CN108538934A - A kind of method that selenized annealing prepares Cu-In-Al-Se solar cell thin-film material after layering electro-deposition - Google Patents
A kind of method that selenized annealing prepares Cu-In-Al-Se solar cell thin-film material after layering electro-deposition Download PDFInfo
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- 238000004070 electrodeposition Methods 0.000 title claims abstract description 70
- 238000000137 annealing Methods 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000010409 thin film Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 41
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000003839 salts Chemical class 0.000 claims abstract description 48
- 239000010408 film Substances 0.000 claims abstract description 47
- 238000000151 deposition Methods 0.000 claims abstract description 46
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 45
- 239000010949 copper Substances 0.000 claims abstract description 45
- 239000011669 selenium Substances 0.000 claims abstract description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052802 copper Inorganic materials 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000008367 deionised water Substances 0.000 claims abstract description 35
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 35
- 239000004411 aluminium Substances 0.000 claims abstract description 30
- 229910052738 indium Inorganic materials 0.000 claims abstract description 28
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- -1 copper indium aluminum selenium Chemical compound 0.000 claims abstract description 11
- 239000012528 membrane Substances 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 50
- 230000008021 deposition Effects 0.000 claims description 41
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 34
- 239000011521 glass Substances 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000001103 potassium chloride Substances 0.000 claims description 25
- 235000011164 potassium chloride Nutrition 0.000 claims description 25
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims description 18
- 239000011733 molybdenum Substances 0.000 claims description 18
- 239000011780 sodium chloride Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 230000005611 electricity Effects 0.000 claims description 11
- 229910001449 indium ion Inorganic materials 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 238000007747 plating Methods 0.000 claims description 8
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 7
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 7
- 229910016747 AlCl3—NaCl—KCl Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 229910052927 chalcanthite Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002471 indium Chemical class 0.000 claims description 2
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 2
- 239000011833 salt mixture Substances 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims 2
- 238000002242 deionisation method Methods 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004062 sedimentation Methods 0.000 description 15
- 150000002739 metals Chemical class 0.000 description 10
- 229910052711 selenium Inorganic materials 0.000 description 10
- 239000002659 electrodeposit Substances 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- VEMHQNXVHVAHDN-UHFFFAOYSA-J [Cu+2].[Cu+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Cu+2].[Cu+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VEMHQNXVHVAHDN-UHFFFAOYSA-J 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- JKXCZYCVHPKTPK-UHFFFAOYSA-N hydrate;trihydrochloride Chemical compound O.Cl.Cl.Cl JKXCZYCVHPKTPK-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- DWGQLIHNAWNSTB-UHFFFAOYSA-N [AlH3].[Se] Chemical compound [AlH3].[Se] DWGQLIHNAWNSTB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 229910000928 Yellow copper Inorganic materials 0.000 description 1
- GQCYCMFGFVGYJT-UHFFFAOYSA-N [AlH3].[S] Chemical compound [AlH3].[S] GQCYCMFGFVGYJT-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
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- AUCDRFABNLOFRE-UHFFFAOYSA-N alumane;indium Chemical compound [AlH3].[In] AUCDRFABNLOFRE-UHFFFAOYSA-N 0.000 description 1
- 238000005269 aluminizing Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical class [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- NMHFBDQVKIZULJ-UHFFFAOYSA-N selanylideneindium Chemical compound [In]=[Se] NMHFBDQVKIZULJ-UHFFFAOYSA-N 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000004073 vulcanization Methods 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
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
Abstract
The invention discloses the methods that selenized annealing after a kind of layering electro-deposition prepares Cu-In-Al-Se solar cell thin-film material.To overcome hydrogen evolution phenomenon caused by aqueous solution electrodeposition aluminium, the present invention first uses fuse salt flexible aluminium film, then copper metal salt is dissolved in deionized water, the acid copper on the film aluminized, indium metal salt is dissolved in deionized water again, aluminize/film of copper on electro-deposition indium, then precursor thin-film selenized annealing obtained into copper indium aluminum selenium membrane.The controllable preparation to thin film composition, crystal structure, pattern etc. is realized by the depositing current density and time of each layer film of hierarchical control.Compared with a step aqueous solution electrodeposition method, the film purity prepared by the present invention is high, without CuxSeyOr InxSeyBinary-phase, compared with high vacuum method, controllability of the present invention is strong, and preparation process is simple, and utilization rate of raw materials is high, of low cost, favorable repeatability, it is easy to accomplish the preparation of large area, high-quality thin film.
Description
Technical field
The invention belongs to photoelectric material new energy fields, are related to a kind of layering of thin-film solar cell photoelectric transition material
Selenized annealing preparation method after electro-deposition, and in particular to after a kind of fuse salt electric deposition aluminum, electro-deposition respectively in aqueous solution
Elemental copper and simple substance indium film, the method that rear selenized annealing forms copper indium aluminum selenium membrane.
