CN105576053B - Copper-zinc-tin-sulfur film solar cell and preparation method thereof - Google Patents
Copper-zinc-tin-sulfur film solar cell and preparation method thereof Download PDFInfo
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- CN105576053B CN105576053B CN201610014462.8A CN201610014462A CN105576053B CN 105576053 B CN105576053 B CN 105576053B CN 201610014462 A CN201610014462 A CN 201610014462A CN 105576053 B CN105576053 B CN 105576053B
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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 97
- 238000002360 preparation method Methods 0.000 title claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 232
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 118
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 118
- 239000011787 zinc oxide Substances 0.000 claims abstract description 116
- 229960001296 zinc oxide Drugs 0.000 claims abstract description 116
- 239000004411 aluminium Substances 0.000 claims abstract description 109
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000000034 method Methods 0.000 claims abstract description 50
- 238000000151 deposition Methods 0.000 claims abstract description 48
- 230000008021 deposition Effects 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 27
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011521 glass Substances 0.000 claims abstract description 18
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 154
- 239000002243 precursor Substances 0.000 claims description 29
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000010409 thin film Substances 0.000 claims description 13
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000006193 liquid solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000002955 immunomodulating agent Substances 0.000 claims description 6
- 229940121354 immunomodulator Drugs 0.000 claims description 6
- 230000002584 immunomodulator Effects 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 159000000013 aluminium salts Chemical class 0.000 claims description 5
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 150000001661 cadmium Chemical class 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- YGSCHSPBVNFNTD-UHFFFAOYSA-N [S].[Sn].[Zn] Chemical compound [S].[Sn].[Zn] YGSCHSPBVNFNTD-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000005486 sulfidation Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical group [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- 238000005496 tempering Methods 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000012876 topography Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000000224 chemical solution deposition Methods 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 230000016507 interphase Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- PDYXSJSAMVACOH-UHFFFAOYSA-N [Cu].[Zn].[Sn] Chemical compound [Cu].[Zn].[Sn] PDYXSJSAMVACOH-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000013082 photovoltaic technology Methods 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 2
- 241000208140 Acer Species 0.000 description 1
- 206010011376 Crepitations Diseases 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000002042 Silver nanowire Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- -1 alkyl hydrosulfide Chemical compound 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000004246 zinc acetate 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
- H01L31/0248—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
-
- 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
- H01L31/1876—Particular processes or apparatus for batch treatment of the devices
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention provides a kind of copper-zinc-tin-sulfur film solar cell, indium tin oxide electro-conductive glass back electrode layer, copper-zinc-tin-sulfur film light absorbing layer, cadmium sulfide buffer layer and aluminium including stacking gradually mix zinc oxide/silver wire/aluminium and mix zinc oxide composite transparent conducting window layer, and the aluminium, which mixes zinc oxide/silver wire/aluminium and mixes zinc oxide composite transparent conducting window layer and mixed for two layers of aluminium, is mingled with one layer of silver wire film among zinc-oxide film.The present invention substitutes Mo back electrodes using indium tin oxide electro-conductive glass, avoids the characteristic of Mo back electrodes and thermally labile in copper-zinc-tin-sulfur film sulfidation, while can realize transparent two sides, improves the device efficiency of copper-zinc-tin-sulfur film solar cell.In addition the ITO/AZO conducting window layers that aluminium mixes zinc oxide/silver wire/aluminium and mix zinc oxide composite transparent conducting window layer and replace vacuum method deposition are prepared using solwution method, reduces copper-zinc-tin-sulfur film solar cell manufacture cost, it is and also very friendly to ambient enviroment.
Description
Technical field
The present invention relates to a kind of photovoltaic technology, more particularly to a kind of quaternary compound copper-zinc-tin-sulfur film type solar cell
With and preparation method thereof.
Background technology
Copper-zinc-tin-sulfur（Abbreviation CZTS）Film component enriches, environmental-friendly, and the absorption coefficient of light is up to 104cm-1, gradually
As the research hotspot of solar cell material.In addition, optical band gap is adjustable（Pass through doped selenium or germanium）, crystal structure and electronics
Structure is similar to copper indium gallium selenide（Record efficiency 21.6%）, it is made to be expected to the photovoltaic technology as high-efficiency and low-cost.At present, respectively
Kind vacuum method and solution methods are used for preparing copper-zinc-tin-sulfur film solar cell.Based on vacuum thermal evaporation and magnetron sputtering skill
Art, copper-zinc-tin-sulfur film solar cell record efficiency are respectively 11.6% and 9.7%；Based on electro-deposition, collosol and gel and nanometer
Particle solution technology, copper-zinc-tin-sulfur film solar cell record efficiency are respectively 8.0%, 10.8% and 12.7%.
