CN103956406B - A kind of antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell - Google Patents
A kind of antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell Download PDFInfo
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- CN103956406B CN103956406B CN201410152965.2A CN201410152965A CN103956406B CN 103956406 B CN103956406 B CN 103956406B CN 201410152965 A CN201410152965 A CN 201410152965A CN 103956406 B CN103956406 B CN 103956406B
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- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 238000000151 deposition Methods 0.000 claims abstract description 78
- 239000010408 film Substances 0.000 claims abstract description 61
- 238000000137 annealing Methods 0.000 claims abstract description 54
- 230000008021 deposition Effects 0.000 claims abstract description 54
- 239000000758 substrate Substances 0.000 claims abstract description 54
- 239000011248 coating agent Substances 0.000 claims abstract description 52
- 238000000576 coating method Methods 0.000 claims abstract description 52
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000010409 thin film Substances 0.000 claims abstract description 32
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 16
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 16
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000889 atomisation Methods 0.000 claims abstract description 15
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 14
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 14
- 239000011787 zinc oxide Substances 0.000 claims abstract description 12
- CETDWAHZEGNBOI-UHFFFAOYSA-N antimony;sulfanylideneindium Chemical compound [Sb].[In]=S CETDWAHZEGNBOI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims abstract description 11
- YOXKVLXOLWOQBK-UHFFFAOYSA-N sulfur monoxide zinc Chemical compound [Zn].S=O YOXKVLXOLWOQBK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 10
- 239000004332 silver Substances 0.000 claims abstract description 10
- 238000000197 pyrolysis Methods 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229960001296 zinc oxide Drugs 0.000 claims abstract description 6
- 238000003854 Surface Print Methods 0.000 claims abstract description 5
- 238000007650 screen-printing Methods 0.000 claims abstract description 5
- 229920002472 Starch Polymers 0.000 claims abstract description 3
- 239000008107 starch Substances 0.000 claims abstract description 3
- 235000019698 starch Nutrition 0.000 claims abstract description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 116
- 239000002243 precursor Substances 0.000 claims description 96
- 239000007789 gas Substances 0.000 claims description 91
- 239000007864 aqueous solution Substances 0.000 claims description 86
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 46
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 45
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 29
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 28
- 239000012153 distilled water Substances 0.000 claims description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- 235000014121 butter Nutrition 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 25
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 238000004062 sedimentation Methods 0.000 claims description 24
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 24
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 21
- 229910052786 argon Inorganic materials 0.000 claims description 20
- 239000012159 carrier gas Substances 0.000 claims description 20
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 18
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 17
- 239000004246 zinc acetate Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 15
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 15
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- 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 14
- 235000019270 ammonium chloride Nutrition 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 239000011733 molybdenum Substances 0.000 claims description 12
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 12
- 238000002207 thermal evaporation Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000011592 zinc chloride Substances 0.000 claims description 10
- 235000005074 zinc chloride Nutrition 0.000 claims description 10
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 8
- 239000001119 stannous chloride Substances 0.000 claims description 8
- 235000011150 stannous chloride Nutrition 0.000 claims description 8
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 239000003570 air Substances 0.000 claims description 7
- 239000005357 flat glass Substances 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000005566 electron beam evaporation Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 claims description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 4
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- PFGAZGKYFFFSEA-UHFFFAOYSA-I aluminum zinc pentaacetate Chemical compound [Al+3].[Zn++].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O PFGAZGKYFFFSEA-UHFFFAOYSA-I 0.000 claims description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 4
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 3
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical group OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 2
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000002985 plastic film Substances 0.000 claims description 2
- 229940045105 silver iodide Drugs 0.000 claims description 2
- 238000002061 vacuum sublimation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- WDLZKULLPVDKJZ-UHFFFAOYSA-L C(C)(=O)[O-].[Zn+2].C(C)(=O)[O-].[Al+3] Chemical compound C(C)(=O)[O-].[Zn+2].C(C)(=O)[O-].[Al+3] WDLZKULLPVDKJZ-UHFFFAOYSA-L 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- PCRGAMCZHDYVOL-UHFFFAOYSA-N copper selanylidenetin zinc Chemical compound [Cu].[Zn].[Sn]=[Se] PCRGAMCZHDYVOL-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (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)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
A kind of antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell, step is: a, provide substrate, prepared by b, conductive layer: at substrate surface atomization pyrolytic deposition fluorine-doped tin dioxide thin film, antimony-doped stannic oxide film or Al-Doped ZnO film; Prepared by c, compacted zone: at conductive layer surface atomization pyrolytic deposition titanium deoxid film or zinc-oxide film; Prepared by d, resilient coating: adopt that atomization pyrolysis or chemical bath are prepared cadmium sulphide membrane, zinc sulfide film on compacted zone surface, mixed antimony indium sulfide thin film, hydrogen-oxygen indium sulfide thin film or zinc oxysulfide film; Prepared by e, absorbed layer: at buffer-layer surface atomization pyrolytic deposition copper-zinc-tin-sulfur film, and carry out annealing in process; Prepared by f, top electrode: adopt screen printing mode starch at absorbed layer surface printing black lead wash or silver and carry out annealing in process.Advantage is: the method low production cost, simple to operate, environmentally friendly, and the industrialization being applicable to solar cell is produced.
Description
Technical field
The invention belongs to solar cell preparations and applicatio field, particularly a kind of antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell.
Background technology
The film preparation of thin film solar cell is relevant with this body structure of battery, thin film solar cell mainly contains two kinds of structures: substrate structure and superstrate structure, wherein CIGS solar cell is the representative in substrate structure, and cadmium-Te solar battery is the representative in superstrate structure.Superstrate structure is relatively simple, easily encapsulates, and this is one of reason of the extensive industrialization of cadmium telluride cells energy, in addition, is also conducive to using on laminated cell.And substrate structure relative complex, main relevant with battery design and preparation technology.
Cadmium telluride (CdTe) battery and Copper Indium Gallium Selenide (CuIn
xga
1-xse
2) battery is market-oriented, but there is expensive even poisonous problem, therefore the solar cell researching and developing low-cost high-efficiency is the core content of theCourse of PV Industry, and find cheapness, environmental protection, semi-conducting material that photovoltaic conversion efficiency is high be the key developing solar cell technology.Novel quaternary semiconductor: as copper-zinc-tin-sulfur (Cu
2znSnS
4be called for short CZTS) and copper-zinc-tin-selenium (Cu
2znSnSe
4be called for short CZTSe), they possess, and light absorption is strong, component rich reserves, the advantage such as nontoxic, is expected to replace cadmium telluride and copper indium gallium selenide cell, becomes efficient, cheap films solar cell of future generation, and realize large-area applications.