Background technology
The deterioration for facing severe Energy situation and ecological environment changes existing energy resource structure, the reproducible green of development
The energy has become the project that countries in the world are extremely paid close attention to.Solar energy is because with most clean environment firendly, inexhaustible, nexhaustible, peace
It attracts attention the features such as stabilization entirely.Chalcopyrite series Cu (In, Ga, Al) (S, Se)2(CIGASS) material was from 70 years 20th century
Since generation occurs, very fast development is obtained, has had become the research hotspot of international photovoltaic circle at present.CIGAS is direct band
Gap material, and the absorption coefficient of light is larger, reaches 105cm-1, opto-electronic conversion theoretical efficiency reaches 25%~30%.Only need 1~2um
Thick film can absorb 99% or more sunlight, so as to substantially reduce the cost of solar cell.Wherein CuInSe2
(CIS) film energy gap is 1.04eV, and the best band gap of solar cell material should be about 1.45eV.It is absorbed too to optimize
Solar spectrum, people become CuIn by adulterating suitable Ga to substitute part In1-xGaxSe2(CIGS) thin-film material, film
Energy gap can adjust within the scope of 1.04eV-1.67eV.German Hydrogen Energies in 2015 and regenerative resource research center (ZSW)
Use the transfer efficiency of the small area CIGS solar cells of coevaporation technique development for 21.7% (Phys.Status Solidi
RRL, 2015,9 (1) 28-31), it is the tidemark of current hull cell.CIGS based thin film solar cells have opto-electronic conversion
It is efficient, capability of resistance to radiation is strong, and be that one of current solar cell development is important the advantages that there is no light-induced degradation problems
Direction.But the use of a large amount of rare precious metals In, Ga, make the development of this kind of battery be restricted to a certain extent.With Al come
CuIn can be formed by substituting rare metal Ga1-xAlxSe2(CIAS) compound semiconductor materials.Compared by changing Al/ (Al+In)
Value, energy gap is adjustable between 1.0-2.6eV.Compared with CIGS, Al, which substitutes Ga, can not only make the taboo of solar cell
Bandwidth covers broader range.And due to the less expensive of Al, cost can also be substantially reduced.And because it is needed
More smaller than Ga alloy opposite alloy concentrations realize the adjusting of identical band gap.For the film of identical band gap, Al ratios are adulterated
Adulterate change smallers of the Ga to the lattice constant of basis material.Therefore CIAS is considered as being based on broad-band gap CIGS solar-electricities
The substitute in pond prepares CIAS thin-film materials and battery, except be conducive to the utilization of resources, it is cost-effective in addition to, moreover it is possible to improve band gap,
The crystalline state for improving film, increases the conductivity of material, shows tempting application prospect.
CIAS absorbed layers thin film preparation process mainly has at present：Vacuum evaporation and magnetron sputtering.Vacuum vapor deposition method be by Cu,
Coevaporation forms compound to tetra- source material of In, Al, Se under vacuum conditions together, i.e. method is steamed in four sources altogether.Prepared by this method
Battery thin film crystal is big, but stringent to equipment requirement, and preparation process is complicated, and expensive, evaporation process is not easily controlled, system
It needs that four copper, indium, aluminium, selenium vapour pressures are differed very big simple substance source and be independently accurately controlled during standby, especially
It is the anti-evaporation of selenium, aluminium and indium selenium compound, very big difficulty is brought to the control of the film ultimate constituent, therefore be difficult real
Existing large-area uniformity and consecutive production.Magnetron sputtering method is first to sputter Cu-In-Al targets in vacuum equipment to form Cu-
Then In-Al predecessors are heat-treated in the atmosphere of Se.Uniformity of film prepared by this method is high, but is similarly
Preparation process is more complicated, and equipment requirement is high and production efficiency is relatively low, and production cost is high, and large-scale production is difficult to carry out.And
Electrodeposition process equipment is simple, can be in various complex surface substrate deposits, it is easy to accomplish the low temperature of continuous large-area film is heavy
Product, electric depositing solution can be used repeatedly, and production cost is low, and production efficiency is high, thus more suitable for industrialized production.At present
The document that report prepares CIAS using electro-deposition method is seldom, and only several documents are all to use a step electricity heavy in aqueous solution
Product method obtains Cu-In-Al-Se films, is then made annealing treatment again, due to Cu2+, In3+, Al3+Sedimentation potential difference compared with
Greatly, especially aluminium is a kind of very active metal, and standard electrode potential is also more negative than hydrogen, and deposition process is not easily controlled, deposition
Film quality it is poor, component nonstoichiometry is than serious.There is Cu in film after annealingxSey, InxSeyDeng two
The presence of first compound, these impurity phases produces very the surface topography and battery performance of CIAS solar absorption layer films
Detrimental effect.
Therefore, it is necessary to explore the cheap preparation process of use cost to be simply layered electro-deposition method, free from admixture two is prepared
The fine copper In-Al-Se solar cell thin-film material of first phase.