However compared with the similar CIGS solar cell efficiency of structure, battery efficiency is still relatively low, factors
Limit the raising of its efficiency.Wherein, optical loss and Mo back electrode thermal instabilitys are wherein two big reasons.Optics damages
It loses：When solar irradiation is mapped to copper-zinc-tin-sulfur film solar cell device surface, light is needed by surface metal gates, transparent led
Electric Window layer, barrier layer and buffer layer get to light absorbing layer, due to phenomena such as occurring to absorb or reflecting, reduce the strong of light
Degree, thereby reduces device efficiency.Molybdenum（Mo）Back electrode thermal instability：The prior art is using high temperature vulcanized copper zinc-tin in the process
Sulphur film can react with Mo, form interphase sulfide at the back of the body interface of copper-zinc-tin-sulfur film and Mo, it is good to affect interface
Good contact, reduces device efficiency.In addition, copper-zinc-tin-sulfur film solar cell is prepared at present frequently with physical vacuum gas phase
The method of deposition prepares indium tin oxide（Abbreviation ITO）Or aluminium mixes zinc oxide（Abbreviation AZO）Conducting window layer, of high cost, operation
Difficulty, and can seriously be restricted when facing extensive deposition and industrialization.
Solwution method deposition ITO or AZO conducting window layers are a more satisfactory selections, of low cost, it can be achieved that big face
Deposition.And the optical property and electric conductivity of ITO or AZO conducting window layers prepared by solwution method deposition have reached vacuum object
ITO or AZO conducting window layers prepared by physical vapor deposition.However, solwution method deposition ITO or AZO conducting window layers all need at present
300 DEG C to 600 DEG C annealing of high temperature are wanted, limit its application in copper-zinc-tin-sulfur film solar cell.Because copper-zinc-tin-sulfur is thin
When film solar cell p-n junction is higher than 250 DEG C of annealing, the cadmium atom in buffer layer cadmium sulfide can be spread, and destroy p-n junction interface
Performance, and then reduce device performance.
The content of the invention
In view of problem above, it is good, it can be achieved that transparent two sides and whole soln process that the present invention provides a kind of back electrode stability
The copper-zinc-tin-sulfur film type solar cell of preparation, with and preparation method thereof.
The present invention provides a kind of copper-zinc-tin-sulfur film solar cell, including the indium tin oxide electro-conductive glass stacked gradually
It is compound that back electrode layer, copper-zinc-tin-sulfur film light absorbing layer, cadmium sulfide buffer layer and aluminium mix zinc oxide/silver wire/aluminium mixes zinc oxide
Bright conducting window layer, it is that two layers of aluminium mixes zinc oxide that the aluminium, which mixes zinc oxide/silver wire/aluminium and mixes zinc oxide composite transparent conducting window layer,
It is mingled with one layer of silver wire film among film.
Further, the length of the silver wire in the silver wire film is 10~20 μm, a diameter of 50~80nm.
The present invention also provides a kind of methods for preparing copper-zinc-tin-sulfur film solar cell, include the following steps：
With indium tin oxide（Indium Tin Oxides, ITO）Electro-conductive glass is battery back electrode, at 50~350 DEG C
At a temperature of, liquid deposition, which prepares copper-zinc-tin-sulfur film absorbed layer, cadmium sulfide buffer layer and aluminium and mixes zinc oxide/silver wire/aluminium, successively mixes
Zinc oxide composite transparent conducting window layer.
The present invention substitutes Mo back electrodes using ITO electro-conductive glass, on the one hand avoids Mo back electrodes and copper-zinc-tin-sulfur film
Chemical heat instability problem（It is high temperature vulcanized during copper-zinc-tin-sulfur film can react with Mo, copper-zinc-tin-sulfur film with
The back of the body interface of Mo forms interphase sulfide, affects the good contact in interface, reduces device efficiency）, on the other hand can be with
The absorbability of light is improved from battery two sides, more photo-generated carriers is excited, and then improves the electric property and electricity of absorbed layer
The device efficiency in pond.
The present invention is using whole low temperature（≦350℃）Solwution method prepares copper-zinc-tin-sulfur film solar cell, is followed successively by low
Warm sol method depositing copper-zinc-tin sulphur film absorption layer, chemical bath deposition cadmium sulfide buffer layer, solwution method deposition of aluminum mix zinc oxide/silver
Line/aluminium mixes zinc oxide composite conductive thin film.Aluminium is prepared especially with low temperature solution polycondensation mix zinc oxide/silver wire/aluminium mix zinc oxide
Composite transparent conducting window layer substitutes the ITO/AZO conducting window layers of vacuum method deposition, and depositing temperature is less than 200 degree, realizes
Whole soln route prepares copper-zinc-tin-sulfur film solar cell, reduces being manufactured into for copper-zinc-tin-sulfur film solar cell
This, raw material are environmental-friendly, and chemical composition is controllable and can realize extensive deposition and industrialization.Using prepared by the method
Solar cell conductive performance and optical property are good.
