enough.Although deviate from Cu:Zn:Sn:S=2:1:1:4, custerite copper-zinc-tin-sulfur film has larger stoichiometric proportion tolerance, and by the known preparation of X-ray diffracting spectrum is still custerite structure.
Fig. 6, Fig. 7 are the present invention in concentration (mM) of rubbing by milli, and in electrolyte, copper sulphate, zinc sulfate concentration are respectively 20,10; Stannous chloride, concentration of sodium thiosulfate are all 10; Trisodium citrate, tartaric acid concentration are respectively 200,100, and the pH value of electrolyte is 4.3.Be-1.1V with constant voltage, sedimentation time is 1200s, and annealing temperature is 500 DEG C, and annealing time is the copper-zinc-tin-sulfur film sample obtained for 30 minutes is example.Multiplication factor: × 5000 and × 10000, as can be seen from the figure copper-zinc-tin-sulfur film sample compactness is better, pattern is homogeneous, visible crystals well-grown.
Fig. 8 is the present invention in concentration (mM) of rubbing by milli, and in electrolyte, copper sulphate, zinc sulfate concentration are respectively 20,10; Stannous chloride, concentration of sodium thiosulfate are all 10; Trisodium citrate, tartaric acid concentration are respectively 200,100, and the pH value of electrolyte is 4.3.Be-1.2V with constant voltage, sedimentation time is 1200s, and annealing temperature is 500 DEG C, and annealing time is the copper-zinc-tin-sulfur film sample obtained for 60 minutes is example.As can be seen from Figure, the absorption band of copper-zinc-tin-sulfur sample all also exists conditions of streaking, and this shows that film surface also exists some unformed states.Can find out that from spectrogram energy gap is 1.62eV, this result and the energy gap reported match.The sample generated of annealing under proving this temperature is copper-zinc-tin-sulfur film, and this energy gap reaches the energy gap required by solar cell.
Embodiment 2
Operating procedure is as follows:
(1) with step (1) in embodiment 1;
(2) with step (2) in embodiment 1;
(3) adopt the copper sulphate of AG, zinc sulfate, stannous chloride, sodium thiosulfate, trisodium citrate, tartaric acid as solute, the electrolyte of preparation 80ml.By concentration (mM) of rubbing in the least, in electrolyte, copper sulphate, zinc sulfate concentration are respectively 20,10; Stannous chloride, concentration of sodium thiosulfate are all 10; Trisodium citrate, tartaric acid concentration are respectively 200,100, and magnetic agitation is until solute dissolves completely, and the pH value of electrolyte is 4.3.
(4) using the ito glass sheet that obtains after cleaning in (2) step as work electrode, silver/silver chlorate is as reference electrode, and platinized platinum is as to electrode.Deposit under-1.05V ~-1.4V constant voltage, sedimentation time is 15 ~ 25 minutes, preliminary obtained copper-zinc-tin-sulfur preformed layer.
(5) with step (5) in embodiment 1;
(6) the copper-zinc-tin-sulfur preformed layer obtained in (5) step is put into quartz boat; again quartz boat is pushed tube furnace zone line; nitrogen is using the flow of 20 ~ 30sccm as protection gas; annealing temperature is respectively 500 DEG C, 550 DEG C; annealing time is attempted at such a temperature respectively; 30 minutes, 60 minutes, taken out when copper-zinc-tin-sulfur film is cooled to 50 DEG C gradually.