Invention content
In order to solve the above technical problem, the present invention provides selenized annealings after a kind of layering electro-deposition to prepare Cu-In-Al-Se too
The method of positive energy battery film material.Since aluminium is a kind of very active metal, standard electrode potential is -1.662eV ratios
Hydrogen is also negative, in order to avoid serious hydrogen evolution phenomenon caused by electric deposition aluminum in aqueous solution, first prepares aluminium chloride, the sodium chloride of melting
With potassium chloride ternary inorganic fused salt system, aluminium film is deposited using two electrode electro-deposition methods in the fuse salt.Then by copper
Metal salt is dissolved in deionized water, the acid copper on the film aluminized, then indium metal salt is dissolved in deionized water, in/copper of aluminizing
Film on electro-deposition indium, then by precursor thin-film under vacuum or inert gas shielding selenized annealing recrystallize, obtain copper and indium
Aluminium selenium film.According to multiple Optimal Experimental, find first in fuse salt after the complete aluminium film of electro-deposition, then electrodeposit metals indium, so
Electrodeposit metals copper again afterwards, then performed thin film selenized annealing can also be obtained to the system of Cu-In-Al-Se solar cell thin-film material
It is standby.Or first electrodeposit metals copper, then electrodeposit metals aluminium film in fuse salt, then electrodeposit metals indium finally will be prefabricated
Film selenized annealing can also obtain Cu-In-Al-Se solar cell thin-film material.Infer from growth mechanism, it will be in annealing process
Selenium powder be changed to the preparation that sulphur powder this method also can be suitably used for copper and indium aluminium sulphur solar battery film material, or anneal in vulcanization
Cu-In-Al-Se sulphur solar battery thin film can be prepared by further carrying out selenized annealing afterwards.We have also carried out two groups of comparisons simultaneously
Experiment, one group of contrast experiment is to dissolve copper chloride, inidum chloride and aluminium chloride to carry out a step electro-deposition in deionized water, because
For Al in aqueous solution3+The standard electrode EMF of ion is -1.662eV also more negative than hydrogen, with Cu2+The standard electrode EMF of ion+
0.337eV and In3+Standard electrode EMF -0.343eV the differences of ion are larger, and are co-deposited the electrode for then needing various elements
Potential is close to each other, so co-deposition copper aluminium three kinds of elements of indium are relatively difficult in aqueous solution, it cannot be to copper aluminium indium in coating
Ratio is accurately controlled.And in aqueous solution due to hydrionic influence, there are a large amount of hydrogen to generate in deposition process,
So that there is a large amount of holes and gap in film surface.Another set contrast experiment is that copper chloride, inidum chloride and aluminium chloride all exist
Molten condition next step electro-deposition, although molten condition can eliminate the influence of liberation of hydrogen, the coating and electro-conductive glass that deposit
The adhesive force of matrix is not strong, and film is easy to fall off, and thin film composition deviation is very serious, and main cause is when three kinds of metals
When element deposits in the molten state simultaneously, the mobility of atom is different under same deposition voltage, and deposition rate is different,
The atomic quantity that the same deposition time is deposited is different, is extremely difficult to the controllable of thin film composition.
Present invention incorporates the advantages of melting mineralization and stratified sedimentation, eliminate the influence of liberation of hydrogen, while passing through control
The controllable preparation to thin film composition, crystal structure, pattern etc. may be implemented in depositing current density and time, and prepared film is pure
Degree is high, without CuxSeyOr InxSeyBinary-phase, compared with high vacuum method, the present invention has preparation process simple, preparation efficiency
Height, utilization rate of raw materials is high, of low cost, favorable repeatability, and controllability is strong, it is easy to accomplish large area, the system of high-quality thin film
It is standby.
The present invention realizes that the technical solution of above-mentioned purpose is：
A kind of method that selenized annealing prepares Cu-In-Al-Se solar cell thin-film material after layering electro-deposition, including it is as follows
Step：
(1) NaCl and KCl are positioned in Muffle furnace after 350~500 DEG C of 4~6h of drying (or roasting), with AlCl3Fully
Mixing, is configured to AlCl3- NaCl-KCl ternary inorganic fused salt systems；
(2) the inorganic fused salt system that heating stepses (1) are obtained, control temperature make salt-mixture melt to 120~140 DEG C；
(3) fuse salt temperature obtained by step (2) is increased to 145~160 DEG C, two aluminium electrodes is inserted into, to fuse salt
Preelectrolysis cleans；
(4) after preelectrolysis, it is anode by cathode, aluminium flake of electro-conductive glass, electricity is carried out in inserting step (3) gained fuse salt
Deposition, deposition are cleaned and are dried with deionized water, absolute ethyl alcohol after the completion, and aluminium film is obtained；
(5) metal salt of copper is dissolved in deionized water, stirring makes it fully dissolve, with the conduction of aluminium film obtained by step (4)
Glass is cathode, is put into copper plating solution as anode using high-purity copper sheet and carries out electro-deposition, with deionized water, anhydrous after the completion of deposition
Ethyl alcohol is cleaned and is dried；
(6) metal salt of indium is dissolved in deionized water, adds the chloride of alkali metal, add ethylenediamine tetra-acetic acid two
Sodium, stirring make it fully dissolve, the electro-conductive glass of the electric deposition aluminum/copper film obtained using step (5) as cathode, with graphite flake or
Indium metal is that anode carries out electro-deposition, is cleaned and is dried with deionized water, absolute ethyl alcohol after the completion of deposition；
(7) performed thin film that step (6) is obtained selenizing in vacuum or inert protective gas containing selenium powder is placed in move back
Fire finally obtains copper indium aluminum selenium membrane solar cell material.
