CN108807145A - A method of preparing efficient copper indium selenide and copper-indium-galliun-selenium film solar cell - Google Patents
A method of preparing efficient copper indium selenide and copper-indium-galliun-selenium film solar cell Download PDFInfo
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- CN108807145A CN108807145A CN201810569850.1A CN201810569850A CN108807145A CN 108807145 A CN108807145 A CN 108807145A CN 201810569850 A CN201810569850 A CN 201810569850A CN 108807145 A CN108807145 A CN 108807145A
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- indium
- solar cell
- thiocarbamide
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- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000011669 selenium Substances 0.000 title claims abstract description 33
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 28
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000010408 film Substances 0.000 claims abstract description 40
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 32
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 29
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052738 indium Inorganic materials 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 24
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 239000010409 thin film Substances 0.000 claims abstract description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- LROWILPKXRHMNL-UHFFFAOYSA-N copper;thiourea Chemical compound [Cu].NC(N)=S LROWILPKXRHMNL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001953 recrystallisation Methods 0.000 claims abstract description 10
- 229910005267 GaCl3 Inorganic materials 0.000 claims abstract description 7
- 229910021617 Indium monochloride Inorganic materials 0.000 claims abstract description 4
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 71
- 239000010410 layer Substances 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 30
- 238000002360 preparation method Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000004528 spin coating Methods 0.000 claims description 21
- 238000000224 chemical solution deposition Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 206010013786 Dry skin Diseases 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 239000011733 molybdenum Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000003643 water by type Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 238000004544 sputter deposition Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- JWNCMVXVWANQND-UHFFFAOYSA-N NC(=S)N.[In] Chemical compound NC(=S)N.[In] JWNCMVXVWANQND-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000003708 ampul Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 239000011229 interlayer Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 claims description 3
- 239000013589 supplement Substances 0.000 claims description 3
- 229910000369 cadmium(II) sulfate Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000031700 light absorption Effects 0.000 abstract description 3
- 239000002250 absorbent Substances 0.000 abstract description 2
- 230000002745 absorbent Effects 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 150000004696 coordination complex Chemical class 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 101150007144 Intu gene Proteins 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000011167 hydrochloric acid Nutrition 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000006193 liquid solution Substances 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 238000001073 sample cooling Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- MOAPOQQDYQRCET-UHFFFAOYSA-N [Cu].[In].[Se]=S Chemical compound [Cu].[In].[Se]=S MOAPOQQDYQRCET-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000928 Yellow copper Inorganic materials 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical group [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02623—Liquid deposition
- H01L21/02628—Liquid deposition using solutions
-
- 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
- H01L31/036—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 their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03923—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of methods preparing efficient copper indium selenide and copper-indium-galliun-selenium film solar cell, pre-synthesis copper and indium or the thiourea complex of gallium, precursor solution is configured as raw material, the light-absorption layer of CIS and CIGS thin film solar cell are prepared with the precursor solution；Compound by finding suitable copper, indium and gallium is used as presoma and prepares precursor solution, to prepare uniform and stable CIS, CIGS the solar cell light absorbent of large area.The method of the present invention is relatively low to the purity requirement of raw material, and copper thiourea complex can be synthesized with copper powder, and the complex of indium and gallium can use the InCl compared with low-purity3·4H2O and GaCl3Then synthesis can be purified by recrystallization and obtain the complex of high-purity, cost of material can be saved by this method.
Description
Technical field
The invention belongs to technical fields, and in particular to a kind of to prepare efficient copper indium selenide and copper-indium-galliun-selenium film solar cell
Method.
Background technology
Copper indium gallium selenide (CuInGaSe2, CIGS) and it is direct band-gap semicondictor material, absorbing ability is strong, and optical band gap is adjustable,
Stability is good.Thin-film solar cells using copper indium gallium selenide (CIGS) as active layer is because materials are few, energy consumption is low and right
The purity requirement of material is relatively low and becomes the new trend of international photovoltaic market development and new hot spot in recent years.By for many years
Development, the efficiency of CIGS solar cells is suitable with crystal silicon cell at present.In December, 2017, Solar Frontier companies
For the CIGS solar cells laboratory highest transfer efficiency of preparation up to 22.9%, [1] is the thin film solar electricity reported at present
Highest photoelectric conversion efficiency in pond.However efficient CIGS solar cells are prepared by vacuum method at present, example
Such as coevaporation method and sputtering method.Vacuum method not only needs complicated equipment, and preparation process is complicated, and is difficult the uniform of control film
Property and repeatability, it is more difficult to realize large area form a film.Recent years, in order to reduce the production cost of CIGS thin film, people start