Claims (9)
1. prepare the method for copper-zinc-tin-sulfur film material in electrically conducting transparent substrate previous step, it is characterized in that, preparation process is as follows:
(1) cleaning of electrically conducting transparent substrate: by electrically conducting transparent substrate cutting, puts into soap lye ultrasonic cleaning by the electrically conducting transparent substrate of well cutting, more repeatedly rinses until cleaning solution foam washes by the electrically conducting transparent substrate water after washing;
With hydrogen peroxide and the substrate of alcohol mixed solution ultrasonic cleaning electrically conducting transparent, again clean with deionized water after taking out electrically conducting transparent substrate;
Be immersed in alcohol solvent for subsequent use after the electrically conducting transparent substrate surface moisture washed is dried up;
(2) deposited electrolyte is prepared: the electrolyte of preparation containing copper, zinc, tin, sulfur material;
(3) electrochemically depositing copper-zinc-tin sulphur preformed layer, adopts electrochemical process three-electrode system and constant potential deposited copper, zinc, tin, sulphur layer in electrically conducting transparent substrate;
(4) the copper-zinc-tin-sulfur layer washed with de-ionized water will deposited;
(5) carry out annealing under nitrogen protection and obtain copper-zinc-tin-sulfur film.
2. the preparation method of copper-zinc-tin-sulfur film material as claimed in claim 1, it is characterized in that, in described step (1), electrically conducting transparent substrate can be selected to mix the indium sesquioxide film (TCO) of tin, the tin dioxide transparent conductive glass (FTO) mixing fluorine, the zinc oxide transparent conductive film (AZO) mixing aluminium or indium oxide tin glass or copper sheet (ITO).
3. the preparation method of copper-zinc-tin-sulfur film material as claimed in claim 1, it is characterized in that, in described step (1), in the mixed solution of hydrogen peroxide and ethanol, the volume ratio of hydrogen peroxide and ethanol is 3:7.
4. the preparation method of copper-zinc-tin-sulfur film material as claimed in claim 1, is characterized in that, in described step (2), by concentration (mM) of rubbing in the least, in electrolyte, copper sulphate, zinc sulfate concentration are respectively 20 ~ 40,10 ~ 170; Stannous chloride, concentration of sodium thiosulfate are all 10 ~ 20; Trisodium citrate, tartaric acid concentration are respectively 200 ~ 300,100 ~ 200.
5. the preparation method of copper-zinc-tin-sulfur film material as claimed in claim 1, it is characterized in that, in described step (2), described electrolyte take deionized water as solvent, trisodium citrate is complexing agent, and tartaric acid is buffer and plays the effect of adjust ph, and the pH value of electrolyte is 3.6 ~ 4.5, when preparing electrolyte, adopt the method for magnetic agitation by various substance dissolves.
6. the preparation method of copper-zinc-tin-sulfur film material as claimed in claim 1, it is characterized in that, in described step (3), adopt work electrode, to electrode and reference electrode three-electrode electro Chemical system, using the electrically conducting transparent substrate cut out as work electrode, platinized platinum as to electrode, silver/silver chlorate as reference electrode.
7. the preparation method of copper-zinc-tin-sulfur film material as claimed in claim 1, it is characterized in that, in described step (3), deposition process adopts constant potential mode, at room temperature carry out without stirring, the selection of constant potential is by cyclic voltammetry to determine suitable electric potential scanning scope, and adjustment obtains suitable sedimentation time by experiment.
8. the preparation method of copper-zinc-tin-sulfur film material as claimed in claim 1, is characterized in that, in described step (4), with the copper-zinc-tin-sulfur film layer of washed with de-ionized water deposition, and carries out drying on hot plate.
9. the preparation method of copper-zinc-tin-sulfur film material as claimed in claim 1; it is characterized in that; in described step (5); copper-zinc-tin-sulfur preformed layer puts into quartz boat, quartz boat is pushed the center of tube furnace, is that the nitrogen of 20 ~ 30sccm is as protection gas with flow; with the velocity gradient of 10 DEG C/min, prefabricated membrane is heated to 500 ~ 560 DEG C; and maintain 1 ~ 1.5 hour at 500 ~ 560 DEG C, when furnace temperature is down to 50 DEG C, take out and obtain black copper zinc-tin-sulfur film finished product.
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| CN106480483A (en) * | 2016-09-20 | 2017-03-08 | 格林美股份有限公司 | Copper-zinc-tin-sulfur film and preparation method thereof |
| CN111293194A (en) * | 2020-03-30 | 2020-06-16 | 中国科学院物理研究所 | Preparation method of copper-zinc-tin-sulfur-selenium thin-film solar cell |
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