Description of the drawings
Fig. 1 is that low temperature whole soln process prepares double-side type copper-zinc-tin-sulfur solar battery structure figure；
Fig. 2 is copper-zinc-tin-sulfur film surface topography map prepared by embodiment 1；
Fig. 3 is copper-zinc-tin-sulfur film sectional view prepared by embodiment 1；
Fig. 4 is copper-zinc-tin-sulfur film X-ray diffractogram prepared by embodiment 1；
Fig. 5 is copper-zinc-tin-sulfur film Raman spectrogram prepared by embodiment 1；
Fig. 6 is cadmium sulphide membrane surface topography map prepared by embodiment 1；
Fig. 7 is AZO/Ag lines/AZO film surface appearance figures prepared by embodiment 1；
Fig. 8 is AZO/Ag lines/light transmittance of AZO films and the graph of absorbing wavelength prepared by embodiment 1；
Fig. 9 is copper-zinc-tin-sulfur solar battery structure figure prepared by embodiment 1；
Figure 10 is copper-zinc-tin-sulfur solar cell I-V graph prepared by embodiment 1.
Specific embodiment
The present invention provides a kind of copper-zinc-tin-sulfur film solar cell, including the indium tin oxide electro-conductive glass stacked gradually
It is compound that back electrode layer, copper-zinc-tin-sulfur film light absorbing layer, cadmium sulfide buffer layer and aluminium mix zinc oxide/silver wire/aluminium mixes zinc oxide
Bright conducting window layer, it is that two layers of aluminium mixes zinc oxide that the aluminium, which mixes zinc oxide/silver wire/aluminium and mixes zinc oxide composite transparent conducting window layer,
It is mingled with one layer of silver wire film among film.Concrete structure diagram is as shown in Figure 1.
The present invention substitutes Mo back electrodes using ITO electro-conductive glass, on the one hand avoids Mo back electrodes and copper-zinc-tin-sulfur film
Chemical heat instability problem（It is high temperature vulcanized during copper-zinc-tin-sulfur film can react with Mo, copper-zinc-tin-sulfur film with
The back of the body interface of Mo forms interphase sulfide, affects the good contact in interface, reduces device efficiency）, on the other hand can be with
The absorbability of light is improved from battery two sides, more photo-generated carriers is excited, and then improves the electric property and electricity of absorbed layer
The device efficiency in pond.
Further, the length of the silver wire in the silver wire film is 10~20 μm, a diameter of 50~80nm.
The present invention adds in silver wire, for improving the electric conductivity that aluminium mixes zinc oxide.The present invention is sent out by many experiments simultaneously
Existing, when silver wire has certain draw ratio, the aluminium mixes zinc oxide/silver wire/aluminium and mixes zinc oxide composite transparent conducting window layer
Just there is good electric conductivity.Wherein described certain draw ratio is that the length of silver wire is 10~20 μm, a diameter of 50~
80nm.Under this draw ratio, the silver wire is uniformly dispersed in ink, will not form aggregate structure, and the silver wire film of preparation is thick
Thin uniform, translucency is good, and electric conductivity is good.
Further, 60~130nm of the silver wire film thickness.
Further, in cross-linked structure between the silver wire in the silver wire film, the cross-linked structure can
Strengthen the electric conductivity of silver wire film, and then reinforcement aluminium mixes zinc oxide/silver wire/aluminium and mixes zinc oxide composite transparent conducting window layer
Electric conductivity.
Further, the silver wire is coated on first layer aluminium and mixes on zinc-oxide film, and mixes zinc oxide films with second layer aluminium
Film mutually merges, and second layer aluminium mixes zinc-oxide film and silver wire film is completely covered.The aluminium mixes zinc-oxide film, and silver wire is thin
The oxidation that can avoid silver wire and the electric conductivity for improving laminated film is completely covered in film.
The present invention also provides a kind of methods for preparing copper-zinc-tin-sulfur film solar cell, include the following steps：
Fin oxide condutire glass is mixed as back electrode using indium, solwution method deposition prepares copper-zinc-tin-sulfur film absorbed layer, sulphur successively
Cadmium buffer layer and aluminium mix zinc oxide/silver wire/aluminium and mix zinc oxide composite transparent conducting window layer, the aluminium mix zinc oxide/silver wire/
Aluminium, which is mixed zinc oxide composite transparent conducting window layer and mixed for two layers of aluminium, is mingled with one layer of silver wire film among zinc-oxide film.