Further, in step (1), NaCl, KCl and AlCl3To analyze pure, AlCl3, NaCl and KCl mass ratio be 7
~9：1~1.05：1~1.05, preferably 8：1：1.
Further, in step (3), the current density of preelectrolysis removal of impurities is 20~200mA/cm2, electrolysis time 0.5
~1h.
Further, in step (4), electro-conductive glass includes molybdenum glass, ito glass and FTO glass.Electro-conductive glass is using
It is preceding first use acetone, ethyl alcohol, isopropanol, arbitrary two kinds in ammonium hydroxide be cleaned by ultrasonic 10~30 minutes, then with deionized water ultrasonic wave
Cleaning 10~30 minutes；The current density of electro-deposition is 1~20A/dm2, electrodeposition time is 1~600 second.
Further, in step (5), copper plating solution is acidiccopper plating liquid, and the formula of wherein acidiccopper plating liquid is
CuSO4·5H2O a concentration of 150~220g/L, H2SO4A concentration of 50~70g/L, electrodeposition temperature are room temperature, the electricity of electro-deposition
Current density is 1~20A/dm2, electrodeposition time is 1~600 second.
Further, the indium salts of step (6) are InCl3、In2(SO4)3Or In (NO3)3In any one, it is prepared
In solution the concentration range of indium ion be 10~300mmol/L, the chloride for the alkali metal being added a concentration of 100~
500mmol/L, the concentration range of disodium ethylene diamine tetraacetate are 10~300mmol/L, the current density range of electro-deposition is 1~
10A/dm2, electrodeposition time is 1~1200 second.
Further, in step (6), the chloride of alkali metal is potassium chloride, lithium chloride or sodium chloride.
It is worth noting that above-mentioned copper ion concentration and indium ion concentration indicates the concentration in electric depositing solution.
Further, during step (7) selenized annealing, need first the layering of preparation is aluminized/copper/indium precursor thin-film and
Selenium powder is put into closed container, and inert protective gas is passed through after vacuumizing, and the container equipped with sample is pushed into annealing furnace, then
Annealing furnace is warming up to 500~600 DEG C of selenized annealings 30~180 minutes, cools down container taking-up in air after the completion of annealing
To room temperature.
Further, the step (4), step (5), step (6) can adjust sequence and be step (4), step (6), walk
Suddenly (5) or step (5), step (4), step (6).
The reagent that the present invention participates in reaction is that analysis is pure, commercially available.
To study structure, pattern, ingredient and the optical property of prepared material, X is carried out to prepared sample and has been penetrated
Line diffraction analysis (XRD), scanning electron microscope analysis (SEM), energy dispersion X-ray spectrum analysis (EDS) and ultraviolet-visible
Light-near-infrared (UV-Vis-NIR) absorption spectroanalysis.
The beneficial effects of the present invention are：
(1) a step electro-deposition method in aqueous solution compared with the existing technology, the present invention use selenizing after layering electro-deposition
Annealing prepares Cu-In-Al-Se solar cell thin-film material, by the electric deposition aluminum film in particular melt salt, effectively eliminates
Then the adverse effect that evolving hydrogen reaction generates aluminium film distinguishes deposited metal copper and indium metal film again, pass through and control electricity
The controllable preparation of the ingredient to film, crystalline phase, pattern etc. may be implemented in current density and electrodeposition time, can overcome one in aqueous solution
The Cu occurred in step electrodeposition processxSeyOr InxSeyThe defect of equal Binary-phases, there are more controllable parameters, deposition process more to hold
Easy to control, film homogeneous grain size, the stoichiometric ratio of deposition are adjustable, pass through the current density and sedimentation time of deposition of aluminum film
Come the concentration of indium ion in electrolyte solution when controlling the deposition of aluminium, or indium film is deposited by control and deposition potential or sink
The product time controls the deposition of indium, to achieve the purpose that control [Al]/[In+Al] ratios, to realize adjusting Cu-In-Al-Se
Energy gap.
(2) the vacuum vapor deposition method needs of the prior art carry out in vacuum environment, need using expensive vacuum equipment and
Complicated preparation process, it is difficult to be suitable for industrialization large-scale production.Compared with high vacuum vapor method, present device is simple,
Large area uniform film can be deposited under low temperature, non-vacuum condition in substrate.The present invention is in antivacuum condition
Lower progress, can not only significantly reduce cost, and simple for process, and controllability is strong, and favorable repeatability, raw material availability are high.
Description of the drawings
Fig. 1 is the X-ray diffractogram of 1 gained sample of embodiment.
Fig. 2 is the scanning electron microscope (SEM) photograph of 1 gained sample of embodiment.
