CN106480483A - 铜锌锡硫薄膜及其制备方法 - Google Patents
铜锌锡硫薄膜及其制备方法 Download PDFInfo
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- CN106480483A CN106480483A CN201610834664.7A CN201610834664A CN106480483A CN 106480483 A CN106480483 A CN 106480483A CN 201610834664 A CN201610834664 A CN 201610834664A CN 106480483 A CN106480483 A CN 106480483A
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- copper
- zinc
- tin
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- sulfur film
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- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 239000003792 electrolyte Substances 0.000 claims abstract description 31
- 238000004070 electrodeposition Methods 0.000 claims abstract description 26
- 238000000151 deposition Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 229910001432 tin ion Inorganic materials 0.000 claims abstract description 6
- 239000010408 film Substances 0.000 claims description 87
- 239000010409 thin film Substances 0.000 claims description 34
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002738 chelating agent Substances 0.000 claims description 7
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003115 supporting electrolyte Substances 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 238000003379 elimination reaction Methods 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- 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 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 230000005518 electrochemistry Effects 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 235000015424 sodium Nutrition 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 12
- 238000005530 etching Methods 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 6
- 231100000004 severe toxicity Toxicity 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 239000011701 zinc Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 3
- 229910002535 CuZn Inorganic materials 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- PDYXSJSAMVACOH-UHFFFAOYSA-N [Cu].[Zn].[Sn] Chemical compound [Cu].[Zn].[Sn] PDYXSJSAMVACOH-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- HDVJLVBMZJTNLY-UHFFFAOYSA-N [Cu].[S].[Sn].[Zn].[Cu] Chemical compound [Cu].[S].[Sn].[Zn].[Cu] HDVJLVBMZJTNLY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 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 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
本发明涉及一种铜锌锡硫薄膜及其制备方法,包括:配制电解液,所述电解液至少包含铜离子、锌离子、锡离子、硫离子、助剂以及溶剂;将表面镀有Cu的基板置入所述电解液中,采用免刻蚀电化学沉积工艺在所述基板上沉积形成铜锌锡硫薄膜,所述铜锌锡硫薄膜的结构式为CuZnaSnbSc,其中,a∈[0,2],b∈[0,2],c∈(0,5]。该制备方法避免使用了剧毒的刻蚀剂且成本低,具有形貌好、成分可控、膜层附着力强、低成本、高效率、高质量和易于实现大面积沉积等优势,有利于其大规模工业推广与应用。
Description
技术领域
本发明涉及光伏材料领域,具体涉及一种铜锌锡硫薄膜及其制备方法。
背景技术
四元化合物Cu2ZnSnS4(CZTS) 与目前光电转化效率最高、研究与应用最为广泛的光吸收层材料Cu(In,Ga)Se2(CIGS)具有相似的晶体结构,而又不含稀贵元素和有毒元素,被普遍认为是可望替代昂贵CIGS的最佳材料之一,已成为目前薄膜太阳能电池领域的研究热点。CZTS的带隙宽度约为1.5eV,接近单结太阳能电池所需的最佳带隙宽度(1.45eV)。同时由于是直接带隙,CZTS具有超过104cm-1的光吸收系数,这使得只需要1~2微米厚度即可吸收大部分的入射太阳光。基于CZTS的薄膜太阳能电池效率也已经达到12.6%,已接近实用的要求。
目前研究制备CZTS薄膜材料的方法有真空和非真空的制备方法。真空法能够较精密地控制膜层的组分,获得高质量的CZTS薄膜,但由于真空法制备薄膜材料必须在高真空下进行、需要昂贵的真空设备、高纯度的原料,同时还存在着原料利用率不高、工艺复杂、难以实现膜层的大面积和连续沉积等问题。这些缺陷限制了CZTS电池大规模的生产和应用。非真空方法中,最常见的是电沉积法,该方法可在低温和非真空条件下进行大面积、多元组分、持续的薄膜沉积,具有设备和工艺简单、成本低廉、界面结合好、材料利用率高(超过95%)等优点。因此用此方法制备太阳能电池用CZTS薄膜成为降低真空法成本、获得大面积高质量薄膜的主要研究方向之一。
由于铜元素在铜锌锡硫生长过程中起到了非常重要的作用,尤其是促进了铜锌锡硫薄膜结晶性能的改善及晶粒的长大。而在Mo基底上电化学沉积的贫铜的方法制备的铜锌锡硫薄膜形貌较差,疏松多孔且颗粒大小不均匀,退火后的显微结构照片如图1所示。故传统电沉积工艺一般沉积富铜的铜锌锡硫预制层并退火,以保证薄膜质量,退火后的显微结构照片如图2所示。但是部分富铜相以Cu2-xS的形态存在于薄膜表面,由于该物相导电性能良好,在后续电池制备中容易导致电池的短路。为解决该问题,大多数研究机构采用的办法是采用氰化钾(KCN)刻蚀薄膜表面的Cu2-xS,此方法保证了薄膜的结晶质量并有效避免了因Cu2-xS引起的电池短路。但KCN作为一种具有剧毒的化学试剂,极大程度上限制了电沉积工艺制备铜锌锡硫的大规模应用及生产。
发明内容
本发明实施例要解决的技术问题在于,提供一种铜锌锡硫薄膜的制备方法,能采用无毒物质制备铜锌锡硫薄膜。
本发明实施例进一步要解决的技术问题在于,提供一种铜锌锡硫薄膜,适合采用无毒物质制备。
为解决上述技术问题,本发明实施例首先采用如下技术方案:一种铜锌锡硫薄膜的制备方法,包括:
配制电解液,所述电解液至少包含:铜离子、锌离子、锡离子、硫离子、助剂以及溶剂;
将表面镀有Cu层的基板置入所述电解液中,采用免刻蚀电化学沉积工艺在所述基板上沉积形成铜锌锡硫薄膜,所述铜锌锡硫半导体薄膜的结构式为CuZnaSnbSc,其中,a∈[0,2],b∈[0,2],c∈(0,5]。
进一步的,所述Cu层厚度为10nm~1000nm。
进一步的,采用溅射、蒸发或电沉积工艺在所述基板表面形成所述Cu层。