The present invention is using whole low temperature（≦350℃）Solwution method prepares copper-zinc-tin-sulfur film solar cell, is followed successively by molten
Glue method depositing copper-zinc-tin sulphur film absorption layer, chemical bath deposition cadmium sulfide buffer layer, solwution method deposition of aluminum mix zinc oxide/silver wire/
Aluminium mixes zinc oxide composite conductive thin film.The present invention realizes whole soln route and prepares copper-zinc-tin-sulfur film solar cell, reduces
The manufacture cost of copper-zinc-tin-sulfur film solar cell, raw material are environmental-friendly, and chemical composition is controllable and can realize big face
Deposition product and industrialization.
1. sol method depositing copper-zinc-tin sulphur film absorption layer
The cryosol depositing copper-zinc-tin sulphur film absorption layer includes the following steps：
Mantoquita, pink salt, zinc salt and sulfur-containing compound are dissolved in organic solvent, prepare copper-zinc-tin-sulfur film presoma
Solution；
Copper-zinc-tin-sulfur precursor sol is deposited on indium tin oxide electro-conductive glass and obtains copper-zinc-tin-sulfur precursor thin-film；
Copper-zinc-tin-sulfur precursor thin-film temper is obtained into copper-zinc-tin-sulfur film.
The mantoquita, pink salt, zinc salt include but not limited at least one of acetate and chlorate.
The sulfur-containing compound includes but not limited at least one of thiocarbamide, sulphur powder, thioacetamide and alkyl hydrosulfide.
The organic solvent includes but not limited to Dimethyl Asian Maple, ethylene glycol monomethyl ether, at least one of second alcohol and water.
In the copper-zinc-tin-sulfur precursor sol of the preparation, the concentration of copper is 0.1~0.5 mol/L, zinc concentration 0.1
~0.5mol/L, the concentration of tin is 0.1~0.5 mol/L, and the concentration of sulfur-containing compound is 2 times of the total concentration of metal salt.Institute
The molar concentration ratio for stating each metal in copper-zinc-tin-sulfur precursor sol is Cu/Zn+Sn=0.8~1.2, Zn/Sn=1.0~1.2.
Mantoquita, pink salt, zinc salt and sulfur-containing compound it should be understood that are dissolved in the process of organic solvent by those skilled in the art
In, heating stirring can also be carried out, heating temperature is 40~50 DEG C.Preferably 45 DEG C.Reaction time is 30~60 min.
The deposition obtains copper-zinc-tin-sulfur precursor thin-film, it is preferred to use spin coating method deposits.
Further, it is described when preparing copper-zinc-tin-sulfur film deposition, spin-on deposition once after, temper immediately,
The temperature is 250~300 DEG C, and tempering time is 2~5 min.Spin-on deposition is further continued for, until copper-zinc-tin-sulfur film system
It is standby to complete.
The tempering directly heats for precursor thin-film is placed into warm table, the technique for being cooled back to room temperature, for removing
The organic solvent contained in film layer improves the crystallinity of film layer.
After the completion of prepared by the copper-zinc-tin-sulfur film, temper once, the organic molten of remnants can also be removed again again
Agent, treatment temperature are 300~350 DEG C, and tempering time is 30~60 min.Preferably 350 DEG C.
The copper-zinc-tin-sulfur film absorber thickness of the preparation is 0.9~1 μm.
The present invention prepares copper zinc-tin using sol method depositing copper-zinc-tin sulphur thin film precursor, the vulcanization annealing of Di Wen≤350 DEG C
Sulphur film.It avoids in the prior art using high temperature vulcanized method, on the one hand so that copper-zinc-tin-sulfur film absorbed layer and ITO back electrodes
High temperature vulcanized due to coefficient of thermal expansion is big CZTS films to be caused easily to come off on ITO back electrodes, another aspect ITO back electrodes are high
In warm sulfidation, decline that electric conductivity can be drastically reduces device performance.
The present invention has found repeatedly to be tempered during copper-zinc-tin-sulfur film is prepared by test of many times, and temperature is 250
It is more suitable between~300 DEG C, if temperature is less than 250 DEG C, prepared copper-zinc-tin-sulfur film absorbed layer because carbon content is excessively high, and
Copper-zinc-tin-sulfur film is caused easily to come off on ITO back electrodes.If temperature is higher than 300 DEG C, will be because of CZTS absorbed layers and ITO
Back electrode can also cause CZTS films easily to come off on ITO back electrodes greatly because of coefficient of thermal expansion.Therefore 250~300 DEG C are one
A suitable temperature, the copper-zinc-tin-sulfur film absorbed layer of temper is highly stable at this temperature, so as to which the electrode prepared is steady
It is qualitative good.