At present, copper-zinc-tin-selenium solar cell main flow uses substrate structure, technology transplant is in CIGS solar cell, although battery efficiency is higher, but the Film preparations such as back electrode, absorbed layer, Window layer, top electrode generally adopt the method for vacuum evaporation or sputtering, manufacturing cost is higher, and usually will adopt the selenization process of severe toxicity, unfavorable to environment.And the copper-zinc-tin-sulfur solar cell of superstrate structure temporarily has no report.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell, and the method low production cost is simple to operate, environmentally friendly, and the industrialization being applicable to solar cell is produced.
Technical solution of the present invention is:
An antivacuum preparation method for superstrate structure copper-zinc-tin-sulfur solar cell, its concrete steps are:
A, provide substrate
Select the sheet glass, transparent plastic sheet or the polyimide piece that clean up as substrate;
Prepared by b, conductive layer
Preparation conductive layer precursor aqueous solution, described conductive layer precursor aqueous solution is ammonium fluoride-butter of tin precursor aqueous solution, trichloride antimony-butter of tin precursor aqueous solution or aluminium salt-zinc acetate precursor aqueous solution, conductive layer precursor aqueous solution becomes gas through ultrasonic atomizatio, becomes that thickness is the fluorine-doped tin dioxide thin film of 0.5 μm ~ 1.5 μm, antimony-doped stannic oxide film or Al-Doped ZnO film be as conductive layer at substrate surface pyrolytic deposition;
Prepared by c, compacted zone
Preparation compacted zone precursor aqueous solution, described compacted zone precursor aqueous solution is isopropyl titanate precursor aqueous solution or isopropyl alcohol zinc precursor solution, compacted zone precursor aqueous solution becomes gas through ultrasonic atomizatio, with compressed air, nitrogen or argon gas for carrier gas, thickness is become to be that the titanium deoxid film of 20nm ~ 200nm or zinc-oxide film are as compacted zone at conductive layer surface pyrolytic deposition;
Prepared by d, resilient coating
Adopt atomization pyrolysis or chemical bath to prepare on compacted zone surface the resilient coating that thickness is 20nm ~ 200nm, described resilient coating is cadmium sulphide membrane, zinc sulfide film, mixes antimony indium sulfide thin film, hydrogen-oxygen indium sulfide thin film or zinc oxysulfide film;
Prepared by e, absorbed layer
Preparation absorbed layer precursor aqueous solution, becomes gas by absorbed layer precursor aqueous solution through ultrasonic atomizatio, and with nitrogen or argon gas for carrier gas, preparing thickness at buffer-layer surface is 1 μm ~ 10 μm copper-zinc-tin-sulfur films, and carries out annealing in process, obtains copper zinc tin sulfur absorption layer;
During preparation absorbed layer precursor aqueous solution, by mantoquita, zinc salt, pink salt and thiocarbamide add in solvent, being mixed with mantoquita concentration is 0.2mol/L ~ 1mol/L, zinc salt concentration is 0.2mol/L ~ 1mol/L, pink salt concentration is 0.2mol/L ~ 1mol/L, thiourea concentration is the mixed solution of 0.5mol/L ~ 5mol/L, described mantoquita is dichloride copper, stannous chloride or cuprous iodide, described zinc salt is zinc dichloride or zinc iodide, described pink salt is stannous chloride, butter of tin or tin tetraiodide, described solvent is N, dinethylformamide (DMF)) and monoethanolamine according to the mixed solution of volume ratio 1:1 ~ 1:5 preparation, dimethyl sulfoxide (DMSO) (DMSO), methyl alcohol, ethanol, one in water,
During annealing in process, pass into hydrogen volume percentage composition be 0.1% ~ 4% nitrogen and hydrogen mixture, hydrogen sulfide volumn concentration be 0.1% ~ 15% hydrogen sulfide diluent gas, high pure nitrogen or argon gas be protection gas, annealing temperature is 300 DEG C ~ 600 DEG C, heating-up time is 0.5min ~ 10min, annealing time is 5min ~ 60min, and temperature fall time is 1min ~ 15min or 30min ~ 60min;
Prepared by f, top electrode
Screen printing mode is adopted to starch at absorbed layer surface printing black lead wash or silver and carry out annealing in process, or adopt vacuum thermal evaporation mode or electron-beam evaporation mode at absorbed layer surface evaporation silver, gold, molybdenum, molybdenum bisuphide, prepare the top electrode that thickness is 50nm ~ 150nm, electric current when vacuum thermal evaporation or electron beam evaporation is 80A ~ 120A; During annealing in process; pass into hydrogen volume percentage composition be 0.1% ~ 4% nitrogen and hydrogen mixture, hydrogen sulfide volumn concentration be 0.1% ~ 15% hydrogen sulfide diluent gas, high pure nitrogen or argon gas be protection gas; annealing temperature is 300 DEG C ~ 600 DEG C; heating-up time is 0.5min ~ 10min; annealing time is 5min ~ 60min, and temperature fall time is 1min ~ 15min or 30min ~ 60min.
Prepare conductive layer, compacted zone, resilient coating, absorbed layer, when carrying out atomization pyrolytic deposition, gas flow remains on 5mL/min ~ 30mL/min, and sedimentation time is 1min ~ 30min, depositing temperature is 300 DEG C ~ 600 DEG C, and spout is 0.5cm ~ 15cm to thermal station distance.
In the ammonium fluoride-butter of tin precursor aqueous solution of step b, the concentration of ammonium fluoride is 1mol/L ~ 2mol/L, the concentration of butter of tin is 0.6mol/L ~ 1mol/L, and solvent is at least one in distilled water, methyl alcohol, ethanol; In trichloride antimony-butter of tin precursor aqueous solution, the concentration 0.6mol/L ~ 1mol/L of trichloride antimony, the concentration of butter of tin are 1mol/L ~ 2mol/L, and solvent is methyl alcohol or ethanol; In aluminium salt-zinc acetate precursor aqueous solution, the concentration 0.6mol/L ~ 1mol/L of aluminium salt, acetic acid zinc concentration are 1mol/L ~ 2mol/L, and solvent is methyl alcohol or ethanol, and described aluminium salt is silver iodide or aluminium acetate.
When step c prepares isopropyl titanate precursor aqueous solution, isopropyl titanate is mixed according to mol ratio 1:1 ~ 1:5 with ethanolic solution; During preparation isopropyl alcohol zinc precursor solution, isopropyl alcohol zinc is mixed according to mol ratio 1:1 ~ 1:5 with ethanolic solution.
When resilient coating is prepared in atomization pyrolysis, first resilient coating precursor aqueous solution is prepared, resilient coating precursor aqueous solution becomes gas through ultrasonic atomizatio, resilient coating is deposited as in compacted zone surface pyrolysis, cadmium sulphide membrane resilient coating, zinc sulfide film resilient coating, mix antimony indium sulfide thin film resilient coating when preparing, pass into nitrogen or argon gas as carrier gas; Time prepared by hydrogen-oxygen indium sulfide thin film resilient coating, zinc oxysulfide foamed film resilient coating, pass into compressed air as carrier gas.