进一步的,所述电解液的溶剂为水或者有机溶剂,电解液中的铜离子、锌离子、锡离子和硫离子的摩尔浓度分别为0~0.15mol/L、0~0.30mol/L、0~0.50mol/L和0~0.3mol/L。
进一步的,所述助剂为络合剂,络合剂的摩尔浓度为0.01~1mol/L,所述络合剂选自柠檬酸钠、硫氰化钾、焦磷酸钾、柠檬酸、乙二胺四乙酸、氨三乙酸、羟基亚乙基二膦酸、酒石酸、氨基磺酸、氰化钾、氟化氨和乙二胺中的一种或几种。
进一步的,所述电解液的pH值范围为0.3~13。
进一步的,所述助剂为能提高电解液的导电性且消除反应离子电迁移的支持电解质。所述的支持电解质选自氯化钠、硫酸钠、硝酸钠、氯化钾、硫酸钾、硝酸钾、氯化铵、氯化锂、硫酸锂、硝酸锂的一种或几种。
进一步的,所述采用免刻蚀电化学沉积工艺在所述基板上沉积形成铜锌锡硫薄膜时,工作电极电位为-6.0~ 1.5V(vsSCE,相对于饱和甘汞电极),沉积温度为20~150℃,沉积时间为10~150分钟,制得薄膜厚度为0.01~5μm。
进一步的,所述将沉积形成的铜锌锡硫薄膜置于含S的气氛条件下热处理,热处理的温度范围为250~550℃,热处理时间为0.1~5.5小时。
另一方面,本发明实施例还提供一种铜锌锡硫薄膜,所述铜锌锡硫薄膜的结构式为CuZnaSnbSc,其中,a∈[0,2],b∈[0,2],c∈(0,5]。
通过采用上述技术方案,本发明至少具有以下有益效果:本发明实施例提出了一种免刻蚀电化学沉积制备铜锌锡硫薄膜的方法,在基底上镀制一层预定厚度的Cu,在镀Cu的基底上沉积符合化学计量比或略贫铜的铜锌锡硫预制层。在后续退火过程中,熔融态的铜硫相促进了Zn与Sn元素的迁移,有利于薄膜的生长。该工艺下获得的薄膜具有与采用富铜薄膜后刻蚀处理的薄膜相当的形貌及结晶性能。
该方法不仅能避免采用物理气相沉积 (PVD) 法和化学气相沉积 (CVD) 法存在的工艺和设备复杂、成本高昂、难以大规模生产等不足,也能有效克服传统电沉积法工艺必须使用剧毒的刻蚀剂等问题。采用免刻蚀电沉积工艺制备的铜锌锡硫薄膜具有薄膜形貌好、成分可控、膜层附着力强、低成本、高效率、高质量和易于实现大面积沉积等优势,是推广大规模工业化生产高质量太阳能电池用铜锌锡硫半导体薄膜的有效手段。
因此,本发明解决了传统恒电位或恒电流沉积铜锌锡硫薄膜必须使用剧毒的KCN对富铜薄膜进行刻蚀处理所带来的难题。该制备方法避免使用了剧毒的刻蚀剂且成本低,易于实现铜锌锡硫薄膜大面积沉积,有利于其大规模工业推广与应用。
附图说明
图1是现有的在Mo基底上电化学沉积贫铜薄膜经退火后的薄膜形貌。
图2是现有的在Mo基底上电化学沉积富铜薄膜经退火后的薄膜形貌。
图3是本发明铜锌锡硫薄膜的制备方法的实施例的流程步骤示意图。
图4是在本发明铜锌锡硫薄膜的制备方法的实施例制得的铜锌锡硫薄膜经退火后的薄膜形貌。
具体实施方式
下面结合附图和具体实施例对本申请作进一步详细说明。应当理解,以下的示意性实施例及说明仅用来解释本发明,并不作为对本发明的限定,而且,在不冲突的情况下,本申请中的实施例及实施例中的特征可以相互结合。
如图3所示,本发明的实施例提供了一种铜锌锡硫薄膜的制备方法,包括:
步骤S11,配制电解液,所述电解液至少包含铜离子、锌离子、锡离子、硫离子、助剂以及溶剂的电解液,提供制备铜锌锡硫薄膜的必要离子;
步骤S12,将表面镀有Cu层的基板置入所述电解液中,采用免刻蚀电化学沉积工艺在所述基板上沉积形成铜锌锡硫薄膜,并产生Zn1-2S1~3、CuS1~3、CuZn1~2S1~4或CuZn0.01~2Sn0.01~ 2S0.01~5中的一种或几种物质, 所述铜锌锡硫薄膜的结构式为CuZnaSnbSc,其中,a∈[0,2],b∈[0,2],c∈(0,5]。
本发明通过采用电解液来提供制备铜锌锡硫薄膜的必要离子,并配合免刻蚀电化学沉积工艺在所述基板上沉积形成铜锌锡硫薄膜,制备的铜锌锡硫薄膜具有薄膜形貌好、成分可控、膜层附着力强、低成本、高效率、高质量和易于实现大面积沉积等优势,并且避免了使用剧毒KCN。
所述Cu层厚度为10nm~1000nm,采用整体贫铜,生成的薄膜表面将不会有针状的Cu2-xS存在,避免对薄膜进行KCN刻蚀处理。
具体实施时,本发明还可包括如下步骤:
步骤S10,采用溅射、蒸发或电沉积工艺在所述基板表面形成所述Cu层。
采用这些工艺镀铜,有利于制备厚度一致的贫铜表面。
所述电解液的溶剂为水或者有机溶剂,电解液中的铜离子、锌离子、锡离子和硫离子的摩尔浓度分别为0~0.15mol/L、0~0.30mol/L、0~0.50mol/L和0~0.3mol/L。上述电解液是制备铜锌锡硫薄膜的必备原材料,为制备铜锌锡硫薄膜提供必要离子。