Further, the cleaning of back electrode, the cleaning are further included before the preparation of the copper-zinc-tin-sulfur film absorbed layer
Include the following steps：
ITO electro-conductive glass is cleaned by ultrasonic 10min using alkaline detergent, acetone, second alcohol and water successively, nitrogen dries up,
Then 10min is cleaned with UV ozone cleaning machine.
The alkaline detergent includes but not limited to soap, glass detergent etc..
2. chemical bath deposition prepares cadmium sulfide buffer layer
The liquid deposition prepares cadmium sulfide buffer layer and includes the following steps to prepare：
Cadmium salt and thiocarbamide are dissolved in the water, ammonium hydroxide is added in, prepares cadmium sulfide precursor solution；
By cadmium sulfide precursor solution, 60~90 DEG C of water-baths deposit to form cadmium sulfide buffer layer on copper-zinc-tin-sulfur film.
The cadmium salt includes but not limited at least one of sulfate, acetate and chlorate.
After the ammonium hydroxide adjusts the pH of solution, the pH is 10~11.
After the cadmium salt and thiocarbamide are dissolved in the water, in the solution concentration of cadmium be 0.01~0.1mol/L, sulphur it is dense
It is Cd/S=1 to spend for 1.0~2.0 mol/L, the concentration of metal ion and the ratio of thiourea concentration:50.The mass percent of ammonium hydroxide
Concentration is 25%~28%.
The water-bath depositing temperature is 60~90 DEG C, deposits 6~10min.
Further, the water-bath, which deposits, to form cadmium sulfide buffer layer and can also make temper, temperature for 150~
200 DEG C, tempering time 5min.
The deposition after cure cadmium buffer layer thickness is 50~80nm.
3. low temperature solution polycondensation, which prepares aluminium, to be mixed zinc oxide/silver wire/aluminium and mixes zinc oxide composite transparent conducting window layer
It is described prepare aluminium and mix zinc oxide/silver wire/aluminium and mix zinc oxide composite transparent conducting window layer include the following steps：
Zinc nitrate, aluminium salt and reducing agent are dissolved in organic solvent and reacted, aluminium is prepared and mixes zinc oxide precursor liquid solution；
Solwution method deposition of aluminum mixes zinc oxide precursor and drives liquid solution on cadmium sulfide buffer layer, at 150~200 DEG C of tempering
Reason obtains first layer aluminium and mixes zinc-oxide film；
Silver wire ink is coated on first layer aluminium to mix on zinc-oxide film, it is thin to obtain silver wire in 120~150 DEG C of tempers
Film；
It repeats solwution method deposition of aluminum and mixes zinc oxide precursor liquid solution on silver wire film, obtained in 150~200 DEG C of tempers
Zinc-oxide film is mixed to second layer aluminium.
The present invention using aluminium mix zinc oxide/silver wire/aluminium mix zinc oxide composite film conducting window layer replacement vacuum method sink
Long-pending ITO or AZO Thin film conductive Window layers, depositing temperature are less than 200 degree, and prepared aluminium mixes zinc oxide/silver wire/aluminium and mixes oxidation
The electric conductivity and optical property of zinc laminated film conducting window layer are good.Its principle is：The present invention uses nitrate and reduction
Immunomodulator compounds react, and are reacted by nitrate with reduction immunomodulator compounds and generate substantial amounts of energy, make the reduction of nitric acid zinc salt straight
Zinc oxide is delivered a child into, further mixes zinc oxide with aluminium salt generation aluminium.The method extraneous need not provide substantial amounts of energy, it can be achieved that
Low temperature（≦200℃）Zinc oxide is prepared, avoids 300 DEG C to 600 DEG C tempers of conventional solution method high temperature.
Reaction process is as follows：
（1）Zinc acetylacetonate（Zn(C5H7O2)2) it is used as reducing agent：
（2）Acetylacetone,2,4-pentanedione（C5H8O2) it is used as reducing agent：
（3）Urea（CO(NH2)2) it is used as reducing agent：
Aluminium prepared by the method mixes zinc-oxide film and can be applied to copper-zinc-tin-sulfur film solar cell preparation, meets device
Part annealing temperature is no more than 250 DEG C of requirement.
The organic solvent includes but not limited to ethylene glycol monomethyl ether, at least one of second alcohol and water.