Seek the method that antivacuum (solwution method) prepares CIGS thin film.Solwution method, which prepares CIGS thin film, can substantially be divided into following three classes：
(1) electro-deposition based on electrochemical principle and electroplating technology.This method is the ripe skill being used widely in electronics industry circle
The preparation of large area film may be implemented in art, but it is one extremely complex to deposit multicomponent semi-conducting material as CIGS
Process because each member is known as different redox potentials and reduction kinetics, in order to control well chemical composition and
The homogeneity of phase generally requires multiple deposition, complex process.The document peak efficiency of the CIGS prepared by this method is 15.4%
[2]；(2) the printed/coated technology based on nano particle suspension.This method be by CIGS nano particles be prepared into suspension or
Person by one or more Cu, In, Ga, S, Se elements and its binary (ternary) nano particle be prepared into suspension by film and after
Continuous crystallization treatment is prepared into CIGS thin film.CIGS document peak efficiencies prepared by this method are 17.1% [3]；(3) it is based on molecule
The printed/coated technology of base precursor solution.Molecular precursor containing Cu, In, Ga, S/Se is directly dissolved in molten by this method
It is prepared into pure solution in agent, then passes through film, heat treatment is prepared into the CIGS thin film of high-crystallinity.This method and other solution
Method is compared and is had the advantage that：A) stoicheiometry of each component is accurately controlled；B) it is easy to control the homogeneity of film；C) letter is prepared
Single, an one-step film forming needs not move through the synthesis of nano particle；D) stock utilization is high, can theoretically reach 100%.Zhang
The CIGS batteries [4] that efficiency is up to 17.3% are prepared by this method Deng using hydrazine as solvent, which is at present by solwution method
The peak of the CIGS hull cell of preparation.However the explosion hazard of hydrazine and hypertoxicity limit its business application.Therefore people open
Beginning finds the replacement solvent of hydrazine, and makes some progress.Hillhouse seminars are with dimethyl sulfoxide (DMSO) (DMSO) for solvent
Copper indium selenide (CIS) solar cell [5] for the CIGS and 13% that efficiency is respectively 14.7% has been made.But with made from DMSO
Precursor solution stability is poor and needs high temperature (120 DEG C) spin coating.Recently, our seminars are by thiocarbamide, CuCl and InCl3It is dissolved in
The precursor solution that can be stored steadily in the long term at room temperature is made in dimethylformamide (DMF) solvent, and with the presoma
Solution is prepared for the CIS solar cells [6] that efficiency is 10.3%.However, due to InCl3In the solution not with thiocarbamide shape
At complex, the uniformity of film of this oxide for be easy to generate indium in membrane-film preparation process and preparation is poor, unfavorable
In the preparation of area battery.For this purpose, exploitation it is new can prepare uniform and stable CIS, CIGS the semiconductor film membrane material of large area
The precursor solution of material is very necessary.
Bibliography；
1.Yoshida.S.Solar Frontier achieves world record thin-film solar cel
Eficiency of 22.9%.2017；Available from:http://www.solar-frontier.com/eng/
news/2017/1220_press.html.
2.Bhattacharya, R.N., et al., 15.4%CuIn (1-x) Ga (x) Se (2)-based
photovoltaic cels from solution-based precursor films.Thin Solid Films,
2000.361:p.396-399.
17.1% Eficient Solar of 3.Brown, G., et al., Device Characteristics of a
Cel Deposited by a Non-Vacuum Printing Method on Flexible Foil.2012 38th Ieee
Photovoltaic Specialists Conference(Pvsc),2012:p.3230-3233.
4.Zhang,T.,et al.,High eficiency solution-processed thin-film Cu(In,
Ga)(Se,S)(2)solar cels.Energy&Environmental Science,2016.9(12):p.3674-3681.
5.Uhl,A.R.,J.K.Katahara,and H.W.Hillhouse,Molecular-ink route to
14.7% eficient Cu (In, Ga) (S, Se) of 13.0%eficient low-bandgap CuIn (S, Se) (2) and
(2)solar cels.Energy&Environmental Science,2016.9(1):p.130-134.
6.Jiang, J., et al., 10.3%Eficient CuIn (S, Se) 2Solar Cels from DMF
Molecular Solution with the Absorber Selenized under High Argon
Pressure.Solar RRL.0(0):p.1800044.
Invention content
Goal of the invention：In order to overcome the deficiencies in the prior art, the present invention provide it is a kind of prepare efficient copper indium selenide and
The method of copper-indium-galliun-selenium film solar cell, before the compound by finding suitable copper, indium and gallium is used as presoma preparation
Liquid solution is driven, to prepare uniform and stable CIS, CIGS the solar cell light absorbent of large area.
Technical solution：To achieve the above object, the technical solution adopted by the present invention is：
A method of efficient copper indium selenide and copper-indium-galliun-selenium film solar cell are prepared, is included the following steps：
Step 1：Metal thiourea complex synthesizes
(1) synthesis copper thiourea complex CuTU3Cl
Copper powder mixing is added in 60 DEG C of thiocarbamide saturated aqueous solutions, 100 DEG C of oil baths, concentrated hydrochloric acid, which is added, makes copper powder dissolve, and filters
It is used in combination acetone to clean, recrystallizes, 60 DEG C of dryings；
(2) synthesis indium thiourea complex InTU3Cl3Or gallium thiourea complex GaTU6Cl3
InCl is added in thiocarbamide saturated aqueous solution at room temperature3·4H2O or GaCl3Mixing, stirring, heating evaporation, room temperature are quiet
It sets, solid, recrystallization, 60 DEG C of dryings is precipitated；
Step 2：Precursor solution is prepared
By the CuTU3Cl and InTU3Cl3Or InTU3Cl3/GaTU6Cl3Mixture is dissolved in DMF solvent, before generation
Drive liquid solution；
Step 3：The preparation of indium sulphur, copper indium gallium sulphur film
The precursor solution is spin-coated on molybdenum glass and generates CIS or CIGS thin film by heat treatment；
Step 4：The preparation of copper indium selenide, CIGS thin-film
By the CIS or CIGS thin film by being heated in the atmosphere of Se, CISSe or CIGSSe films are generated；
Step 5：Copper indium selenide, the assembling of copper indium gallium selenium solar cell device
CdS buffer layers, radio-frequency sputtering Window layer, last hot evaporation Ni/Al top electrodes are deposited on absorbed layer after selenization.