所述助剂为络合剂,摩尔浓度为0.01~1mol/L,成份选自柠檬酸钠、硫氰化钾、焦磷酸钾、柠檬酸、乙二胺四乙酸、氨三乙酸、羟基亚乙基二膦酸、酒石酸、氨基磺酸、氰化钾、氟化氨和乙二胺中的一种或几种。上述络合剂是制备铜锌锡硫薄膜的必备原材料,可形成稳定的新离子,用于制备形貌好、成分可控的薄膜。
具体实施时,还可采用稀盐酸或氢氧化钠将所述电解液的pH调整到范围为0.3~13,通过PH值的调整可以控制电沉积过程中金属离子的析出以及成膜速度。
所述助剂为能提高电解液的导电性且消除反应离子电迁移的支持电解质,所述支持电解质可选自氯化钠、硫酸钠、硝酸钠、氯化钾、硫酸钾、硝酸钾、氯化铵、氯化锂、硫酸锂、硝酸锂的一种或几种。通过采用上述支持电解质,可以提高电解液的导电性且消除反应离子电迁移,提高铜锌锡硫薄膜在基板上的附着力。
所述采用免刻蚀电化学沉积工艺在所述基板上沉积形成铜锌锡硫薄膜时,工作电极电位为-6.0~ 1.5V(vsSCE),沉积温度为20~150℃,沉积时间为10~150分钟,制得薄膜厚度为0.01~5μm。上述工艺为制备铜锌锡硫薄膜的基本工艺,通过上述工艺可制备低成本、高质量的铜锌锡硫薄膜。
所述将沉积形成的铜锌锡硫薄膜置于含S的气氛条件下热处理,热处理的温度范围为250~550℃,热处理时间为0.1~5.5小时。熔融态的铜硫相促进了Zn与Sn元素的迁移,有利于薄膜的生长,改善了薄膜的结晶质量。
本发明还提供一种铜锌锡硫薄膜,所述铜锌锡硫薄膜的结构式为CuZnaSnbSc,其中,a∈[0,2],b∈[0,2],c∈(0,5]。上述铜锌锡硫薄膜制备过程中未使用剧毒的KCN,其铜锌锡硫薄膜具有形貌好、成分可控、膜层附着力强、低成本、高效率、高质量和易于实现大面积沉积等优势。
以下提供几个具体实施例来说明本发明铜锌锡硫薄膜的制备方法的具体操作过程。
实施例1
采用溅射工艺,在Mo玻璃基底上镀制50nm厚度的Cu。在溶质组成为0.15mol/L Cu(NO3)2,0.30mol/L ZnCl3,0.5mol/L SnCl3,0.30mol/L H2SO3,1mol/L 氯化钾,1mol/L 柠檬酸三钠的500ml水溶液中,用稀盐酸或氢氧化钠将其pH调整至0.3;以镀Cu的Mo玻璃为工作电极,大面积Pt网为对电极,饱和甘汞电极(SCE)为参比电极;工作电极电位0.5V(vsSCE),在阴极基底上沉积3~5微米厚的含铜、锌、锡和硫的薄膜CuZnaSnbSc,其中,a∈[0,2],b∈[0,2],c∈(0,5];电解液体系温度为80℃,沉积时间为10分钟。最后将制得的铜锌锡硫薄膜置于含S的氩气中,在250℃温度下热处理5.5小时。
实施例2
采用电沉积工艺,在Mo玻璃基底上镀制80nm厚度的Cu。在溶质组成为0.003mol/LCuCl2,0.01mol/L ZnCl3,0.001mol/L SO2,0.1mol/L 氯化锂,0.2mol/L 柠檬酸三钠的500ml水溶液中,用稀盐酸或氢氧化钠将其pH调整至1.8;以镀Cu的Mo玻璃为工作电极,大面积石墨片为对电极,饱和甘汞电极(SCE)为参比电极;工作电极电位-0.6V(vsSCE);在阴极基底上沉积0.1~2微米厚的含铜、锌和硫的CuZn1~2S1~4薄膜;电解液体系温度为20℃,沉积时间为20分钟。
实施例3
实施例2中的Cu的厚度由80nm调至95nm,沉积电位调至1.5V(vsSCE),其他条件不变,最终可得到形貌更好的CuZnaSb薄膜材料,其中,a∈[0,2],b∈(0,5]。
实施例4
采用电沉积工艺,在Mo玻璃基底上镀制105nm厚度的Cu。在溶质组成为0.02mol/LCuSO4,0.04mol/L Zn2(SO4)3,0.1mol/L Sn2(SO4)3,0.04mol/L SO2,1mol/L 硫酸钠的500ml二甲基亚砜(DMSO)与水混合体系中(摩尔比为1:1~50:1),用稀盐酸或氢氧化钠将其pH调整至5;以镀Cu的Mo为工作电极,大面积Pt网为对电极,双盐桥系统连接的饱和甘汞电极(SCE)为参比电极;工作电极电位-2.5V(vsSCE);在阴极基底上沉积3~5微米厚的含铜、锌、锡和硫的薄膜CuZnaSnbSc,其中,a∈[0,2],b∈[0,2],c∈(0,5];电解液体系温度为80℃,沉积时间为90分钟。最后将制得的铜锌锡硫薄膜置于含S的真空中,在400℃温度下热处理3.1小时。
实施例5
用二甲基甲酰胺(DMF)代替实施例4中的二甲基亚砜(DMSO)和水,其他与实施例4相同,最终可制备出铜锌锡硫薄膜材料。
实施例6