Fig. 3 is the energy dispersion X-ray spectrogram of 1 gained sample of embodiment.
Fig. 4 is ultraviolet-visible-near-infrared absorption spectrogram of 1 gained sample of embodiment.
Specific implementation mode
In order to better understand the present invention, by detailed description below combination attached drawing to technical scheme of the present invention into
Row further illustrates and describes, but present disclosure is not limited solely to the following examples.
Embodiment 1
A kind of method that selenized annealing prepares Cu-In-Al-Se solar cell thin-film material after layering electro-deposition, preparation process
It is as follows：
(1) it will analyze after pure NaCl and KCl be positioned over the dry 5h of 400 DEG C of Muffle furnace, with the pure AlCl of analysis3By AlCl3、
NaCl、KCl 8：1：1 mass ratio is sufficiently mixed, and is configured to AlCl3- NaCl-KCl ternary inorganic fused salt systems；
(2) thermal-arrest blender is used to heat, the inorganic fused salt system that step (1) is obtained, control temperature makes mixing to 130 DEG C
Salt melts；
(3) fuse salt temperature obtained by step (2) is increased to 150 DEG C, two aluminium electrodes is inserted into, to fuse salt preelectrolysis
The current density of removal of impurities, preelectrolysis removal of impurities is 50mA/cm2, electrolysis time 0.5h；
(4) molybdenum glass acetone, EtOH Sonicate are cleaned 30 minutes, then is done after twenty minutes with deionized water ultrasonic cleaning
It is dry.By clean molybdenum glass be cathode aluminium flake it is that electrodeposit metals aluminium is carried out in fuse salt obtained by anode inserting step (3), electricity is heavy
Long-pending current density is 7.5A/dm2, sedimentation time is 60 seconds, is cleaned and is done with deionized water, absolute ethyl alcohol after the completion of deposition
It is dry；
(5) 10g Salzburg vitriols are dissolved in 50ml deionized waters, adding the stirring of 3g sulfuric acid keeps it fully molten
Solution, be configured to acid copper sulfate copper facing electrolyte solution, the molybdenum glass of the electric deposition aluminum obtained using step (4) as cathode, with
High-purity copper sheet is that anode carries out electro-deposition, and the current density of electro-deposition is 10A/dm2, and sedimentation time is 60 seconds, after the completion of deposition
It is cleaned and is dried with deionized water, absolute ethyl alcohol；
(6) four trichloride hydrate indiums are dissolved in deionized water, add potassium chloride, stirring makes it fully dissolve, shape
At a concentration of 100mmol/L of indium ion, potassium chloride concentration 400mmol/L, a concentration of 50mmol/ of disodium ethylene diamine tetraacetate
The electrolyte solution of L, the molybdenum glass of the electric deposition aluminum/copper obtained using step (5) carry out electricity as cathode, by anode of graphite flake
The current density of deposition, electro-deposition is 2.5A/dm2, sedimentation time is 180 seconds.With deionized water, absolute ethyl alcohol after the completion of deposition
It cleans and dries；
(7) it is 10cm the performed thin film that step (6) is obtained to be placed in the volume containing 4mg selenium powders-3Closed container in,
Argon gas is passed through after vacuumizing；Container equipped with sample is pushed into annealing furnace, then annealing furnace is warming up to 550 DEG C of selenized annealings 60
Minute, container taking-up is cooled to room temperature in air after the completion of annealing, finally obtains copper indium aluminum selenium membrane solar cell material
Material.
The XRD spectrum and partial enlarged view of copper indium aluminum selenium membrane obtained by the present embodiment are shown in that Fig. 1, scanning electron microscope (SEM) photograph are shown in Fig. 2,
Energy spectrum diagram is shown in Fig. 3；Study of ultraviolet-visible-near infrared figure is shown in Fig. 4.
Fig. 1 gives embodiment 1 and prepares the XRD spectrum of sample and the partial enlarged view of characteristic diffraction peak.Each feature of sample
The position of diffraction maximum corresponds to (112) of Cu-In-Al-Se tetragonal crystal system, (220)/(204) and (116)/(312) crystal plane direction, built-in
Partial enlarged view show the characteristic diffraction peak of (112) crystal plane direction compared with copper indium selenide standard card collection of illustrative plates (JCPDS#80-0535) to
Right avertence is moved, and is deviated to the left compared with copper aluminium selenium standard card collection of illustrative plates (JCPDS#75-0101), because of the radius (In of indium ion3+,)
More than aluminum ions radius (Al3+,), when aluminium displacement indium, according to bragg's formula：2dsin θ=n λ, can lead to structure cell
Lattice constant becomes smaller, and reaction is deviated in X-ray characteristic diffraction peak to big angular direction, does not have other in the XRD diffraction maximums of product
Diffraction miscellaneous peak, illustrate it is proposed by the present invention layering electro-deposition after selenized annealing prepare be pure phase yellow copper structure copper and indium
Aluminium selenium.
The scanning electron microscope (SEM) photograph of Fig. 2 can be seen that the film of generation is formed by particle solid matter, surfacing, and consistency is high, brilliant
Grain is uniform in size, is completely covered substrate, and the adhesion of film and substrate is preferable.