Further, in step 1, the synthesis copper thiourea complex CuTU3The specific method of Cl is：
Weighing thiocarbamide and being added in 60 DEG C of hot water makes thiocarbamide dissolving saturation, adds copper powder mixing, makes rubbing for thiocarbamide and copper
You are than being 4：1；100 DEG C of oil baths, concentrated hydrochloric acid, which is added, makes copper powder dissolve, and continues oil bath and stirring, and supplement ultra-pure water until solution
Become clear；It filters, filtrate stands cooling, and white elongate column solid is precipitated, filters and is cleaned with acetone, and carries out weight
Crystallization, the 60 DEG C of dryings of last baking oven.
Further, in step 1, the synthesis indium thiourea complex InTU3Cl3Specific method be：
At room temperature, weighing thiocarbamide and being added in ultra-pure water makes thiocarbamide dissolving saturation, adds InCl3·4H2O makes thiocarbamide and indium
Molar ratio be 3：1~4：1, stirring is until solution clear；80 DEG C of heated solutions evaporate 3/5~4/5 water, stop
Heating, is stored at room temperature, and solid is precipitated, and recrystallized, the 60 DEG C of dryings of last baking oven.
Further, in step 1, the synthesis gallium thiourea complex GaTU6Cl3Specific method be：
At room temperature, weighing thiocarbamide and being added in ultra-pure water makes thiocarbamide dissolving saturation, adds GaCl3, make rubbing for thiocarbamide and gallium
You are than being 3：1~4：1, stirring is until solution clear；60 DEG C of heated solution evaporations, until thering is solid precipitation, stopping to heat,
It is stored at room temperature, solid is precipitated, and recrystallized, the 60 DEG C of dryings of last baking oven.
Further, in step 2, the CuTU3Cl and InTU3Cl3Or InTU3Cl3/GaTU6Cl3Mixture by Cu,
Molar ratio Cu/In=0.6-1.2 or Cu/ (In+Ga)=0.6-1.2 of In, Ga, Ga/ (In+Ga)=0-0.5 are dissolved into DMF
In solvent；InTU3Cl3Molar concentration 0.2-1.0 mol/Ls in DMF.
Further, precursor solution preparation method is specially：Weigh InTU3Cl3, DMF and stirring magneton, room temperature is added
Lower stirring, waits for InTU3Cl3CuTU is weighed after being completely dissolved3Cl is added in solution, and stirring at room temperature obtains nothing up to being completely dissolved
The transparent mixed solution of color.
Further, in step 3, spin speed is 600~8000 revs/min, and spin-coating time is 0s~300s, heating temperature
Degree is 150~600 DEG C, and heating time is 1~100min.
Further, in step 4, selenylation reaction carries out under oxygen-free environment, and the pressure in selenizing quartz ampoule is 0.1MPa
~1.0MPa heating temperatures are 300~600 DEG C, and heating time is 5~300 minutes；.
Further, in step 5, by depositing one layer of CdS buffer layer on the absorbed layer of chemical bath deposition after selenization,
Then the Window layer of radio-frequency sputtering i-ZnO containing 30nm and 200nm ITO, last hot evaporation layer of Ni/Al top electrodes.
Further, the process of chemical bath deposition is：150mL ultra-pure waters, 22mL are added into a water-bath beaker
18.46mmol/L CdSO4With 28mL ammonium hydroxide, it is passed through the 65 DEG C of hot water heated in advance into water-bath beaker interlayer and passes through magnetic
Power blender is stirred continuously, and the thiocarbamide of 22mL 0.75mol/L is added after 1min, continues to heat and stir 11min；The thickness of CdS layer
Degree is 15~50nm.
Advantageous effect：The method provided by the invention for preparing efficient copper indium selenide and copper-indium-galliun-selenium film solar cell, is adopted
The method taken is the thiourea complex of pre-synthesis copper and indium or gallium, then configures forerunner by raw material of the complex of these synthesis
Liquid solution prepares the light-absorption layer of CIS or CIGS thin film solar cell with the precursor solution.This method has following excellent
Point：(1) relatively low to the purity requirement of raw material, copper thiourea complex can be synthesized with copper powder, the complex of indium and gallium can with compared with
The InCl of low-purity3·4H2O and GaCl3Then synthesis can be purified by recrystallization and obtain the complex of high-purity, by this
Method can save cost of material.(2) cuprous ion with thiocarbamide be coordinated after can it is stable in the air+I valences, indium and gallium ion with
It can prevent from hydrolyzing after thiocarbamide coordination, raw material is convenient for storage.(3) after metal is coordinated with thiocarbamide, carbon-sulphur coordinate bond is formd, favorably
Metal sulfide is formed in heat treatment process after spin coating, while preventing the generation of oxide.