The reduction immunomodulator compounds include but not limited at least one of zinc acetylacetonate, acetylacetone,2,4-pentanedione and urea.
It is 0.1~0.2mol/L that the zinc nitrate and reduction immunomodulator compounds, which are dissolved in the concentration after organic solvent, each metal
Molar concentration ratio for Al/Zn=1%~3%, be preferably 2%.
Can also be heated in the zinc nitrate, aluminium salt and reduction immunomodulator compounds reaction process, the heating temperature for 50~
60 DEG C, when the reaction time is 20~24 small.
The solwution method deposition of aluminum makees temper after mixing zinc oxide precursor body thin film, and temper temperature is 150~200
DEG C, 10~15min of temper.
The preparation method of the silver wire includes the following steps：By silver salt, potassium bromide and polyvinylpyrrolidone（Referred to as
PVP）Organic solvent is dissolved in, 170 DEG C of reactions under the conditions of inert gas shielding, you can prepare silver wire.
Further, silver wire is dissolved in the organic solvent of low boiling point low carbon content, forms silver wire ink, by coating
It is mixed in aluminium on zinc oxide precursor body thin film.The concentration of the dissolved silver wire in organic solvent is 0.2~1.0mL/g.
The organic solvent of the low boiling point low carbon content, is the organic solvent of 1~4 relatively low carbon of boiling point, and low carbon content has
The fused of zinc oxide is mixed beneficial to silver wire and aluminium, and the readily volatilized removal of low boiling point.
The silver wire ink spin coating can also make temper, and temperature is 120~150 DEG C, is preferably 150 DEG C, instead
It is 30~60s between seasonable.
Further, the side for forming the step of first, second layer of aluminium mixes zinc-oxide film and Multiple depositions being respectively adopted
Method is reached.For example, can first layer aluminium first be mixed zinc-oxide film Multiple depositions, 6~8 layers are preferably deposited, is then coated with one layer
Silver wire, then aluminium is mixed into zinc-oxide film and deposits 6~8 layers.The step of first, second layer of aluminium is mixed zinc-oxide film by the present invention is distinguished
Effectively silver wire can be covered using the method for Multiple depositions, silver wire is avoided to aoxidize, and be connected with each other silver wire, enhance it and lead
Electrical property.
The silver wire film thickness of the preparation is 60~130nm, the first layer aluminium mix zinc oxide films film thickness for 80~
100nm, second layer aluminium mix zinc oxide films film thickness for 120~150nm.
The present invention, which using low temperature solution polycondensation prepares aluminium and mixes zinc oxide/silver wire/aluminium, mixes zinc oxide composite transparent conducting window layer
ITO the and AZO conductive films of vacuum method deposition are substituted, depositing temperature is less than 200 degree, the battery conductive performance and optics of preparation
It is functional, it realizes whole low temperature solution polycondensation and prepares copper-zinc-tin-sulfur film solar cell.And it is not used in preparation process
Expensive Pvd equipment, of low cost, raw material are environmental-friendly.
Embodiment
For technical scheme is allowed to be clearer and more comprehensible, spy lifts preferred embodiment, elaborates, protection of the invention
Scope is not limited by the following examples.It is all within the marrow of the present invention and principle, any modification for being made, equivalent substitution,
Improve etc., it should all be included in the protection scope of the present invention.
Embodiment 1
(1) 30 × 30 mm of substrate ITO electro-conductive glass using alkaline cleaning fluid, acetone, isopropanol and high-purity is gone successively
Ionized water is cleaned by ultrasonic 15 minutes, then nitrogen drying then will to substrate surface ozone clean 10 minutes using UV cleaning machines
It is spare that it is put into vacuum drying chamber；
(2) prepared by copper zinc tin sulfur absorption layer：Copper acetate, zinc acetate, stannic chloride and thiocarbamide are weighed respectively is dissolved in ethylene glycol first
Ether solvents, 45 DEG C of 30 min of reaction are that can obtain copper-zinc-tin-sulfur precursor sol, metal ion in copper-zinc-tin-sulfur precursor sol
Concentration proportion for Cu/ (Zn+Sn)=0.8, Zn/Sn=1.2, it is molten using the method depositing copper-zinc-tin sulphur presoma of spin-on deposition
Glue obtains copper-zinc-tin-sulfur precursor thin-film in ITO conductive glass surfaces.Then vulcanize in 350 DEG C of argon atmospheres at tempering
Manage 60 min, you can obtain copper-zinc-tin-sulfur film absorbed layer.Fig. 2 is the surface topography map of copper-zinc-tin-sulfur film, and film surface has
A little crackles, grain size are 100nm or so.Fig. 3 be copper-zinc-tin-sulfur film Cross Section Morphology figure, general 1 μm or so of film thickness,
White portion is ito glass, the general 150nm of thickness.Fig. 4 is the XRD experimental results of copper-zinc-tin-sulfur film, the results showed that synthesis
Copper-zinc-tin-sulfur film be Kesterite crystal structures, XRD diffraction maximums along（101）,（112）,（200）,（220）,（312）With
（332）Crystal face.Fig. 5 is the Raman experimental results of copper-zinc-tin-sulfur film, and the copper-zinc-tin-sulfur film for further illustrating synthesis is
Kesterite crystal structures are generated without impurity phase.