The power spectrum graphs open-birth of Fig. 3 at product there was only copper, indium, aluminium and selenium element, the stoichiometric ratio of composition is copper：
Indium：Aluminium：Selenium=1.13：0.81：0.21：1.85.
Fig. 4 is that embodiment 1 prepares the UV-visible-near infrared absorption figure of sample, and wave spectrum wave-length coverage is from 400nm
To 1800nm.There is good absorption from being can be found that in figure in entire ultraviolet-visible range more.According to forbidden band formula：(αhv
)2~hv fittings show that the energy gap of the copper indium aluminum selenium membrane material prepared in the present embodiment is 1.42eV, and prepared is thin
Film has the feature of high efficiency thin-film solar cells.Sample prepared by other embodiment has similar characterization result.
Embodiment 2
A kind of method that selenized annealing prepares Cu-In-Al-Se solar cell thin-film material after layering electro-deposition, preparation process
It is as follows：
(1) it will analyze after pure NaCl and KCl be positioned over the dry 5h of 400 DEG C of Muffle furnace, with the pure AlCl of analysis3By AlCl3、
NaCl、KCl 8：1：1 mass ratio is fully mixed, is configured to AlCl3- NaCl-KCl ternary inorganic fused salt systems；
(2) thermal-arrest blender is used to heat, the inorganic fused salt system that step (1) is obtained, control temperature makes mixing to 130 DEG C
Salt melts.
(3) fuse salt temperature obtained by step (2) is increased to 150 DEG C, two aluminium electrodes is inserted into, to fuse salt preelectrolysis
The current density of removal of impurities, preelectrolysis removal of impurities is 5A/dm2, electrolysis time 0.5h；
(4) molybdenum glass acetone, EtOH Sonicate are cleaned 20 minutes, then is done after twenty minutes with deionized water ultrasonic cleaning
It is dry.By clean molybdenum glass be cathode aluminium flake it is that electrodeposit metals aluminium is carried out in fuse salt obtained by anode inserting step (3), electricity is heavy
Long-pending current density is 7A/dm2, sedimentation time is 60 seconds, is cleaned and is dried with deionized water, absolute ethyl alcohol after the completion of deposition；
(5) four trichloride hydrate indiums are dissolved in deionized water, add potassium chloride, stirring makes it fully dissolve, shape
At a concentration of 100mmol/L of indium ion, potassium chloride concentration 400mmol/L, a concentration of 50mmol/ of disodium ethylene diamine tetraacetate
The electrolyte solution of L, the molybdenum glass of the electric deposition aluminum obtained using step (4) are carried out electricity as anode as cathode, using graphite flake and sunk
The current density of product, electro-deposition is 2.5A/dm2, sedimentation time is 180 seconds, is washed with deionized water, absolute ethyl alcohol after the completion of deposition
It is net and dry；
(6) 10g Salzburg vitriols are dissolved in 50ml deionized waters, adding the stirring of 3g sulfuric acid keeps it fully molten
Solution, be configured to acid copper sulfate copper facing electrolyte solution, the molybdenum glass of the electric deposition aluminum/indium obtained using step (5) as cathode,
Electro-deposition is carried out by anode of high-purity copper sheet, the current density of electro-deposition is 10A/dm2, sedimentation time is 60 seconds.Deposition is completed
Deionized water, absolute ethyl alcohol is used to clean and dry afterwards；
(7) it is 10cm the performed thin film that step (6) is obtained to be placed in the volume containing 4mg selenium powders-3Closed container in,
Argon gas is passed through after vacuumizing；Container equipped with sample is pushed into annealing furnace, then annealing furnace is warming up to 550 DEG C of selenized annealings 60
Minute, container taking-up is cooled to room temperature in air after the completion of annealing, finally obtains copper indium aluminum selenium membrane solar cell material
Material.