Description of the drawings
The XRD spectrum of the copper thiourea complex of Fig. 1 synthesis
The XRD spectrum of the indium thiourea complex of Fig. 2 synthesis
The XRD spectrum of the gallium thiourea complex of Fig. 3 synthesis
The CuIn (Se, S) that Fig. 4 is prepared using metal complex as raw material2XRD spectrum
The CuIn (Se, S) that Fig. 5 is prepared using metal complex as raw material2XRD spectrum (pressurization selenizing)
The cross-section SEM images for the CIS solar cells that Fig. 6 is prepared using metal complex as raw material
The cross-section SEM images (pressurization selenizing) for the CIS solar cells that Fig. 7 is prepared using metal complex as raw material
The J-V curves for the CIS solar cells that Fig. 8 is prepared using metal complex as raw material
The J-V curves for the CIGS and CIS solar cells that Fig. 9 is prepared using metal complex as raw material.
Specific implementation mode
The present invention main method be：Then the thiourea complex of pre-synthesis copper and indium or gallium being matched with what these were synthesized
It is that raw material configures precursor solution to close object, and the light-absorption layer of CIS or CIGS thin film solar cell are prepared with the precursor solution.
It is as follows：
Step 1：Metal thiourea complex synthesizes.
(1) synthesis copper thiourea complex (CuTU3Cl)
Weighing appropriate thiocarbamide and being added in 60 DEG C of hot water makes thiocarbamide that can just be saturated, after thiocarbamide is completely dissolved thereto
A certain amount of copper powder is added, it is 4 to make the molar ratio of thiocarbamide and copper：1.Then said mixture in 100 DEG C of oil baths and is stirred, it is past
Appropriate concentrated hydrochloric acid, which is wherein added, makes copper powder dissolve, and continues oil bath and stirring, until solution becomes clear.Then it takes out while hot
Filtrate Slow cooling is precipitated white elongate column solid, obtained solid is filtered and is cleaned with acetone by filter.By what is obtained
Solid product is recrystallized, by the product oven drying after recrystallization.
(2) synthesis indium thiourea complex (InTU3Cl3)
Weighing appropriate thiocarbamide and being added at room temperature in ultra-pure water makes thiocarbamide be completely dissolved and forms saturated solution, is charged with
A certain amount of InCl3·4H2O, it is 3 to make the molar ratio of thiocarbamide and indium：1~4：1, stirring makes solution become clear, and 80 DEG C add
Hot solution evaporates 3/5~4/5 water, and be stored at room temperature makes solid be precipitated for a period of time.Obtained solid product is tied again
Crystalline substance, by the product oven drying after recrystallization.
(3) synthesis gallium thiourea complex (GaTU6Cl3)
Weighing in the ultra-pure water of appropriate thiocarbamide addition at room temperature makes thiocarbamide that can just be saturated, past after thiocarbamide is completely dissolved
A certain amount of GaCl is wherein added3, it is 3 to make the molar ratio of thiocarbamide and gallium：1~4：1, stirring makes solution become clear, and 60
DEG C heated solution evaporates part water until there is solid precipitation, stops heating, standing makes more solids be precipitated.The solid that will be obtained
Product is recrystallized, by the product oven drying after recrystallization.
Step 2：Precursor solution is prepared
Copper and indium (or copper and indium, gallium) and the complex of thiocarbamide are dissolved into DMF solvent by a certain percentage, stirring makes
It is completely dissolved generation precursor solution.
Step 3：The preparation of indium sulphur, copper indium gallium sulphur film
The precursor solution that step 2 is prepared is spin-coated on molybdenum glass and generates CuInS by heat treatment2(CIS) or
Person Cu (In, Ga) S2(CIGS) film.Spin speed may be configured as 600~8000 revs/min, spin-coating time may be configured as 0s~
300s, heating temperature section are 150~600 DEG C, and heating time is 1~100min.
Step 4：The preparation of copper indium selenide, CIGS thin-film
The step is the CIS that will be generated in step 3 or CIGS thin film by being heated in the atmosphere of Se, with the parts Se
CuIn (S, Se) is generated respectively after substitution S atom2, Cu (In, Ga) (S, Se)2, selenidation process simultaneously improve formation film crystallization
Degree and photoelectric property.The air in quartz ampoule must be emptied before selenizing and be filled with argon gas, it is ensured that selenylation reaction is in oxygen-free environment
Lower progress.Heating temperature is 300~600 DEG C, and heating time is 5~300 minutes.
Step 4：Copper indium selenide, the assembling of copper indium gallium selenium solar cell device
By depositing one layer of CdS buffer layer on the absorbed layer of chemical bath deposition (CBD) after selenization, then radio-frequency sputtering contains
The Window layer of 30nm i-ZnO and 200nm ITO, last hot evaporation layer of Ni/Al top electrodes.