(3) prepared by cadmium sulfide buffer layer：Formulating vulcanization cadmium solution concentration 0.15mol/L, thiourea solution concentration 0.75mol/
L；Vulcanization cadmium solution and thiourea solution 20ml are measured respectively in 250nm beakers, add the ammonium hydroxide 28ml of concentration 25%~28%, it is high
Pure deionized water about 135ml so that Cd ions and S ion concentrations are 1:50, it is 10~11 that ammonium hydroxide, which adjusts aqueous solution pH,；Water-bath is sunk
60~90 DEG C of accumulated temperature degree, 6~10min of deposition are the cadmium sulfide buffer layer of available 50~80nm.Fig. 6 is that sedimentation time is
The cadmium sulfide surface topography map of 8min, the cadmium sulfide grain size of synthesis is about 100 ~ 200nm, film thickness 70nm.
(4) aluminium mixes zinc oxide/silver wire/aluminium and mixes zinc oxide composite transparent conducting window layer：Zinc nitrate and acetylacetone,2,4-pentanedione is molten
Solution in ethylene glycol monomethyl ether solvent 60 DEG C reaction 24 it is small when, obtain aluminium and mix zinc oxide precursor liquid solution；Solwution method deposition of aluminum mixes oxygen
Change zinc precursor solution on cadmium sulfide buffer layer, i.e. can obtain aluminium mixes zinc-oxide film to 200 DEG C of tempers, is repeated 6 times；It is molten
Liquid method deposition silver wire ink is mixed in aluminium on zinc-oxide film, and 150 DEG C of processing 1 min, UV handle 2 min；Then solwution method is repeated
Deposition of aluminum mixes zinc oxide precursor liquid solution in silver wire film surface, and i.e. can obtain aluminium mixes zinc-oxide film to 150 DEG C of tempers, weight
It is 8 times multiple；200 degree of 10 min of annealing, which can obtain aluminium and mix zinc oxide/silver wire/aluminium, again mixes zinc oxide composite transparent conductive window
Layer.
Fig. 7 mixes the surface topography map that zinc oxide/silver wire/aluminium mixes zinc oxide composite transparent conducting window layer, silver wire position for aluminium
It is mixed in aluminium inside zinc oxide film, the aluminium of synthesis mixes Zinc oxide nanoparticle size for 20 ~ 40nm.Fig. 8 mixes zinc oxide/silver for aluminium
Line/aluminium mixes the light transmittance of zinc oxide composite transparent conducting window layer and the graph of absorbing wavelength, as can be seen from the figure exists
After 450-1000nm, light transmittance can reach more than 90%.From the following table 1 it can also be seen that aluminium, which mixes zinc oxide/silver wire/aluminium, mixes oxidation
Zinc film is compared with aluminium mixes zinc-oxide film, silver wire film, and light transmittance is not much different, but sheet resistance is much smaller.
Table 1, which for aluminium mixes zinc oxide/silver wire/aluminium and mixes zinc-oxide film and aluminium, mixes zinc-oxide film, silver wire light transmittance and surface
Resistance compares
| Sample | Light transmittance（% is in 550nm） | Sheet resistance（Ω/cm2） |
| Aluminium mixes zinc-oxide film | 100 | 2.79×108 |
| Silver wire film | 92.9 | ＜ 100 |
| Aluminium mixes zinc oxide/silver wire/aluminium and mixes zinc-oxide film | 92.8 | ＜ 50 |
(5) it is sequentially depositing according to above-mentioned steps and can obtain two-sided copper-zinc-tin-sulfur film solar cell, battery structure
For：glass/ITO/CZTS/CdS/AZO/AgNWs/AZO.Fig. 9 cuts for whole soln process copper-zinc-tin-sulfur film solar cell device
Face figure.Figure 10 is the IV graphs of whole soln process copper-zinc-tin-sulfur film solar cell, and device efficiency is 0.023% as seen from the figure,
Open-circuit voltage is 120mV, short-circuit current density 0.57mA/cm2, fill factor, curve factor 33.7%.