Embodiment 3
A kind of method that selenized annealing prepares Cu-In-Al-Se solar cell thin-film material after layering electro-deposition, preparation process
It is as follows：
(1) 10g Salzburg vitriols are dissolved in 50ml deionized waters, adding the stirring of 3g sulfuric acid keeps it fully molten
Solution, be configured to acid copper sulfate copper facing electrolyte solution, molybdenum glass acetone, EtOH Sonicate cleaned 20 minutes, then spend from
Sub- water ultrasonic cleaning is dried after twenty minutes.It is cathode by clean molybdenum glass, electro-deposition, electricity is carried out by anode of high-purity copper sheet
The current density of deposition is 10A/dm2, sedimentation time is 60 seconds, is cleaned and is done with deionized water, absolute ethyl alcohol after the completion of deposition
It is dry；
(2) it will analyze after pure NaCl and KCl be positioned over the dry 5h of 400 DEG C of Muffle furnace, with the pure AlCl of analysis3By AlCl3、
NaCl、KCl 8：1：1 mass ratio is sufficiently mixed, and is configured to AlCl3- NaCl-KCl ternary inorganic fused salt systems；
(3) thermal-arrest blender is used to heat, the inorganic fused salt system that step (2) is obtained, control temperature makes mixing to 130 DEG C
Salt melts；
(4) fuse salt temperature obtained by step (3) is increased to 150 DEG C, two aluminium electrodes is inserted into, to fuse salt preelectrolysis
The current density of removal of impurities, preelectrolysis removal of impurities is 10A/dm2, electrolysis time is 20 minutes；
(5) by copper-plated molybdenum glass obtained by step (1) be cathode aluminium flake be in fuse salt obtained by anode inserting step (4) into
The current density of row electrodeposit metals aluminium, electro-deposition is 10A/dm2, sedimentation time is 45 seconds.Deposition after the completion of with deionized water,
Absolute ethyl alcohol is cleaned and is dried；
(6) four trichloride hydrate indiums are dissolved in deionized water, add potassium chloride, stirring makes it fully dissolve, shape
At a concentration of 200mmol/L of indium ion, potassium chloride concentration 500mmol/L, disodium ethylene diamine tetraacetate it is a concentration of
The electrolyte solution of 100mmol/L, the molybdenum glass of the acid copper/aluminium obtained using step (5) are sun with graphite flake as cathode
Pole carries out electro-deposition, and the current density of electro-deposition is 5A/dm2, sedimentation time is 90 seconds.With deionized water, nothing after the completion of deposition
Water-ethanol is cleaned and is dried；
(7) it is 10cm the performed thin film that step (6) is obtained to be placed in the volume containing 4mg selenium powders-3Closed container in,
Argon gas is passed through after vacuumizing；Container equipped with sample is pushed into annealing furnace, then annealing furnace is warming up to 550 DEG C of selenized annealings 60
Minute, container taking-up is cooled to room temperature in air after the completion of annealing, finally obtains copper indium aluminum selenium membrane solar cell material
Material.
Embodiment 4
A kind of method that selenized annealing prepares Cu-In-Al-Se solar cell thin-film material after layering electro-deposition, preparation process
It is as follows：
(1) it will analyze after pure NaCl and KCl be positioned over the dry 5h of 400 DEG C of Muffle furnace, with the pure AlCl of analysis3By AlCl3、
NaCl、KCl 8：1：1 mass ratio is sufficiently mixed, and is configured to AlCl3- NaCl-KCl ternary inorganic fused salt systems；
(2) thermal-arrest blender is used to heat, the inorganic fused salt system that step (1) is obtained, control temperature makes mixing to 130 DEG C
Salt melts；
(3) fuse salt temperature obtained by step (2) is increased to 150 DEG C, two aluminium electrodes is inserted into, to fuse salt preelectrolysis
The current density of removal of impurities, preelectrolysis removal of impurities is 15A/dm2, electrolysis time is 10 minutes；
(4) molybdenum glass acetone, EtOH Sonicate are cleaned 30 minutes, then is done after twenty minutes with deionized water ultrasonic cleaning
It is dry.By clean molybdenum glass be cathode aluminium flake it is that electrodeposit metals aluminium is carried out in fuse salt obtained by anode inserting step (3), electricity is heavy
Long-pending current density is 15A/dm2, sedimentation time is 60 seconds, is cleaned and is dried with deionized water, absolute ethyl alcohol after the completion of deposition；
(5) 10g Salzburg vitriols are dissolved in 50ml deionized waters, adding the stirring of 3g sulfuric acid keeps it fully molten
Solution, be configured to acid copper sulfate copper facing electrolyte solution, the molybdenum glass of the electric deposition aluminum obtained using step (4) as cathode, with
High-purity copper sheet is that anode carries out electro-deposition, and the current density of electro-deposition is 20A/dm2, sedimentation time is 60 seconds.After the completion of deposition
It is cleaned and is dried with deionized water, absolute ethyl alcohol；
(6) four trichloride hydrate indiums are dissolved in deionized water, add potassium chloride, stirring makes it fully dissolve, shape
At a concentration of 200mmol/L of indium ion, potassium chloride concentration 500mmol/L, disodium ethylene diamine tetraacetate it is a concentration of
The electrolyte solution of 100mmol/L, the molybdenum glass of the electric deposition aluminum/copper obtained using step (5) are sun with graphite flake as cathode
Pole carries out electro-deposition, and the current density of electro-deposition is 5A/dm2, sedimentation time is 180 seconds, with deionized water, nothing after the completion of deposition
Water-ethanol is cleaned and is dried；
(7) it is 10cm the performed thin film that step (6) is obtained to be placed in the volume containing 8mg selenium powders-3Closed container in,
Argon gas is passed through after vacuumizing；Container equipped with sample is pushed into annealing furnace, then annealing furnace is warming up to 550 DEG C of selenized annealings 60
Minute, container taking-up is cooled to room temperature in air after the completion of annealing, finally obtains copper indium aluminum selenium membrane solar cell material
Material.