The present invention is further described with reference to the accompanying drawings and examples.
According to following embodiments, the present invention can be better understood from.However, as it will be easily appreciated by one skilled in the art that real
It applies specific material proportion, process conditions and its result described in example and is merely to illustrate the present invention, without that should will not limit
The present invention described in detail in claims processed.
Embodiment 1：Thiourea complex with the copper of synthesis, indium is that raw material prepares precursor solution, and is prepared with the solution
CIS solar cells.
Synthesize copper thiourea complex (CuTU3Cl)：It measures 50mL ultra-pure waters and 250mL beakers is added, be heated to 60 DEG C, then
10.05g thiocarbamides are charged with, are stirred to clarify.It weighs 2.008g copper powders to be added in above-mentioned solution, 100 DEG C of oil baths wait for temperature
30mL concentrated hydrochloric acids are added after being raised to 100 DEG C, observes that red copper powder disappears, white solid occurs, white solid continues to increase simultaneously
In cotton-shaped, supplement 30mL ultra-pure waters make solid dissolve.Then it filters while hot, filtrate is stood and is cooled down, bottom of the beaker after a period of time
There are a large amount of white elongate column solids in portion.Obtained solid is filtered and is washed with acetone, 60mL ultra-pure waters recrystallization is added,
The square pyramid shape solid of rule is obtained, obtained solid is put into vacuum drying oven, 60 DEG C of drying.
Synthesize indium thiourea complex (InTU3Cl3)：It weighs 5.8002g thiocarbamides to be added in 250mL beakers, be charged with
50mL ultra-pure waters, stirring make thiocarbamide be completely dissolved, weigh 7.5347g InCl3·4H2O is added thereto, and stirs a whole night.It will be molten
80 DEG C of heating of liquid, evaporate 3/5ths water, stop heating, white solid occurs in beaker bottom after standing a period of time.It will
Obtained solid recrystallizes, and the solid after recrystallization is put into vacuum drying oven, 60 DEG C of dryings 5 hours.
Synthesize gallium thiourea complex (GaTU6Cl3)：It weighs 1.4217g thiocarbamides to be added in 50mL beakers, be charged with
14mL ultra-pure waters, stirring make thiocarbamide be completely dissolved, weigh 0.98g GaCl3It is added thereto, has observed white smoke generation, stirred
Mixing makes solution become to clarify.60 DEG C of heated solutions evaporate part water until there is solid precipitation, stop heating, standing makes more solid
Body is precipitated.20mL ultra-pure waters are added into obtained solid to be recrystallized, the solid after recrystallization is put into vacuum drying oven,
60 DEG C of dryings 5 hours.
Precursor solution is prepared：Weigh the InTU of 2.187g synthesis3Cl3It is added in the sample bottle of 20mL, adds DMF8mL
With stirring magneton, stirs at room temperature, wait for InTU3Cl3CuTU is weighed after being completely dissolved3Cl 1.365g are added in solution, at room temperature
Stirring obtains the mixed solution of water white transparency up to being completely dissolved.
The preparation of indium sulphur (CIS) film：The good molybdenum glass of pre-wash is fixed on the sucker of sol evenning machine, setting ginseng
After number (spin speed is 4000 revs/min, spin-coating time 60s), precursor solution is taken out with needle tubing, through 0.2 μm of filter membrane mistake
Solution is added dropwise on molybdenum glass after filter, solution is made to be paved with the surface of molybdenum glass, starts spin coating.After spin coating, sample is put
To be previously heated in 340 DEG C of thermal station heat (annealing) 1min.After sample cooling, above spin coating-heating process is repeated 7 times
Required thickness is can reach, spin coating terminates.
The preparation of copper indium selenium sulfide (CISSe) film：The CIS samples that spin coating is got well and is heat-treated are put into graphite, are weighed
0.35g selenium grains are symmetrically disposed at sample surrounding.Then graphite is put into tube furnace, valve is fastened, vacuumizing makes in pipe
Vacuum degree reaches 3 × 10-1Torr, then argon gas is passed through in pipe, 3 times are repeated above operation to empty the air in pipe, it is ensured that selenium
Change reaction to carry out under oxygen-free environment.Heating parameters (heating temperature is 570 DEG C, heats 20min) are set, adjusts intake valve and goes out
The size of air valve makes the pressure in quartz ampoule be an atmospheric pressure, opens tube furnace after reaching the time, selenylation reaction terminates to continue
Logical argon gas takes out sample until being cooled to room temperature.
It is prepared by device：Sample after selenizing is put into ammonium sulfide solution and impregnates 15min to remove the CuSe on surface, then
It takes out sample to be rinsed with deionized water, one layer of CdS buffer layer is deposited by chemical bath deposition (CBD).The mistake of chemical bath deposition
Cheng Wei：150mL ultra-pure waters, the CdSO of 22mL 18.46mmol/L are added into a water-bath beaker4With 28mL ammonium hydroxide, past water-bath
It is passed through the 65 DEG C of hot water heated in advance in beaker interlayer and is stirred continuously by magnetic stirring apparatus, 22mL is added after 1min
The thiocarbamide of 0.75mol/L continues to heat and stir 11min.The thickness of CdS layer is about 30nm.Then radio-frequency sputtering i- containing 30nm
The Window layer of ZnO and 200nm ITO, last hot evaporation layer of Ni/Al top electrodes.
