CN108807145B - Method for preparing efficient copper indium selenide and copper indium gallium selenide thin-film solar cell - Google Patents
Method for preparing efficient copper indium selenide and copper indium gallium selenide thin-film solar cell Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 61
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000010409 thin film Substances 0.000 title claims abstract description 45
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 136
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 28
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 23
- 229910052738 indium Inorganic materials 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- LROWILPKXRHMNL-UHFFFAOYSA-N copper;thiourea Chemical compound [Cu].NC(N)=S LROWILPKXRHMNL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910005267 GaCl3 Inorganic materials 0.000 claims abstract description 6
- 229910021617 Indium monochloride Inorganic materials 0.000 claims abstract description 5
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 81
- 238000010438 heat treatment Methods 0.000 claims description 59
- 239000010410 layer Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 37
- 239000007787 solid Substances 0.000 claims description 29
- 238000004528 spin coating Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 238000005303 weighing Methods 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 19
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 19
- 239000012498 ultrapure water Substances 0.000 claims description 19
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000011669 selenium Substances 0.000 claims description 16
- 238000000224 chemical solution deposition Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 12
- 238000010521 absorption reaction Methods 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
- 101150007144 Intu gene Proteins 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- JWNCMVXVWANQND-UHFFFAOYSA-N NC(=S)N.[In] Chemical class NC(=S)N.[In] JWNCMVXVWANQND-UHFFFAOYSA-N 0.000 claims description 8
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 150000003585 thioureas Chemical class 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229910000369 cadmium(II) sulfate Inorganic materials 0.000 claims description 5
- LCUOIYYHNRBAFS-UHFFFAOYSA-N copper;sulfanylideneindium Chemical compound [Cu].[In]=S LCUOIYYHNRBAFS-UHFFFAOYSA-N 0.000 claims description 5
- 239000011229 interlayer Substances 0.000 claims description 5
- 238000002207 thermal evaporation Methods 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 claims description 3
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 8
- 230000031700 light absorption Effects 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 2
- 238000001953 recrystallisation Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 239000010408 film Substances 0.000 description 14
- 229910052711 selenium Inorganic materials 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 150000004696 coordination complex Chemical class 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 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
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- -1 gallium ions Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical group [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 241001123946 Gaga Species 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- 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
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- 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
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02612—Formation types
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- H01L21/02623—Liquid deposition
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Abstract
The invention discloses a method for preparing high-efficiency copper indium selenide and copper indium gallium selenide thin-film solar cells, which comprises the steps of synthesizing a thiourea complex of copper and indium or gallium in advance, preparing a precursor solution by taking the thiourea complex as a raw material, and preparing a light absorption layer of a CIS and a CIGS thin-film solar cell by using the precursor solution; a precursor solution is prepared by searching suitable compounds of copper, indium and gallium as precursors so as to prepare large-area uniform and stable CIS and CIGS solar cell light absorption materials. The method has low requirement on the purity of the raw materials, the copper thiourea complex can be synthesized by using copper powder, and the complex of indium and gallium can be synthesized by using InCl with low purity3·4H2O and GaCl3The complex with high purity can be obtained by synthesis and then purification through recrystallization, and the method can save the cost of raw materials.
Description
Technical Field
The invention belongs to the technical field, and particularly relates to a method for preparing efficient copper indium diselenide and copper indium gallium diselenide thin-film solar cells.
Background
Copper indium gallium selenide (CuInGaSe)2CIGS) is a direct band gap semiconductor material, and has strong light absorption capacity, adjustable optical band gap and good stability. Thin film solar cells using Copper Indium Gallium Selenide (CIGS) as an active layer have become a new trend and a new hot spot in the development of the international photovoltaic market in recent years due to less material consumption, low production energy consumption and relatively low requirement on the purity of the material. Over the years of development, CIGS solar cells have now been comparable in efficiency to crystalline silicon cells. The highest conversion efficiency of CIGS solar cell laboratory prepared by SolarFrontier reaches 22.9 percent in 12 months in 2017, [ 1%]Is the highest photoelectric conversion efficiency in the thin film solar cell reported at present. Currently, however, high efficiency CIGS solar cells are fabricated by vacuum processes such as co-evaporation and sputtering. The vacuum method not only requires complicated equipment and a complicated