Claims (9)
1. a kind of method that selenized annealing prepares Cu-In-Al-Se solar cell thin-film material after layering electro-deposition, feature exist
In including the following steps：
(1) NaCl and KCl are placed in Muffle furnace after 350~500 DEG C of dry 4~6h, then with AlCl3It is sufficiently mixed, is configured to
AlCl3- NaCl-KCl ternary inorganic fused salt systems；
(2) the inorganic fused salt system that heating stepses (1) are obtained, control temperature make salt-mixture melt to 120~140 DEG C；
(3) fuse salt temperature obtained by step (2) is increased to 145~160 DEG C, two aluminium electrodes is inserted into, to the pre- electricity of fuse salt
Solution removal of impurities；
(4) it is cathode aluminium flake as anode using electro-conductive glass after preelectrolysis, electro-deposition is carried out in fuse salt obtained by inserting step (3),
It is cleaned and is dried with deionized water, absolute ethyl alcohol after the completion of deposition, obtain aluminium film；
(5) metal salt of copper is dissolved in deionized water, stirring makes it fully dissolve, the electro-deposition aluminium film obtained with step (4)
Electro-conductive glass be cathode, be put into copper plating solution as anode using high-purity copper sheet and carry out electro-deposition, deposition after the completion use deionization
Water, absolute ethyl alcohol are cleaned and are dried；
(6) metal salt of indium is dissolved in deionized water, adds the chloride of alkali metal, adds disodium ethylene diamine tetraacetate,
Stirring makes it fully dissolve, and the electro-conductive glass of the electric deposition aluminum/copper film obtained using step (5) is cathode, with graphite flake or gold
It is that anode carries out electro-deposition to belong to indium, is cleaned and is dried with deionized water, absolute ethyl alcohol after the completion of deposition；
(7) performed thin film that step (6) is obtained is placed in selenized annealing in vacuum or inert protective gas containing selenium powder, most
After obtain copper indium aluminum selenium membrane solar cell material.
2. selenized annealing prepares Cu-In-Al-Se solar cell thin-film material after layering electro-deposition according to claim 1
Method, it is characterised in that：In step (1), NaCl, KCl and AlCl3To analyze pure, AlCl3, NaCl and KCl mass ratio be 7~
9：1~1.05：1~1.05.
3. selenized annealing prepares Cu-In-Al-Se solar cell thin-film material after layering electro-deposition according to claim 1
Method, it is characterised in that：In step (3), the current density of preelectrolysis removal of impurities is 20~200mA/cm2, electrolysis time be 0.5~
1h。
4. selenized annealing prepares Cu-In-Al-Se solar cell thin-film material after layering electro-deposition according to claim 1
Method, it is characterised in that：In step (4), electro-conductive glass includes molybdenum glass, ito glass, FTO glass.Electro-conductive glass is before use
Arbitrary two kinds in acetone, ethyl alcohol, isopropanol, ammonium hydroxide are first used to be cleaned by ultrasonic 10~30 minutes, then clear with deionized water ultrasonic wave
It washes 10~30 minutes；The current density of electro-deposition is 1~20A/dm2, electrodeposition time is 1~600 second.
5. selenized annealing prepares Cu-In-Al-Se solar cell thin-film material after layering electro-deposition according to claim 1
Method, it is characterised in that：In step (5), copper plating solution is acidiccopper plating liquid, and the formula of wherein acidiccopper plating liquid is
CuSO4·5H2O 150~220g/L, H2SO450~70g/L, electrodeposition temperature are room temperature, the current density of electro-deposition is 1~
20A/dm2, electrodeposition time is 1~600 second.
6. selenized annealing prepares Cu-In-Al-Se solar cell thin-film material after layering electro-deposition according to claim 1
Method, it is characterised in that：In step (6), indium salts InCl3、In2(SO4)3Or In (NO3)3In any one, it is prepared
In solution the concentration range of indium ion be 10~300mmol/L, the chloride for the alkali metal being added a concentration of 100~
The concentration range of 500mmol/L, disodium ethylene diamine tetraacetate are 10~300mmol/L, and the current density of electro-deposition is 1~10A/
dm2, electrodeposition time is 1~1200 second.
7. selenized annealing prepares Cu-In-Al-Se solar cell thin-film material after layering electro-deposition according to claim 1
Method, it is characterised in that：In step (6), the chloride of alkali metal is potassium chloride, lithium chloride or sodium chloride.
8. selenized annealing prepares Cu-In-Al-Se solar cell thin-film material after layering electro-deposition according to claim 1
Method, it is characterised in that：During step (7) selenized annealing, need first the layering of preparation is aluminized/copper/indium precursor thin-film and
Selenium powder is put into closed container, and inert protective gas is passed through after vacuumizing, and the container equipped with sample is pushed into annealing furnace, then
Annealing furnace is warming up to 450~600 DEG C of selenized annealings 30~180 minutes, cools down container taking-up in air after the completion of annealing
To room temperature.
9. selenized annealing prepares Cu-In-Al-Se solar cell thin-film material after layering electro-deposition according to claim 1
Method, it is characterised in that：The step (4), step (5), step (6) can adjust sequence as step (4), step (6), step
(5) or step (5), step (4), step (6).
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