Embodiment 2：Thiourea complex with the copper of synthesis, indium is that raw material prepares precursor solution, and is prepared with the solution
CIS solar cells.
Precursor solution is prepared：Complex used in the implementation case is to be synthesized in embodiment 1.Weigh 1.018g synthesis
InTU3Cl3It is added in the sample bottle of 20mL, adds DMF 3.8mL and stirring magneton, stir at room temperature, wait for InTU3Cl3It is complete
CuTU is weighed after fully dissolved3Cl 0.63g are added in solution, and stirring at room temperature obtains the mixing of water white transparency up to being completely dissolved
Solution.
The preparation of indium sulphur (CIS) film：Washed molybdenum glass is fixed on the sucker of sol evenning machine, arrange parameter (rotation
It is 4000 revolutions per seconds to apply speed, spin-coating time 60s).Precursor solution is taken out with needle tubing, changes syringe needle into filter tip, after filtering
Solution is added dropwise on molybdenum glass, so that solution is paved with the surface of molybdenum glass, turns on the switch, carries out spin coating.After spin coating, this
Sample is placed in thermal station, and adjustment parameter (heating temperature is 340 DEG C, heating time 1min), is turned on the switch, is carried out hot place
Reason.Heating finishes.After sample cooling, spin coating is re-started, then be heat-treated, step is as above, can reach after 7 times repeatedly
Required thickness, spin coating terminate.
The preparation of copper indium selenium sulfide (CISSe) film：This selenizing is carried out at 0.155MPa.Spin coating is got well and is heat-treated
CIS samples are put into graphite, are weighed 0.35g selenium grains and are symmetrically disposed at sample surrounding.Then graphite is put into tube furnace,
Valve is fastened, vacuumizing makes vacuum degree in pipe reach 3 × 10-1Torr, then argon gas is passed through in pipe, it repeats above operation 3 times
To empty the air in pipe, it is ensured that selenylation reaction carries out under oxygen-free environment.Heating parameters are arranged, and (heating temperature is 570 DEG C, is added
Hot 20min), adjusting intake valve and air outlet valve makes the pressure in quartz ampoule remain 0.155MPa.Heating is opened after reaching the time
Tube furnace, selenylation reaction terminates to continue logical argon gas until being cooled to room temperature takes out sample.
It is prepared by device：Sample after selenizing is put into ammonium sulfide solution and impregnates 15min to remove the CuSe on surface, then
It takes out sample to be rinsed with deionized water, one layer of CdS buffer layer is deposited by chemical bath deposition (CBD).The mistake of chemical bath deposition
Cheng Wei：150mL ultra-pure waters, the CdSO of 22mL 18.46mmol/L are added into a water-bath beaker4With 28mL ammonium hydroxide, past water-bath
It is passed through the 65 DEG C of hot water heated in advance in beaker interlayer and is stirred continuously by magnetic stirring apparatus, 22mL is added after 1min
The thiocarbamide of 0.75mol/L continues to heat and stir 11min.The thickness of CdS layer is 30nm~50nm.Then radio-frequency sputtering contains
The Window layer of 30nm i-ZnO and 200nm ITO, last hot evaporation layer of Ni/Al top electrodes.
Embodiment 3：Thiourea complex with the copper of synthesis, indium and gallium is raw material preparation precursor solution, and with the solution
Prepare CIGS and CIS solar cells.
Precursor solution is prepared：Complex used in the implementation case is to be synthesized in embodiment 1.
(1) CIGS precursor solutions：Weigh the InTU of 0.45g synthesis3Cl3It is added in the sample bottle of 20mL, DMF is added
3mL is stirred at room temperature, waits for InTU3Cl3CaTU is weighed after being completely dissolved6Cl30.16g is added in solution, makes the atom of gallium and indium
Than Ga/ (In+Ga)=0.2, stirring at room temperature is eventually adding CuTU up to being completely dissolved3Cl 0.35g, stir to dissolve
To the mixed solution of water white transparency.
(2) CIS precursor solutions：Weigh the InTU of 0.75g synthesis3Cl3It is added in the sample bottle of 20mL, adds DMF
3mL and stirring magneton, stir, wait for InTU at room temperature3Cl3CuTU is weighed after being completely dissolved3Cl 0.47g are added in solution, room temperature
Lower stirring obtains the mixed solution of water white transparency up to being completely dissolved.
The preparation of copper indium gallium sulphur (CIGS) film：The good molybdenum glass of pre-wash is fixed on the sucker of sol evenning machine, if
After setting parameter (spin speed is 3600 revs/min, spin-coating time 60s), precursor solution is taken out with needle tubing, is filtered through 0.2 μm
Solution is added dropwise on molybdenum glass after membrane filtration, solution is made to be paved with the surface of molybdenum glass, starts spin coating.After spin coating, by sample
Product, which are put into, to be previously heated to heat (annealing) 1min in 340 DEG C of thermal station).After sample cooling, it is heated to repeat the above spin coating-
Journey 8 times can reach required thickness, and spin coating terminates.