When preparing cadmium sulphide membrane, the concentration first preparing cadmium acetate is 0.05mol/L ~ 0.5mol/L, the concentration of thiocarbamide is the resilient coating precursor aqueous solution of 0.2mol/L ~ 1mol/L, and wherein solvent is distilled water, methyl alcohol or ethanol; When preparing zinc sulfide film, first prepare that acetic acid zinc concentration is 0.05mol/L ~ 0.5mol/L, the concentration of thiocarbamide is the resilient coating precursor aqueous solution of 0.2mol/L ~ 1mol/L, wherein solvent is distilled water, methyl alcohol or ethanol; When antimony indium sulfide thin film is mixed in preparation, first the concentration preparing indium trichloride is 0.1mol/L ~ 0.6mol/L, the concentration of trichloride antimony is 0.05mol/L ~ 0.5mol/L, the concentration of thiocarbamide is the resilient coating precursor aqueous solution of 0.2mol/L ~ 1mol/L, and wherein solvent is methyl alcohol or ethanol; When preparing hydrogen-oxygen indium sulfide thin film, first prepare the resilient coating precursor aqueous solution that indium trichloride concentration is 0.1mol/L ~ 0.6mol/L, thiourea concentration is 0.2mol/L ~ 1mol/L, wherein solvent is distilled water, methyl alcohol or ethanol; When preparing zinc oxysulfide film, first prepare the resilient coating precursor aqueous solution that zinc acetate concentration is 0.1mol/L ~ 0.6mol/L, thiourea concentration is 0.2mol/L ~ 1mol/L, wherein solvent is distilled water, methyl alcohol or ethanol.
Chemical bath is adopted to prepare resilient coating, time prepared by cadmium sulphide membrane, cadmium acetate, ammonium chloride, thiocarbamide and ammoniacal liquor are equipped with in the beaker of distilled water, are mixed with that cadmium acetate concentration is 0.05mol/L ~ 0.5mol/L, ammonium chloride concentration is 0.2mol/L ~ 1mol/L, thiourea concentration is 0.2mol/L ~ 1mol/L, ammonia concn is the mixed solution of 0.2mol/L ~ 1mol/L; The substrate preparing conductive layer and compacted zone is put into beaker, at-10 DEG C ~ 90 DEG C, reacts 10min ~ 100min, form cadmium sulphide membrane on compacted zone surface;
Time prepared by zinc sulfide film, zinc acetate, ammonium chloride, thiocarbamide and ammoniacal liquor being added is equipped with in the beaker of distilled water, is mixed with that zinc acetate concentration is 0.05mol/L ~ 0.5mol/L, ammonium chloride concentration is 0.2mol/L ~ 1mol/L, thiourea concentration is 0.2mol/L ~ 1mol/L, ammonia concn is the mixed solution of 0.2mol/L ~ 1mol/L; The substrate preparing conductive layer and compacted zone is put into beaker, at-10 DEG C ~ 90 DEG C, reacts 10min ~ 100min, form zinc sulfide film on compacted zone surface;
Mix antimony indium sulfide thin film when preparing, indium trichloride, trichloride antimony, thiocarbamide and ammoniacal liquor being added is equipped with in the beaker of distilled water, is mixed with that indium trichloride concentration is 0.1mol/L ~ 0.6mol/L, trichloride antimony concentration is 0.05mol/L ~ 0.5mol/L, thiourea concentration is 0.2mol/L ~ 1mol/L and ammonia concn is the mixed solution of 0.1mol/L ~ 0.5mol/L; The substrate preparing conductive layer and compacted zone is put into beaker, at-10 DEG C ~ 90 DEG C, reacts 10min ~ 100min, formed on compacted zone surface and mix antimony indium sulfide thin film;
Time prepared by hydrogen-oxygen indium sulfide thin film, indium trichloride, thiocarbamide and ammoniacal liquor being added is equipped with in the beaker of distilled water, is mixed with that indium trichloride concentration is 0.1mol/L ~ 0.6mol/L, thiourea concentration is 0.2mol/L ~ 1mol/L, the mixed solution of ammonia concn 0.2-1 mole often liter; The substrate preparing conductive layer and compacted zone is put into beaker, at-10 DEG C ~ 90 DEG C, reacts 10min ~ 100min, form hydrogen-oxygen indium sulfide thin film on compacted zone surface;
During zinc oxysulfide film preparation, zinc acetate, thiocarbamide and ammoniacal liquor are added and is equipped with in the beaker of distilled water, be mixed with that zinc acetate concentration is 0.05mol/L ~ 0.6mol/L, thiourea concentration is 0.2mol/L ~ 1mol/L, ammonia concn is 0.2mol/L ~ 1mol/L; The substrate preparing conductive layer and compacted zone is put into beaker, at-10 DEG C ~ 90 DEG C, reacts 10min ~ 100min, form zinc oxysulfide film on compacted zone surface.
Described black lead wash is mixed according to mass ratio 10:3 ~ 10:2,10:2 ~ 10:1 respectively electrically conductive graphite and cellulose, terpinol, and the purity of Vacuum sublimation or electron beam evaporation material silver used, gold, molybdenum or molybdenum bisuphide is 99.9% ~ 99.99%.
During cleaning substrate, substrate is put in beaker, pours acetone into, ultrasonic cleaning 5min ~ 8min, then use alcohol ultrasonic cleaning 5min ~ 8min, then with saturated NaOH alcohol solution dipping ultrasonic cleaning 20min ~ 25min, finally use deionized water rinsing, natural drying.
Beneficial effect of the present invention:
(1) in preparation process, except preparing top electrode, all retes carry out completely under non-vacuum condition, preparing thin-film process mainly adopts atomization pyrolysis or chemical bath to carry out, use raw material is cheap inorganic salts, raw material availability is high, has the advantage of low production cost compared with the vacuum evaporation of routine or sputtering and selenization process.
(2) adopt the mode of atomization pyrolysis to be applicable to the preparation of large-area solar cell, be conducive to the industrialization of solar cell.
(3) advantages of nontoxic raw materials used in cell manufacturing process, avoids poisonous selenization process, safety non-pollution, environmentally friendly.
Accompanying drawing explanation
Fig. 1 is the XRD figure of fluorine-doped tin dioxide conductive layer of the present invention;
Fig. 2 is the XRD figure of cadmium sulfide resilient coating of the present invention;
Fig. 3 is the XRD figure of copper zinc tin sulfur absorption layer of the present invention;
Fig. 4 is the Raman spectrogram of copper zinc tin sulfur absorption layer of the present invention;
Fig. 5 is the scanning electron microscope (SEM) photograph of copper zinc tin sulfur absorption layer of the present invention;
Fig. 6 is the XRD figure of antimony-doped stannic oxide conductive layer of the present invention;
Fig. 7 is the XRD figure of zinc sulphide resilient coating of the present invention;
Fig. 8 is the XRD figure of Al-Doped ZnO conductive layer of the present invention.