采用蒸发工艺,在Mo玻璃基底上镀制210nm厚度的Cu。在500ml用摩尔比为1:1.5~1:3.0的氯化胆碱(C5H14ONCl)和尿素((NH2)2CO)混合成的离子液体中溶解0.04mol CuCl2,0.04mol ZnCl3,0.02mol SnCl3,0.06M SCl4(均为无水氯化物),并以此为光电解体系,用稀盐酸或氢氧化钠将其pH调整至4;以镀Cu的Mo为工作电极,大面积Pt网为对电极,Pt丝为参比电极;工作电极电位-0.8V(vsSCE);在基底上沉积0.01~1微米厚的含铜、锌、锡和硫的薄膜CuZnaSnbSc,其中,a∈[0,2],b∈[0,2],c∈(0,5];电沉积过程在氩气或氮气气氛的手套箱中进行(含水量为1ppm以下),电解液体系温度为150℃,沉积时间为10分钟。
以上实施例中,不同参数做出的产品不同主要为说明本发明所涉及的制备铜锌锡硫薄膜方法的普适性,通过以上实施例制备的产品虽然形貌、成分都有所差异,但是按照以上实施例均可制备出相应的薄膜材料。
通过以上实施例实验,在其他条件相同的情况下,对比了传统电沉积制备铜锌锡硫薄膜方法与本发明制备铜锌锡硫薄膜方法所制备的薄膜形貌,图1、图2、图4给出了不同工艺下制备铜锌锡硫薄膜经退火后的形貌分析。通过扫描电镜形貌可以观察到,在图1中Mo基底上电化学沉积的贫铜铜锌锡硫薄膜形貌较差,疏松多孔且颗粒大小不均匀,在图2中Mo基底上电化学沉积的富Cu铜锌锡硫薄膜经过KCN刻蚀后获得的薄膜形貌较前者有了大幅改善,表面形貌变得致密平整且颗粒均有所长大,符合高效率器件的要求,这得益于Cu在铜锌锡硫薄膜生长过程中所起到的作用,但是薄膜表面附着较多细小颗粒,经检测该颗粒为富铜相。而在图4中采用本发明方法在镀Cu的Mo基底上电化学沉积的贫Cu铜锌锡硫薄膜获得了与经过KCN刻蚀的富Cu铜锌锡硫薄膜相当的形貌,这说明在Mo基于上镀制一层Cu亦促进了薄膜的生长。此外,由图4样品表面形貌图可知,由于采用了薄膜整体贫铜的成分,故薄膜表面并未有针状的Cu2-xS的存在,不需要再对薄膜进行KCN刻蚀处理,这说明该工艺不但获得了与传统电沉积工艺质量相当的铜锌锡硫薄膜,而且实现了贫铜薄膜免KCN刻蚀的制备。
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同范围限定。
Claims (10)
1.一种铜锌锡硫薄膜的制备方法,其特征在于,包括:
配制电解液,所述电解液至少包含:铜离子、锌离子、锡离子、硫离子、助剂以及溶剂;
将表面镀有Cu层的基板置入所述电解液中,采用免刻蚀电化学沉积工艺在所述基板上沉积形成铜锌锡硫薄膜,所述铜锌锡硫薄膜的结构式为CuZnaSnbSc,其中,a∈[0,2],b∈[0,2],c∈(0,5]。
2.如权利要求1所述的铜锌锡硫薄膜的制备方法,其特征在于,所述Cu层厚度为10nm~1000nm。
3.如权利要求1或2所述的铜锌锡硫薄膜的制备方法,其特征在于,采用溅射、蒸发或电沉积工艺在所述基板表面形成所述Cu层。
4.如权利要求1所述的铜锌锡硫薄膜的制备方法,其特征在于,所述电解液的溶剂为水或者有机溶剂,电解液中铜离子的摩尔浓度∈[0,0.15]mol/L、锌离子的摩尔浓度∈[0,0.30]mol/L、锡离子的摩尔浓度∈[0,0.50]mol/L、硫离子的摩尔浓度∈(0,0.3]mol/L。
5.如权利要求1所述的铜锌锡硫薄膜的制备方法,其特征在于,所述助剂为络合剂,络合剂的摩尔浓度为0.01~1mol/L,所述络合剂选自柠檬酸钠、硫氰化钾、焦磷酸钾、柠檬酸、乙二胺四乙酸、氨三乙酸、羟基亚乙基二膦酸、酒石酸、氨基磺酸、氰化钾、氟化氨和乙二胺中的一种或几种。
6.如权利要求1或4所述的铜锌锡硫薄膜的制备方法,其特征在于,所述电解液的pH范围为0.3~13。
7.如权利要求1所述的铜锌锡硫薄膜的制备方法,其特征在于,所述助剂为能提高电解液的导电性且消除反应离子电迁移的支持电解质,所述支持电解质选自氯化钠、硫酸钠、硝酸钠、氯化钾、硫酸钾、硝酸钾、氯化铵、氯化锂、硫酸锂、硝酸锂的一种或几种。
8.如权利要求1所述的铜锌锡硫薄膜的制备方法,其特征在于,所述采用免刻蚀电化学沉积工艺在所述基板上沉积形成铜锌锡硫薄膜时,工作电极电位为-6.0~ 1.5V(vsSCE),沉积温度为20~150℃,沉积时间为10~150分钟,制得薄膜厚度为0.01~5μm。
9.如权利要求1所述的铜锌锡硫薄膜的制备方法,其特征在于,所述将沉积形成的铜锌锡硫薄膜置于含S的气氛条件下热处理,热处理的温度范围为250~550℃,热处理时间为0.1~5.5小时。
10.一种铜锌锡硫薄膜,其特征在于,所述铜锌锡硫薄膜的结构式为CuZnaSnbSc,其中,a∈[0,2],b∈[0,2],c∈(0,5]。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112246269A (zh) * | 2020-10-14 | 2021-01-22 | 吉林化工学院 | 一种C3N4-Cu2ZnSnS4复合光催化剂在光还原Cr6+中的应用 |