The preparation of Cu-In-Ga-Se-S (CIGSSe) film：The CIGS samples that spin coating is got well and is heat-treated are put into graphite,
It weighs 0.35g selenium grains and is symmetrically disposed at sample surrounding.Then graphite is put into tube furnace, valve is fastened, vacuumizing makes
Vacuum degree reaches 3 × 10 in pipe-1Torr, then argon gas is passed through in pipe, repeat above operation 3 times to empty the air in pipe, really
Selenylation reaction is protected to carry out under oxygen-free environment.Heating parameters (heating temperature is 570 DEG C, heats 20min) are set, intake valve is adjusted
Make the pressure in quartz ampoule be an atmospheric pressure with the size of air outlet valve, opens tube furnace after reaching the time, selenylation reaction terminates
Continue logical argon gas until being cooled to room temperature takes out sample.
It is prepared by device：Sample after selenizing is put into ammonium sulfide solution and impregnates 15min to remove the CuSe on surface, then
It takes out sample to be rinsed with deionized water, one layer of CdS buffer layer is deposited by chemical bath deposition (CBD).The mistake of chemical bath deposition
Cheng Wei：150mL ultra-pure waters, the CdSO of 22mL 18.46mmol/L are added into a water-bath beaker4With 28mL ammonium hydroxide, past water-bath
It is passed through the 65 DEG C of hot water heated in advance in beaker interlayer and is stirred continuously by magnetic stirring apparatus, 22mL is added after 1min
The thiocarbamide of 0.75mol/L continues to heat and stir 11min.The thickness of CdS layer is 30-50nm.Then radio-frequency sputtering contains 30nm
The Window layer of i-ZnO and 200nm ITO, last hot evaporation layer of Ni/Al top electrodes.
The elemental analysis result of 1 synthetic compound of table
The mass fraction of each element is listed in table 1, the mass fraction for indicating according to target chemical formula calculating in bracket.
As shown in Figure 1, the copper thiourea complex of synthesis has CuTU3Cl3Crystal structure.
As shown in Fig. 2, the indium thiourea complex of synthesis has InTU3Cl3Crystal structure.
As shown in figure 3, the gallium thiourea complex of synthesis has crystal structure.
As shown in figure 4, the CuIn (Se, S) prepared as raw material using metal complex2Absorbed layer has yellow copper structure, does not have
It is found secondary phase.
As shown in figure 5, the CuIn (Se, S) for selenizing preparation of pressurizeing using metal complex as raw material2Absorbed layer has chalcopyrite
Structure does not find secondary phase.
As shown in fig. 6, absorber thickness is 1 μm, absorbed layer is fine and close, and crystallite dimension is close to film thickness.
As shown in fig. 7, absorber thickness is 1 μm, absorbed layer has a small amount of hole after selenizing of pressurizeing, but absorbed layer still relatively causes
It is close.
As shown in figure 8, CIS solar battery efficiencies prepared by the precursor solution for being 0.85 with copper and indium molar ratio are
7.4%, open-circuit voltage 335.1mV, short circuit current 40.1mA/cm2, fill factor 0.52, battery performance is good.Pass through tune
It saves raw material copper and indium molar ratio or incorporation gallium, battery performance also has the space advanced optimized.
As shown in figure 9, the figure is the J-V songs of the CIS and CIGS solar cells prepared with metal complex in embodiment 3
Line is added after gallium as can be seen from this figure, and the open-circuit voltage of battery significantly improves.
The above is only a preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of method preparing efficient copper indium selenide and copper-indium-galliun-selenium film solar cell, it is characterised in that：Including following step
Suddenly：
Step 1：Metal thiourea complex synthesizes
(1) synthesis copper thiourea complex CuTU3Cl
Copper powder mixing is added in 60 DEG C of thiocarbamide saturated aqueous solutions, 100 DEG C of oil baths, concentrated hydrochloric acid, which is added, makes copper powder dissolve, and suction filtration is used in combination
Acetone cleans, recrystallization, 60 DEG C of dryings；
(2) synthesis indium thiourea complex InTU3Cl3Or gallium thiourea complex GaTU6Cl3
InCl is added in thiocarbamide saturated aqueous solution at room temperature3·4H2O or GaCl3Mixing, stirring, heating evaporation are stored at room temperature, and are analysed
Go out solid, recrystallizes, 60 DEG C of dryings；
Step 2：Precursor solution is prepared
By the CuTU3Cl and InTU3Cl3Or InTU3Cl3/GaTU6Cl3Mixture is dissolved in DMF solvent, and it is molten to generate presoma
Liquid；
Step 3：The preparation of indium sulphur, copper indium gallium sulphur film
The precursor solution is spin-coated on molybdenum glass and generates CIS or CIGS thin film by heat treatment；
Step 4：The preparation of copper indium selenide, CIGS thin-film
By the CIS or CIGS thin film by being heated in the atmosphere of Se, CISSe or CIGSSe films are generated；
Step 5：Copper indium selenide, the assembling of copper indium gallium selenium solar cell device
CdS buffer layers, radio-frequency sputtering Window layer, last hot evaporation Ni/Al top electrodes are deposited on absorbed layer after selenization.