Embodiment
Embodiment 1
A, provide substrate
Select sheet glass as substrate, substrate is put in beaker, pours acetone into, ultrasonic cleaning 5min, then use alcohol ultrasonic cleaning 5min, then with saturated NaOH alcohol solution dipping ultrasonic cleaning 20min, finally use deionized water rinsing, natural drying;
Prepared by b, conductive layer
Ammonium fluoride and butter of tin are added in distilled water the concentration preparing ammonium fluoride is 1mol/L, the concentration of butter of tin is the ammonium fluoride of 0.6mol/L-butter of tin precursor aqueous solution, ammonium fluoride-butter of tin precursor aqueous solution becomes gas through ultrasonic atomizatio, thickness is become to be that the fluorine-doped tin dioxide thin film of 0.5 μm is as conductive layer at substrate surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 5mL/min, sedimentation time is 1min, depositing temperature is 300 DEG C, and spout is 0.5cm to thermal station distance;
Prepared by c, compacted zone
Isopropyl titanate and ethanolic solution are mixed according to mol ratio 1:1 and is mixed with isopropyl titanate precursor aqueous solution, isopropyl titanate precursor aqueous solution becomes gas through ultrasonic atomizatio, take compressed air as carrier gas, thickness is become to be that the titanium deoxid film of 20nm is as compacted zone at conductive layer surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 5mL/min, sedimentation time is 1min, and depositing temperature is 300 DEG C, and spout is 0.5cm to thermal station distance;
Prepared by d, resilient coating
Cadmium acetate and thiocarbamide are added in distilled water the concentration being mixed with cadmium acetate is 0.05mol/L, the concentration of thiocarbamide is the cadmium acetate of 0.2mol/L-thiocarbamide precursor aqueous solution, cadmium acetate-thiocarbamide precursor aqueous solution becomes gas through ultrasonic atomizatio, nitrogen buffer gas, the cadmium sulphide membrane resilient coating that thickness is 20nm is prepared on compacted zone surface, during pyrolytic deposition, gas flow remains on 5mL/min, sedimentation time is 1min, and depositing temperature is 300 DEG C, and spout is 0.5cm to thermal station distance;
Prepared by e, absorbed layer
Dichloride copper, zinc dichloride, stannous chloride and thiocarbamide are added in methyl alcohol, be mixed with the absorbed layer precursor aqueous solution that dichloride copper concentration is 0.2mol/L, zinc dichloride concentration is 0.2mol/L, stannous chloride concentration is 0.2mol/L, thiourea concentration is 0.5mol/L, absorbed layer precursor aqueous solution is become gas through ultrasonic atomizatio, nitrogen buffer gas, thickness is become to be 1 μm of copper-zinc-tin-sulfur film at buffer-layer surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 5mL/min, sedimentation time is 1min depositing temperature is 100 DEG C, and spout is 0.5cm to thermal station distance; Then carry out annealing in process, during annealing in process, pass into the nitrogen and hydrogen mixture that hydrogen volume percentage composition is 0.1%, annealing temperature is 300 DEG C, and the heating-up time is 0.5min, and annealing time is 60min, and temperature fall time is 1min, obtains copper zinc tin sulfur absorption layer;
Prepared by f, top electrode
Adopt screen printing mode at absorbed layer surface printing black lead wash; described black lead wash is mixed according to mass ratio 10:3:2 respectively electrically conductive graphite and cellulose, terpinol; then annealing in process is carried out; obtain the top electrode that thickness is 500nm, during annealing in process, pass into high pure nitrogen for protection gas; annealing temperature is 300 DEG C; heating-up time is 0.5min, and annealing time is 60min, and temperature fall time is 1min.
Embodiment 2
A, provide substrate
Select sheet glass as substrate, substrate is put in beaker, pours acetone into, ultrasonic cleaning 8min, then use alcohol ultrasonic cleaning 8min, then with saturated NaOH alcohol solution dipping ultrasonic cleaning 25min, finally use deionized water rinsing, natural drying;
Prepared by b, conductive layer
Ammonium fluoride and butter of tin are added in ethanol the concentration preparing ammonium fluoride is 2mol/L, the concentration of butter of tin is the ammonium fluoride of 1mol/L-butter of tin precursor aqueous solution, ammonium fluoride-butter of tin precursor aqueous solution becomes gas through ultrasonic atomizatio, thickness is become to be that the fluorine-doped tin dioxide thin film of 1.5 μm is as conductive layer at substrate surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 30mL/min, sedimentation time is 30min, depositing temperature is 600 DEG C, and spout is 15cm to thermal station distance;
Prepared by c, compacted zone
Isopropyl titanate and ethanolic solution are mixed according to mol ratio 1:5 and is mixed with isopropyl titanate precursor aqueous solution, isopropyl titanate precursor aqueous solution becomes gas through ultrasonic atomizatio, nitrogen buffer gas, thickness is become to be that the titanium deoxid film of 200nm is as compacted zone at conductive layer surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 30mL/min, sedimentation time is 30min, and depositing temperature is 600 DEG C, and spout is 15cm to thermal station distance;
Prepared by d, resilient coating
Cadmium acetate and thiocarbamide are added in distilled water the concentration being mixed with cadmium acetate is 0.5mol/L, the concentration of thiocarbamide is the cadmium acetate of 1mol/L-thiocarbamide precursor aqueous solution, cadmium acetate-thiocarbamide precursor aqueous solution becomes gas through ultrasonic atomizatio, take argon gas as carrier gas, the cadmium sulphide membrane resilient coating that thickness is 200nm is prepared on compacted zone surface, during pyrolytic deposition, gas flow remains on 30mL/min, sedimentation time is 30min, and depositing temperature is 600 DEG C, and spout is 15cm to thermal station distance;
Prepared by e, absorbed layer
Cuprous iodide, zinc iodide, tin tetraiodide and thiocarbamide are added in ethanol, be mixed with the absorbed layer precursor aqueous solution that cuprous iodide concentration is 1mol/L, zinc iodide concentration is 1mol/L, tin tetraiodide concentration is 1mol/L, thiourea concentration is 5mol/L, absorbed layer precursor aqueous solution is become gas through ultrasonic atomizatio, take argon gas as carrier gas, thickness is become to be 10 μm of copper-zinc-tin-sulfur films at buffer-layer surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 30mL/min, sedimentation time is 30min, depositing temperature is 600 DEG C, and spout is 15cm to thermal station distance; Then carry out annealing in process, during annealing in process, pass into argon gas, annealing temperature is 600 DEG C, and the heating-up time is 10min, and annealing time is 5min, and temperature fall time is 60min, obtains copper zinc tin sulfur absorption layer;
Prepared by f, top electrode
Adopt screen printing mode at absorbed layer surface printing silver slurry, then carry out annealing in process, obtain the top electrode that thickness is 150nm, during annealing in process, pass into argon gas, annealing temperature is 600 DEG C, heating-up time is 10min, and annealing time is 5min, and temperature fall time is 60min.