preparation process, but also is difficult to control the uniformity and the repeatability of the film and to realize large-area film formation. In recent years, a method for preparing a CIGS thin film without vacuum (solution method) has been sought in order to reduce the production cost of the CIGS thin film. The solution method for preparing CIGS thin films can be roughly classified into the following three types: (1) electrodeposition and electroplating techniques based on electrochemical principles. The method is a mature technology widely applied in the electronic industry, and can realize the preparation of a large-area film, but the deposition of a multi-component semiconductor material such as CIGS is a very complex process, because each element has different oxidation-reduction potential and reduction kinetics, and multi-step deposition is often required in order to well control the chemical composition and phase uniformity, and the process is complex. The highest efficiency of CIGS produced by this method is 15.4% [2 ]](ii) a (2) Printing/coating techniques based on suspensions of nanoparticles. The method is to prepare CIGS nano particles into turbid liquid or prepare one or more Cu, In, Ga, S and Se elements and binary (ternary) nano particles thereof into turbid liquid, and prepare the CIGS film through film coating and subsequent crystallization treatment. The highest efficiency of CIGS prepared by the method is 17.1% [3 ]](ii) a (3) Printing/coating techniques based on molecular-based precursor solutions. According to the method, a molecular precursor containing Cu, In, Ga and S/Se is directly dissolved In a solvent to prepare a pure solution, and then the CIGS thin film with high crystallinity is prepared through film coating and heat treatment. Compared with other solution methods, the method has the following advantages: a) the chemical proportion of each component is accurately controlled; b) the uniformity of the film is easy to control; c) the preparation is simple, one-step film forming is realized, and the synthesis of nano particles is not needed; d) the material utilization rate is high and can reach 100 percent theoretically. The method for preparing the CIGS battery with the efficiency as high as 17.3 percent by using hydrazine as a solvent such as Zhang]This efficiency is the highest value for CIGS thin film cells currently produced by solution processes. However, the explosive and highly toxic nature of hydrazine has limited its commercial use. Therefore, alternative solvents for hydrazine have been sought and certain progress has been made. The Hillhouse subject group was efficiently obtained using dimethyl sulfoxide (DMSO) as a solventCIGS 14.7% and CIS 13% respectively [5 ]]. However, the precursor solution prepared in DMSO has poor stability and requires high temperature (120 ℃) spin coating. Recently, our group of topics consisted of thiourea, CuCl and InCl3Dissolving in dimethyl formamide (DMF) solvent to obtain precursor solution which can be stored stably at room temperature for a long time, and preparing the CIS solar cell with the efficiency of 10.3 percent by using the precursor solution [6 ]]. However, due to InCl3No complex is formed with thiourea in the solution, so that indium oxide is easily generated in the film preparation process, and the prepared film has poor uniformity and is not beneficial to the preparation of large-area batteries. Therefore, it is necessary to develop a new precursor solution capable of preparing a large-area uniform and stable CIS and CIGS semiconductor thin film material.
References to the literature;
1.Yoshida.S.Solar Frontier achieves world record thin-film solar celeficiency 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)-basedphotovoltaic cels from solution-based precursor films.Thin Solid Films,2000.361:p.396-399.
3.Brown,G.,et al.,Device Characteristics of a 17.1％Eficient SolarCel Deposited by a Non-Vacuum Printing Method on Flexible Foil.2012 38th IeeePhotovoltaic 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 to13.0％eficient low-bandgap CuIn(S,Se)(2)and 14.7％eficient Cu(In,Ga)(S,Se)(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 DMFMolecular Solution with the Absorber Selenized under High ArgonPressure.Solar RRL.0(0):p.1800044.
disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention provides a method for preparing efficient copper indium selenide and copper indium gallium selenide thin-film solar cells.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing high-efficiency copper indium selenide and copper indium gallium selenide thin-film solar cells comprises the following steps:
the method comprises the following steps: synthesis of metal thiourea complexes
(1) Synthesis of copper thiourea Complex CuTU3Cl
Adding copper powder into saturated thiourea aqueous solution at 60 ℃, mixing, carrying out oil bath at 100 ℃, adding concentrated hydrochloric acid to dissolve the copper powder, carrying out suction filtration, cleaning with acetone, recrystallizing, and drying at 60 ℃;
(2) synthesis of indium thiourea complexes InTU3Cl3Or gallium thiourea complex GaTU6Cl3
Adding InCl into saturated thiourea solution at room temperature3·4H2O or GaCl3Mixing, stirring, heating for evaporation, standing at room temperature, precipitating solid, recrystallizing, and drying at 60 deg.C;
step two: preparation of precursor solution
Mixing the CuTU3Cl and InTU3Cl3Or InTU3Cl3/GaTU6Cl3Dissolving the mixture in a DMF solvent to generate a precursor solution;
step three: preparation of copper indium sulfide and copper indium gallium sulfide thin film
Spin-coating the precursor solution on molybdenum glass and heating to generate a CIS or CIGS thin film;
step four: preparation of copper indium selenide and copper indium gallium selenide thin films
Heating the CIS or CIGS thin film in Se atmosphere to generate a CISSe or CIGSSe thin film;
step five: copper indium selenium and copper indium gallium selenium solar cell device assembly
Depositing a CdS buffer layer on the selenized absorption layer, sputtering a window layer by radio frequency, and finally thermally evaporating a Ni/Al top electrode.