CN113574211A (zh) * | 2018-12-17 | 2021-10-29 | 赛峰飞机发动机公司 | 用于γ-γ”镍基超级合金的电化学加工的电解质 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101514470A (zh) * | 2009-02-20 | 2009-08-26 | 陕西科技大学 | 一种ZnS:Cu光学薄膜的制备方法 |
CN103714976A (zh) * | 2013-12-26 | 2014-04-09 | 中国矿业大学 | 一种染料敏化太阳能电池用Cu3SnS4纳米材料对电极及其制备方法 |
US20150243831A1 (en) * | 2010-08-31 | 2015-08-27 | International Business Machines Corporation | Electrodeposition of thin-film cells containing non-toxic elements |
CN105140335A (zh) * | 2015-07-17 | 2015-12-09 | 扬州大学 | 在透明导电基底上一步制备铜锌锡硫薄膜的方法 |
CN105702319A (zh) * | 2016-04-28 | 2016-06-22 | 厦门大学 | 耐弯折透明硫化铜导电膜及其制备方法 |
-
2016
- 2016-09-20 CN CN201610834664.7A patent/CN106480483A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101514470A (zh) * | 2009-02-20 | 2009-08-26 | 陕西科技大学 | 一种ZnS:Cu光学薄膜的制备方法 |
US20150243831A1 (en) * | 2010-08-31 | 2015-08-27 | International Business Machines Corporation | Electrodeposition of thin-film cells containing non-toxic elements |
CN103714976A (zh) * | 2013-12-26 | 2014-04-09 | 中国矿业大学 | 一种染料敏化太阳能电池用Cu3SnS4纳米材料对电极及其制备方法 |
CN105140335A (zh) * | 2015-07-17 | 2015-12-09 | 扬州大学 | 在透明导电基底上一步制备铜锌锡硫薄膜的方法 |
CN105702319A (zh) * | 2016-04-28 | 2016-06-22 | 厦门大学 | 耐弯折透明硫化铜导电膜及其制备方法 |
Non-Patent Citations (3)
Title |
---|
C.P. CHAN等: ""preparation of Cu2ZnSnS4 films by electrodeposition using ionic liquids"", 《SOLAR ENERGY MATERIALS & SOLAR CELLS》 * |
JIAHUA TAO等: ""synthesis and characterization of Cu2ZnSnS4 thin films by the sulfurization of co-electrodeposited Cu-Zn-Sn-S precursor layers for solar cell applications"", 《RSC ADVANCES》 * |
SAMBHAJI M. PAWAR等: ""Fabrication of Cu2ZnSnS4 thin film solar cell using single step electrodeposition method"", 《JAPANESE JOURNAL OF APPLIED PHYSICS》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113574211A (zh) * | 2018-12-17 | 2021-10-29 | 赛峰飞机发动机公司 | 用于γ-γ”镍基超级合金的电化学加工的电解质 |
CN112246269A (zh) * | 2020-10-14 | 2021-01-22 | 吉林化工学院 | 一种C3N4-Cu2ZnSnS4复合光催化剂在光还原Cr6+中的应用 |
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