Embodiment 3
A, provide substrate
Select polyimide piece as substrate, substrate is put in beaker, pours acetone into, ultrasonic cleaning 6min, then use alcohol ultrasonic cleaning 6min, then with saturated NaOH alcohol solution dipping ultrasonic cleaning 22min, finally use deionized water rinsing, natural drying;
Prepared by b, conductive layer
Ammonium fluoride and butter of tin are added in methyl alcohol the concentration preparing ammonium fluoride is 1.5mol/L, the concentration of butter of tin is the ammonium fluoride of 0.8mol/L-butter of tin precursor aqueous solution, ammonium fluoride-butter of tin precursor aqueous solution becomes gas through ultrasonic atomizatio, thickness is become to be that the fluorine-doped tin dioxide thin film of 1 μm is as conductive layer at substrate surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, depositing temperature is 400 DEG C, and spout is 8cm to thermal station distance; The XRD figure of fluorine-doped tin dioxide thin film conductive layer as shown in Figure 1, in figure, a represents commodity fluorine-doped tin dioxide (FTO), b represents in the present invention the fluorine-doped tin dioxide (FTO) being atomized pyrolysismethod and obtaining, as seen from Figure 1, the two spectrogram is substantially identical, shows that the fluorine-doped tin dioxide (FTO) obtained is pure phase;
Prepared by c, compacted zone
Isopropyl titanate and ethanolic solution are mixed according to mol ratio 1:2 and is mixed with isopropyl titanate precursor aqueous solution, isopropyl titanate precursor aqueous solution becomes gas through ultrasonic atomizatio, take argon gas as carrier gas, thickness is become to be that the titanium deoxid film of 100nm is as compacted zone at conductive layer surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, and depositing temperature is 400 DEG C, and spout is 8cm to thermal station distance;
Prepared by d, resilient coating
Cadmium acetate and thiocarbamide are added in distilled water the concentration being mixed with cadmium acetate is 0.2mol/L, the concentration of thiocarbamide is the cadmium acetate of 0.5mol/L-thiocarbamide precursor aqueous solution, cadmium acetate-thiocarbamide precursor aqueous solution becomes gas through ultrasonic atomizatio, take argon gas as carrier gas, the cadmium sulphide membrane resilient coating that thickness is 100nm is prepared on compacted zone surface, during pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, and depositing temperature is 400 DEG C, and spout is 8cm to thermal station distance; The XRD figure of cadmium sulfide resilient coating as shown in Figure 2;
Prepared by e, absorbed layer
Dichloride copper, zinc dichloride, butter of tin and thiocarbamide are added in solvent, be mixed with the absorbed layer precursor aqueous solution that dichloride copper concentration is 0.2mol/L, zinc dichloride concentration is 0.2mol/L, butter of tin concentration is 0.2mol/L, thiourea concentration is 0.5mol/L, described solvent is DMF (DMF)) and the mixed solution prepared according to volume ratio 1:1 of monoethanolamine; Absorbed layer precursor aqueous solution is become gas through ultrasonic atomizatio, take argon gas as carrier gas, becomes thickness to be 5 μm of copper-zinc-tin-sulfur films at buffer-layer surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, and depositing temperature is 400 DEG C, and spout is 8cm to thermal station distance; Then carry out annealing in process, during annealing in process, pass into high pure nitrogen for protection gas, annealing temperature is 400 DEG C, and the heating-up time is 5min, and annealing time is 30min, and temperature fall time is 15min, obtains copper zinc tin sulfur absorption layer; As shown in Figure 3, as shown in Figure 4, as shown in Figure 5, copper zinc tin sulfur absorption layer is evenly distributed the scanning electron microscope (SEM) photograph of copper zinc tin sulfur absorption layer the Raman spectrogram of copper zinc tin sulfur absorption layer the XRD figure of copper zinc tin sulfur absorption layer as seen from Figure 5;
Prepared by f, top electrode
Adopt vacuum thermal evaporation mode; be that the gold (Au) of 99.9% is at absorbed layer surface gold evaporation by purity; then annealing in process is carried out; obtain the top electrode that thickness is 100nm, during annealing in process, pass into high pure nitrogen for protection gas; annealing temperature is 400 DEG C; heating-up time is 5min, and annealing time is 30min, and temperature fall time is 15min.
Embodiment 4
A, provide substrate
Select sheet glass as substrate, substrate is put in beaker, pours acetone into, ultrasonic cleaning 6min, then use alcohol ultrasonic cleaning 6min, then with saturated NaOH alcohol solution dipping ultrasonic cleaning 22min, finally use deionized water rinsing, natural drying;
Prepared by b, conductive layer
Trichloride antimony and butter of tin are added in methyl alcohol the concentration preparing ammonium fluoride is 0.8mol/L, the concentration of butter of tin is the trichloride antimony of 1.5mol/L-butter of tin precursor aqueous solution, trichloride antimony-butter of tin precursor aqueous solution becomes gas through ultrasonic atomizatio, thickness is become to be that the antimony-doped stannic oxide film of 1 μm is as conductive layer at substrate surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, depositing temperature is 400 DEG C, and spout is 8cm to thermal station distance; The XRD figure of antimony-doped stannic oxide film conductive layer as shown in Figure 6; The square resistance obtaining antimony-doped stannic oxide with four probe method test is 10 Ω/;
Prepared by c, compacted zone
Isopropyl alcohol zinc and ethanolic solution are mixed according to mol ratio 1:2 and is mixed with isopropyl alcohol zinc precursor solution, isopropyl alcohol zinc precursor solution becomes gas through ultrasonic atomizatio, take compressed air as carrier gas, thickness is become to be that the zinc-oxide film of 100nm is as compacted zone at conductive layer surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, and depositing temperature is 400 DEG C, and spout is 8cm to thermal station distance;
Prepared by d, resilient coating
Zinc acetate, ammonium chloride, thiocarbamide and ammoniacal liquor being added is equipped with in the beaker of distilled water, is mixed with that zinc acetate concentration is 0.05mol/L, ammonium chloride concentration is 0.2mol/L, thiourea concentration is 0.2mol/L, ammonia concn is the mixed solution of 0.2mol/L; The substrate preparing conductive layer and compacted zone is put into beaker, at-10 DEG C, reacts 10min, forming thickness on compacted zone surface is the zinc sulfide film of 100nm; The XRD figure of zinc sulphide resilient coating as shown in Figure 7;
Prepared by e, absorbed layer
Stannous chloride, zinc iodide, butter of tin and thiocarbamide are added in ethanol, be mixed with the absorbed layer precursor aqueous solution that stannous chloride concentration is 0.5mol/L, zinc iodide concentration is 0.5mol/L, butter of tin concentration is 0.5mol/L, thiourea concentration is 2mol/L, absorbed layer precursor aqueous solution is become gas through ultrasonic atomizatio, take argon gas as carrier gas, thickness is become to be 5 μm of copper-zinc-tin-sulfur films at buffer-layer surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, depositing temperature is 400 DEG C, and spout is 8cm to thermal station distance; Then carry out annealing in process, during annealing in process, pass into high pure nitrogen for protection gas, annealing temperature is 400 DEG C, and the heating-up time is 5min, and annealing time is 30min, and temperature fall time is 15min, obtains copper zinc tin sulfur absorption layer;