2. the method according to claim 1 for preparing efficient copper indium selenide and copper-indium-galliun-selenium film solar cell, feature
It is：In step 1, the synthesis copper thiourea complex CuTU3The specific method of Cl is：
Weighing thiocarbamide and being added in 60 DEG C of hot water makes thiocarbamide dissolving saturation, adds copper powder mixing, makes the molar ratio of thiocarbamide and copper
It is 4：1；100 DEG C of oil baths, concentrated hydrochloric acid, which is added, makes copper powder dissolve, and continues oil bath and stirring, and supplement ultra-pure water until solution becomes
Clear；It filters, filtrate stands cooling, and white elongate column solid is precipitated, filters and is cleaned with acetone, and tied again
Crystalline substance, the 60 DEG C of dryings of last baking oven.
3. the method according to claim 1 for preparing efficient copper indium selenide and copper-indium-galliun-selenium film solar cell, feature
It is：In step 1, the synthesis indium thiourea complex InTU3Cl3Specific method be：
At room temperature, weighing thiocarbamide and being added in ultra-pure water makes thiocarbamide dissolving saturation, adds InCl3·4H2O makes rubbing for thiocarbamide and indium
You are than being 3：1~4：1, stirring is until solution clear；80 DEG C of heated solutions evaporate 3/5~4/5 water, stop heating,
It is stored at room temperature, solid is precipitated, and recrystallized, the 60 DEG C of dryings of last baking oven.
4. the method according to claim 1 for preparing efficient copper indium selenide and copper-indium-galliun-selenium film solar cell, feature
It is：In step 1, the synthesis gallium thiourea complex GaTU6Cl3Specific method be：
At room temperature, weighing thiocarbamide and being added in ultra-pure water makes thiocarbamide dissolving saturation, adds GaCl3, make the molar ratio of thiocarbamide and gallium be
3：1~4：1, stirring is until solution clear；60 DEG C of heated solution evaporations stop heating, room temperature is quiet until there is solid precipitation
It sets, solid is precipitated, and recrystallized, the 60 DEG C of dryings of last baking oven.
5. the method according to claim 1 for preparing efficient copper indium selenide and copper-indium-galliun-selenium film solar cell, feature
It is：In step 2, the CuTU3Cl and InTU3Cl3Or InTU3Cl3/GaTU6Cl3Mixture presses the molar ratio of Cu, In, Ga
Cu/In=0.6-1.2 or Cu/ (In+Ga)=0.6-1.2, Ga/ (In+Ga)=0-0.5 are dissolved into DMF solvent；
InTU3Cl3Molar concentration 0.2-1.0 mol/Ls in DMF.
6. efficient copper indium selenide and the method for copper-indium-galliun-selenium film solar cell are prepared according to claim 1 or 5, it is special
Sign is：Precursor solution preparation method is specially：Weigh InTU3Cl3, DMF and stirring magneton is added, stirs, waits at room temperature
InTU3Cl3CuTU is weighed after being completely dissolved3Cl is added in solution, and stirring at room temperature obtains water white transparency up to being completely dissolved
Mixed solution.
7. the method according to claim 1 for preparing efficient copper indium selenide and copper-indium-galliun-selenium film solar cell, feature
It is：In step 3, spin speed is 600~8000 revs/min, and spin-coating time is 0s~300s, and heating temperature is 150~600
DEG C, heating time is 1~100min.
8. the method according to claim 1 for preparing efficient copper indium selenide and copper-indium-galliun-selenium film solar cell, feature
It is：In step 4, selenylation reaction carries out under oxygen-free environment, and the pressure in selenizing quartz ampoule heats for 0.1MPa~1.0MPa
Temperature is 300~600 DEG C, and heating time is 5~300 minutes；.
9. the method according to claim 1 for preparing efficient copper indium selenide and copper-indium-galliun-selenium film solar cell, feature
It is：In step 5, by depositing one layer of CdS buffer layer, then radio-frequency sputtering on the absorbed layer of chemical bath deposition after selenization
The Window layer of i-ZnO containing 30nm and 200nm ITO, last hot evaporation layer of Ni/Al top electrodes.
10. the method according to claim 9 for preparing efficient copper indium selenide and copper-indium-galliun-selenium film solar cell, feature
It is：The process of chemical bath deposition is：150mL ultra-pure waters are added into a water-bath beaker, 22mL 18.46mmol/L's
CdSO4With 28mL ammonium hydroxide, 65 DEG C of hot water heated in advance and continuous by magnetic stirring apparatus are passed through into water-bath beaker interlayer
It stirs, the thiocarbamide of 22mL 0.75mol/L is added after 1min, continue to heat and stir 11min；The thickness of CdS layer be 15~
50nm。
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