Claims (8)
1. a kind of copper-zinc-tin-sulfur film solar cell, including indium tin oxide electro-conductive glass back electrode layer, the copper stacked gradually
Zinc-tin-sulfur film light absorbing layer, cadmium sulfide buffer layer and aluminium mix zinc oxide/silver wire/aluminium and mix zinc oxide composite transparent conductive window
Layer, it is that two layers of aluminium mixes folder among zinc-oxide film that the aluminium, which mixes zinc oxide/silver wire/aluminium and mixes zinc oxide composite transparent conducting window layer,
Miscellaneous one layer of silver wire film；The length of silver wire in the silver wire film is 10~20 μm, a diameter of 50~80nm；The silver wire is thin
Film thickness is 60~130nm；The aluminium mixes the aluminium that zinc oxide/silver wire/aluminium is mixed in zinc oxide composite transparent conducting window layer and mixes oxygen
It is 6-8 layers to change zinc.
2. copper-zinc-tin-sulfur film solar cell as described in claim 1, which is characterized in that the silver wire in the silver wire film
Between be in cross-linked structure.
3. copper-zinc-tin-sulfur film solar cell as described in claim 1, which is characterized in that the silver wire is coated on first layer
Aluminium is mixed on zinc-oxide film, and is mixed zinc-oxide film with second layer aluminium and mutually merged, and second layer aluminium mixes zinc-oxide film by silver wire
Film is completely covered.
4. a kind of method for preparing copper-zinc-tin-sulfur film solar cell as described in claim 1, includes the following steps：
Fin oxide condutire glass is mixed as back electrode using indium, solwution method deposition prepares copper-zinc-tin-sulfur film absorbed layer, cadmium sulfide successively
Buffer layer and aluminium mix zinc oxide/silver wire/aluminium and mix zinc oxide composite transparent conducting window layer, and the aluminium is mixed zinc oxide/silver wire/aluminium and mixed
Zinc oxide composite transparent conducting window layer is mixed for two layers of aluminium is mingled with one layer of silver wire film among zinc-oxide film；
It is described prepare aluminium and mix zinc oxide/silver wire/aluminium and mix zinc oxide composite transparent conducting window layer include the following steps：
Zinc nitrate, aluminium salt and reducing agent are dissolved in organic solvent and reacted, aluminium is prepared and mixes zinc oxide precursor liquid solution；
Solwution method deposition of aluminum mixes zinc oxide precursor liquid solution on cadmium sulfide buffer layer, and is obtained in 150~200 DEG C of tempers
One layer of aluminium mixes zinc-oxide film；
Silver wire ink is coated on first layer aluminium to mix on zinc-oxide film, silver wire film is obtained in 120~150 DEG C of tempers；
It repeats solwution method deposition of aluminum and mixes zinc oxide precursor liquid solution on silver wire film, the is obtained in 150~200 DEG C of tempers
Two layers of aluminium mix zinc-oxide film.
5. preparation method as claimed in claim 4, which is characterized in that the copper-zinc-tin-sulfur film absorbed layer for preparing is including as follows
Step：
Mantoquita, pink salt, zinc salt and sulfur-containing compound are dissolved in organic solvent, prepare copper-zinc-tin-sulfur precursor sol；
By copper-zinc-tin-sulfur precursor sol spin-on deposition on indium tin oxide electro-conductive glass, it is thin to obtain copper-zinc-tin-sulfur presoma
Film；
Copper-zinc-tin-sulfur precursor thin-film is obtained into copper-zinc-tin-sulfur film in 300~350 DEG C of tempers.
6. preparation method as claimed in claim 4, which is characterized in that the cadmium sulfide buffer layer for preparing includes the following steps：
Cadmium salt and thiocarbamide are dissolved in the water, ammonium hydroxide is added in, prepares cadmium sulfide precursor solution；
By cadmium sulfide precursor solution, 60~90 DEG C of water-baths deposit to form cadmium sulfide buffer layer on copper-zinc-tin-sulfur film.
7. preparation method as claimed in claim 4, which is characterized in that first, second layer of aluminium of the formation mixes zinc-oxide film
The step of the methods of Multiple depositions be respectively adopted reach.
8. preparation method as claimed in claim 4, which is characterized in that the zinc nitrate, aluminium salt and reduction immunomodulator compounds reaction
It is heated in the process, the heating temperature is 50~60 DEG C, when the reaction time is 20~24 small；It is described that the second layer is prepared
Aluminium is mixed after zinc-oxide film in 150~200 DEG C of 10~15min of temper.
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