Prepared by f, top electrode
Adopt vacuum thermal evaporation mode purity be the silver (Ag) of 99.9% at absorbed layer surface evaporation silver, obtain the top electrode that thickness is 100nm, electric current during vacuum thermal evaporation is 80A;
Embodiment 5
A, provide substrate
Select sheet glass as substrate, substrate is put in beaker, pours acetone into, ultrasonic cleaning 6min, then use alcohol ultrasonic cleaning 6min, then with saturated NaOH alcohol solution dipping ultrasonic cleaning 22min, finally use deionized water rinsing, natural drying;
Prepared by b, conductive layer
Concentration trichloride antimony and butter of tin being added to the water preparation ammonium fluoride is 0.6mol/L, the concentration of butter of tin is the trichloride antimony of 1mol/L-butter of tin precursor aqueous solution, trichloride antimony-butter of tin precursor aqueous solution becomes gas through ultrasonic atomizatio, thickness is become to be that the antimony-doped stannic oxide film of 1 μm is as conductive layer at substrate surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, depositing temperature is 400 DEG C, and spout is 8cm to thermal station distance;
Prepared by c, compacted zone
Isopropyl alcohol zinc and ethanolic solution are mixed according to mol ratio 1:2 and is mixed with isopropyl alcohol zinc precursor solution, isopropyl alcohol zinc precursor solution becomes gas through ultrasonic atomizatio, take compressed air as carrier gas, thickness is become to be that the zinc-oxide film of 100nm is as compacted zone at conductive layer surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, and depositing temperature is 400 DEG C, and spout is 8cm to thermal station distance;
Prepared by d, resilient coating
Zinc acetate, ammonium chloride, thiocarbamide and ammoniacal liquor being added is equipped with in the beaker of distilled water, is mixed with that zinc acetate concentration is 0.05mol/L, ammonium chloride concentration is 0.2mol/L, thiourea concentration is 1mol/L, ammonia concn is the mixed solution of 1mol/L; The substrate preparing conductive layer and compacted zone is put into beaker, at 90 DEG C, reacts 100min, forming thickness on compacted zone surface is the zinc sulfide film of 100nm;
Prepared by e, absorbed layer
Dichloride copper, zinc dichloride, butter of tin and thiocarbamide are added in solvent, be mixed with the absorbed layer precursor aqueous solution that dichloride copper concentration is 1mol/L, zinc dichloride concentration is 1mol/L, butter of tin concentration is 1mol/L, thiourea concentration is 5mol/L, described solvent is DMF (DMF)) and the mixed solution prepared according to volume ratio 1:5 of monoethanolamine; Absorbed layer precursor aqueous solution is become gas through ultrasonic atomizatio, take argon gas as carrier gas, becomes thickness to be 5 μm of copper-zinc-tin-sulfur films at buffer-layer surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, and depositing temperature is 400 DEG C, and spout is 8cm to thermal station distance; Then carry out annealing in process, during annealing in process, pass into high pure nitrogen for protection gas, annealing temperature is 400 DEG C, and the heating-up time is 5min, and annealing time is 30min, and temperature fall time is 15min, obtains copper zinc tin sulfur absorption layer;
Prepared by f, top electrode
Employing vacuum thermal evaporation mode purity is the molybdenum bisuphide (MoS of 99.9%
2) at absorbed layer surface evaporation molybdenum bisuphide, obtain the top electrode that thickness is 100nm, electric current during vacuum thermal evaporation is 120A;
Embodiment 6
A, provide substrate
Select sheet glass as substrate, substrate is put in beaker, pours acetone into, ultrasonic cleaning 6min, then use alcohol ultrasonic cleaning 6min, then with saturated NaOH alcohol solution dipping ultrasonic cleaning 22min, finally use deionized water rinsing, natural drying;
Prepared by b, conductive layer
Concentration trichloride antimony and butter of tin being added to the water preparation ammonium fluoride is 4mol/L, the concentration of butter of tin is the trichloride antimony of 2mol/L-butter of tin precursor aqueous solution, trichloride antimony-butter of tin precursor aqueous solution becomes gas through ultrasonic atomizatio, thickness is become to be that the antimony-doped stannic oxide film of 1 μm is as conductive layer at substrate surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, depositing temperature is 400 DEG C, and spout is 8cm to thermal station distance;
Prepared by c, compacted zone
Isopropyl alcohol zinc and ethanolic solution are mixed according to mol ratio 1:2 and is mixed with isopropyl alcohol zinc precursor solution, isopropyl alcohol zinc precursor solution becomes gas through ultrasonic atomizatio, take compressed air as carrier gas, thickness is become to be that the zinc-oxide film of 100nm is as compacted zone at conductive layer surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, and depositing temperature is 400 DEG C, and spout is 8cm to thermal station distance;
Prepared by d, resilient coating
Zinc acetate, ammonium chloride, thiocarbamide and ammoniacal liquor being added is equipped with in the beaker of distilled water, is mixed with that zinc acetate concentration is 0.2mol/L, ammonium chloride concentration is 0.5mol/L, thiourea concentration is 0.5mol/L, ammonia concn is the mixed solution of 0.5mol/L; The substrate preparing conductive layer and compacted zone is put into beaker, at 50 DEG C, reacts 50min, forming thickness on compacted zone surface is the zinc sulfide film of 100nm;
Prepared by e, absorbed layer
Dichloride copper, zinc dichloride, butter of tin and thiocarbamide are added in solvent, be mixed with the absorbed layer precursor aqueous solution that dichloride copper concentration is 0.5mol/L, zinc dichloride concentration is 0.5mol/L, butter of tin concentration is 0.5mol/L, thiourea concentration is 2mol/L, described solvent is DMF (DMF)) and the mixed solution prepared according to volume ratio 1:2 of monoethanolamine; Absorbed layer precursor aqueous solution is become gas through ultrasonic atomizatio, take argon gas as carrier gas, becomes thickness to be 5 μm of copper-zinc-tin-sulfur films at buffer-layer surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, and depositing temperature is 400 DEG C, and spout is 8cm to thermal station distance; Then carry out annealing in process, during annealing in process, pass into high pure nitrogen for protection gas, annealing temperature is 400 DEG C, and the heating-up time is 5min, and annealing time is 30min, and temperature fall time is 15min, obtains copper zinc tin sulfur absorption layer;
Prepared by f, top electrode
Adopt purity to be 99.9% molybdenum (Mo) vacuum thermal evaporation mode at absorbed layer surface evaporation molybdenum, obtain the top electrode that thickness is 100nm, the electric current of vacuum thermal evaporation is 100A.
Embodiment 7
The preparation of step b conductive layer: aluminium acetate and zinc acetate being added in methyl alcohol concentration 1mol/L, the acetic acid zinc concentration of preparing aluminium acetate is that the aluminium acetate-zinc acetate precursor aqueous solution aluminium acetate-zinc acetate precursor aqueous solution of 1mol/L becomes gas through ultrasonic atomizatio, thickness is become to be that the Al-Doped ZnO film of 1 μm is as conductive layer at substrate surface pyrolytic deposition, during pyrolytic deposition, gas flow remains on 15mL/min, sedimentation time is 15min, depositing temperature is 400 DEG C, and spout is 8cm to thermal station distance; The XRD figure of Al-Doped ZnO film as shown in Figure 8; (step a, step c ~ step f) is with embodiment 3 for other step.
Claims (9)
1. an antivacuum preparation method for superstrate structure copper-zinc-tin-sulfur solar cell, is characterized in that: concrete steps are:
A, provide substrate
Select the sheet glass, transparent plastic sheet or the polyimide piece that clean up as substrate;
Prepared by b, conductive layer
Preparation conductive layer precursor aqueous solution carries out atomization pyrolytic deposition, described conductive layer precursor aqueous solution is ammonium fluoride-butter of tin precursor aqueous solution, trichloride antimony-butter of tin precursor aqueous solution or aluminium salt-zinc acetate precursor aqueous solution, conductive layer precursor aqueous solution becomes gas through ultrasonic atomizatio, becomes that thickness is the fluorine-doped tin dioxide thin film of 0.5 μm ~ 1.5 μm, antimony-doped stannic oxide film or Al-Doped ZnO film be as conductive layer at substrate surface pyrolytic deposition;
Prepared by c, compacted zone
Preparation compacted zone precursor aqueous solution carries out atomization pyrolytic deposition, described compacted zone precursor aqueous solution is isopropyl titanate precursor aqueous solution or isopropyl alcohol zinc precursor solution, compacted zone precursor aqueous solution becomes gas through ultrasonic atomizatio, with compressed air, nitrogen or argon gas for carrier gas, thickness is become to be that the titanium deoxid film of 20nm ~ 200nm or zinc-oxide film are as compacted zone at conductive layer surface pyrolytic deposition;
Prepared by d, resilient coating
Adopt atomization pyrolysis or chemical bath to prepare on compacted zone surface the resilient coating that thickness is 20nm ~ 200nm, described resilient coating is cadmium sulphide membrane, zinc sulfide film, mixes antimony indium sulfide thin film, hydrogen-oxygen indium sulfide thin film or zinc oxysulfide film;
Prepared by e, absorbed layer
Preparation absorbed layer precursor aqueous solution carries out atomization pyrolytic deposition, absorbed layer precursor aqueous solution is become gas through ultrasonic atomizatio, with nitrogen or argon gas for carrier gas, becomes thickness to be 1 μm ~ 10 μm copper-zinc-tin-sulfur films at buffer-layer surface pyrolytic deposition, and carry out annealing in process, obtain copper zinc tin sulfur absorption layer;
During preparation absorbed layer precursor aqueous solution, by mantoquita, zinc salt, pink salt and thiocarbamide add in solvent, being mixed with mantoquita concentration is 0.2mol/L ~ 1mol/L, zinc salt concentration is 0.2mol/L ~ 1mol/L, pink salt concentration is 0.2mol/L ~ 1mol/L, thiourea concentration is the mixed solution of 0.5mol/L ~ 5mol/L, described mantoquita is dichloride copper, stannous chloride or cuprous iodide, described zinc salt is zinc dichloride or zinc iodide, described pink salt is stannous chloride, butter of tin or tin tetraiodide, described solvent is N, the mixed solution that dinethylformamide and monoethanolamine are prepared according to volume ratio 1:1 ~ 1:5, dimethyl sulfoxide (DMSO), methyl alcohol, ethanol, one in water,
During annealing in process, pass into hydrogen volume percentage composition be 0.1% ~ 4% nitrogen and hydrogen mixture, hydrogen sulfide volumn concentration be 0.1% ~ 15% hydrogen sulfide diluent gas, high pure nitrogen or argon gas be protection gas, annealing temperature is 300 DEG C ~ 600 DEG C, heating-up time is 0.5min ~ 10min, annealing time is 5min ~ 60min, and temperature fall time is 1min ~ 15min or 30min ~ 60min;
Prepared by f, top electrode
Screen printing mode is adopted to starch at absorbed layer surface printing black lead wash or silver and carry out annealing in process, or adopt vacuum thermal evaporation mode or electron-beam evaporation mode, at absorbed layer surface evaporation silver, gold, molybdenum or molybdenum bisuphide, prepare the top electrode that thickness is 50nm ~ 150nm, electric current when vacuum thermal evaporation or electron beam evaporation is 80A ~ 120A; During annealing in process; pass into hydrogen volume percentage composition be 0.1% ~ 4% nitrogen and hydrogen mixture, hydrogen sulfide volumn concentration be 0.1% ~ 15% hydrogen sulfide diluent gas, high pure nitrogen or argon gas be protection gas; annealing temperature is 300 DEG C ~ 600 DEG C; heating-up time is 0.5min ~ 10min; annealing time is 5min ~ 60min, and temperature fall time is 1min ~ 15min or 30min ~ 60min.
2. the antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell according to claim 1, is characterized in that:
Prepare conductive layer, compacted zone, resilient coating, absorbed layer, when carrying out atomization pyrolytic deposition, gas flow remains on 5mL/min ~ 30mL/min, and sedimentation time is 1min ~ 30min, depositing temperature is 300 DEG C ~ 600 DEG C, and spout is 0.5cm ~ 15cm to thermal station distance.
3. the antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell according to claim 1, is characterized in that:
In the ammonium fluoride-butter of tin precursor aqueous solution of step b, the concentration of ammonium fluoride is 1mol/L ~ 2mol/L, the concentration of butter of tin is 0.6mol/L ~ 1mol/L, and solvent is at least one in distilled water, methyl alcohol, ethanol; In trichloride antimony-butter of tin precursor aqueous solution, the concentration 0.6mol/L ~ 1mol/L of trichloride antimony, the concentration of butter of tin are 1mol/L ~ 2mol/L, and solvent is methyl alcohol or ethanol; In aluminium salt-zinc acetate precursor aqueous solution, the concentration 0.6mol/L ~ 1mol/L of aluminium salt, acetic acid zinc concentration are 1mol/L ~ 2mol/L, and solvent is methyl alcohol or ethanol, and described aluminium salt is silver iodide or aluminium acetate.
4. the antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell according to claim 1, is characterized in that:
When step c prepares isopropyl titanate precursor aqueous solution, isopropyl titanate is mixed according to mol ratio 1:1 ~ 1:5 with ethanolic solution; During preparation isopropyl alcohol zinc precursor solution, isopropyl alcohol zinc is mixed according to mol ratio 1:1 ~ 1:5 with ethanolic solution.
5. the antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell according to claim 1, is characterized in that:
When resilient coating is prepared in atomization pyrolysis, first resilient coating precursor aqueous solution is prepared, resilient coating precursor aqueous solution becomes gas through ultrasonic atomizatio, resilient coating is deposited as in compacted zone surface pyrolysis, cadmium sulphide membrane resilient coating, zinc sulfide film resilient coating, mix antimony indium sulfide thin film resilient coating when preparing, pass into nitrogen or argon gas as carrier gas; Time prepared by hydrogen-oxygen indium sulfide thin film resilient coating, zinc oxysulfide foamed film resilient coating, pass into compressed air as carrier gas.
6. the antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell according to claim 5, is characterized in that:
When preparing cadmium sulphide membrane, the concentration first preparing cadmium acetate is 0.05mol/L ~ 0.5mol/L, the concentration of thiocarbamide is the resilient coating precursor aqueous solution of 0.2mol/L ~ 1mol/L, and wherein solvent is distilled water, methyl alcohol or ethanol; When preparing zinc sulfide film, first prepare that acetic acid zinc concentration is 0.05mol/L ~ 0.5mol/L, the concentration of thiocarbamide is the resilient coating precursor aqueous solution of 0.2mol/L ~ 1mol/L, wherein solvent is distilled water, methyl alcohol or ethanol; When antimony indium sulfide thin film is mixed in preparation, first the concentration preparing indium trichloride is 0.1mol/L ~ 0.6mol/L, the concentration of trichloride antimony is 0.05mol/L ~ 0.5mol/L, the concentration of thiocarbamide is the resilient coating precursor aqueous solution of 0.2mol/L ~ 1mol/L, and wherein solvent is methyl alcohol or ethanol; When preparing hydrogen-oxygen indium sulfide thin film, first prepare the resilient coating precursor aqueous solution that indium trichloride concentration is 0.1mol/L ~ 0.6mol/L, thiourea concentration is 0.2mol/L ~ 1mol/L, wherein solvent is distilled water, methyl alcohol or ethanol; When preparing zinc oxysulfide film, first prepare the resilient coating precursor aqueous solution that zinc acetate concentration is 0.1mol/L ~ 0.6mol/L, thiourea concentration is 0.2mol/L ~ 1mol/L, wherein solvent is distilled water, methyl alcohol or ethanol.
7. the antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell according to claim 1, it is characterized in that: adopt chemical bath to prepare resilient coating, time prepared by cadmium sulphide membrane, cadmium acetate, ammonium chloride, thiocarbamide and ammoniacal liquor are equipped with in the beaker of distilled water, are mixed with that cadmium acetate concentration is 0.05mol/L ~ 0.5mol/L, ammonium chloride concentration is 0.2mol/L ~ 1mol/L, thiourea concentration is 0.2mol/L ~ 1mol/L, ammonia concn is the mixed solution of 0.2mol/L ~ 1mol/L; The substrate preparing conductive layer and compacted zone is put into beaker, at-10 DEG C ~ 90 DEG C, reacts 10min ~ 100min, form cadmium sulphide membrane on compacted zone surface;
Time prepared by zinc sulfide film, zinc acetate, ammonium chloride, thiocarbamide and ammoniacal liquor being added is equipped with in the beaker of distilled water, is mixed with that zinc acetate concentration is 0.05mol/L ~ 0.5mol/L, ammonium chloride concentration is 0.2mol/L ~ 1mol/L, thiourea concentration is 0.2mol/L ~ 1mol/L, ammonia concn is the mixed solution of 0.2mol/L ~ 1mol/L; The substrate preparing conductive layer and compacted zone is put into beaker, at-10 DEG C ~ 90 DEG C, reacts 10min ~ 100min, form zinc sulfide film on compacted zone surface;
Mix antimony indium sulfide thin film when preparing, indium trichloride, trichloride antimony, thiocarbamide and ammoniacal liquor being added is equipped with in the beaker of distilled water, is mixed with that indium trichloride concentration is 0.1mol/L ~ 0.6mol/L, trichloride antimony concentration is 0.05mol/L ~ 0.5mol/L, thiourea concentration is 0.2mol/L ~ 1mol/L and ammonia concn is the mixed solution of 0.1mol/L ~ 0.5mol/L; The substrate preparing conductive layer and compacted zone is put into beaker, at-10 DEG C ~ 90 DEG C, reacts 10min ~ 100min, formed on compacted zone surface and mix antimony indium sulfide thin film;
Time prepared by hydrogen-oxygen indium sulfide thin film, indium trichloride, thiocarbamide and ammoniacal liquor being added is equipped with in the beaker of distilled water, is mixed with that indium trichloride concentration is 0.1mol/L ~ 0.6mol/L, thiourea concentration is 0.2mol/L ~ 1mol/L, the mixed solution of ammonia concn 0.2-1 mole often liter; The substrate preparing conductive layer and compacted zone is put into beaker, at-10 DEG C ~ 90 DEG C, reacts 10min ~ 100min, form hydrogen-oxygen indium sulfide thin film on compacted zone surface;
During zinc oxysulfide film preparation, zinc acetate, thiocarbamide and ammoniacal liquor are added and is equipped with in the beaker of distilled water, be mixed with that zinc acetate concentration is 0.05mol/L ~ 0.6mol/L, thiourea concentration is 0.2mol/L ~ 1mol/L, ammonia concn is 0.2mol/L ~ 1mol/L; The substrate preparing conductive layer and compacted zone is put into beaker, at-10 DEG C ~ 90 DEG C, reacts 10min ~ 100min, form zinc oxysulfide film on compacted zone surface.
8. the antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell according to claim 1, it is characterized in that: described black lead wash is mixed according to mass ratio 10:3 ~ 10:2,10:2 ~ 10:1 respectively electrically conductive graphite and cellulose, terpinol, the purity of Vacuum sublimation or electron beam evaporation material silver used, gold, molybdenum or molybdenum bisuphide is 99.9% ~ 99.99%.
9. the antivacuum preparation method of superstrate structure copper-zinc-tin-sulfur solar cell according to claim 1, it is characterized in that: during cleaning substrate, substrate is put in beaker, pour acetone into, ultrasonic cleaning 5min ~ 8min, then use alcohol ultrasonic cleaning 5min ~ 8min, then with saturated NaOH alcohol solution dipping ultrasonic cleaning 20min ~ 25min, finally use deionized water rinsing, natural drying.
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| CN116397200B (en) * | 2023-06-08 | 2023-08-08 | 合肥工业大学 | Single-source thermal evaporation preparation method of molybdenum-copper laminated substrate of copper-antimony-selenium light absorption layer |
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