Further, in the step one, the synthetic copper thiourea complex CuTU3The specific method of Cl is as follows:
weighing thiourea, adding the thiourea into hot water at 60 ℃ to dissolve the thiourea to saturation, adding copper powder, and mixing until the molar ratio of the thiourea to the copper is 4: 1; performing oil bath at 100 ℃, adding concentrated hydrochloric acid to dissolve the copper powder, continuously performing oil bath and stirring, and supplementing ultrapure water until the solution becomes clear and transparent; and (4) carrying out suction filtration, standing and cooling the filtrate, separating out white long columnar solid, carrying out suction filtration, washing with acetone, recrystallizing, and finally drying in an oven at 60 ℃.
Further, in the step one, the indium thiourea complex InTU is synthesized3Cl3The specific method comprises the following steps:
weighing thiourea, adding the thiourea into ultrapure water at room temperature to dissolve the thiourea to saturation, and adding InCl3·4H2O, the molar ratio of thiourea to indium is 3: 1-4: 1, stirring until the solution is clear and transparent; heating the solution at 80 ℃, evaporating 3/5-4/5 water, stopping heating, standing at room temperature, separating out solids, recrystallizing, and finally drying in an oven at 60 ℃.
Further, in the step one, the gallium thiourea complex GaTU is synthesized6Cl3The specific method comprises the following steps:
weighing thiourea, adding the thiourea into ultrapure water at room temperature to dissolve and saturate the thiourea, and adding GaCl3And enabling the molar ratio of thiourea to gallium to be 3: 1-4: 1, stirring until the solution is clear and transparent; heating the solution at 60 ℃ for evaporation until a solid is separated out, stopping heating, standing at room temperature, separating out the solid, recrystallizing, and finally drying in an oven at 60 ℃.
Further, in the second step, the CuTU3Cl and InTU3Cl3Or InTU3Cl3/GaTU6Cl3The mixture is Cu/In 0.6-1.2 or Cu/(In +according to the mol ratio of Cu, In and GaGa 0.6-1.2, Ga/(In + Ga) 0-0.5 is dissolved In DMF solvent; InTU3Cl3The molar concentration in DMF is 0.2-1.0 mol/l.
Further, the preparation method of the precursor solution specifically comprises the following steps: weighing InTU3Cl3Adding DMF and stirring magneton, stirring at room temperature, standing for InTU3Cl3Weighing CuTU after completely dissolving3Cl was added to the solution, and stirred at room temperature until it was completely dissolved, to obtain a colorless transparent mixed solution.
Further, in the third step, the spin-coating speed is 600-8000 rpm, the spin-coating time is 0-300 s, the heating temperature is 150-600 ℃, and the heating time is 1-100 min.
Further, in the fourth step, the selenization reaction is carried out in an oxygen-free environment, the pressure in the selenized quartz tube is 0.1 MPa-1.0 MPa, the heating temperature is 300-600 ℃, and the heating time is 5-300 minutes; .
Further, in the fifth step, a CdS buffer layer is deposited on the selenized absorption layer through chemical bath deposition, then a window layer containing 30nm i-ZnO and 200nm ITO is subjected to radio frequency sputtering, and finally a Ni/Al top electrode is subjected to thermal evaporation.
Further, the chemical bath deposition process comprises the following steps: a water bath beaker was charged with 150mL of ultrapure water, 22mL of 18.46mmol/L CdSO4Adding 28mL of ammonia water, introducing preheated 65 ℃ hot water into the interlayer of the water bath beaker, continuously stirring by using a magnetic stirrer, adding 22mL of 0.75mol/L thiourea after 1min, and continuously heating and stirring for 11 min; the thickness of the CdS layer is 15-50 nm.
Has the advantages that: the method for preparing the high-efficiency copper indium selenide and copper indium gallium selenide thin-film solar cell adopts the method that thiourea complexes of copper and indium or gallium are synthesized in advance, then precursor solution is prepared by taking the synthesized complexes as raw materials, and the precursor solution is used for preparing a light absorption layer of the CIS or CIGS thin-film solar cell. The method has the following advantages: (1) the purity requirement of raw materials is low, the copper thiourea complex can be synthesized by copper powder, and the complex of indium and gallium can be synthesized by InCl with low purity3·4H2O and GaCl3Synthesized and then passed throughThe complex with high purity can be obtained by purification through recrystallization, and the cost of raw materials can be saved through the method. (2) Cuprous ions can be stabilized at a valence of + I in the air after being coordinated with thiourea, indium and gallium ions can be prevented from being hydrolyzed after being coordinated with thiourea, and the raw materials are convenient to store. (3) After the metal is coordinated with thiourea, a carbon-sulfur coordination bond is formed, which is beneficial to forming metal sulfide in the heat treatment process after spin coating and simultaneously preventing the generation of oxide.
Drawings
FIG. 1 XRD pattern of the synthesized copper thiourea complex
FIG. 2 XRD pattern of synthesized indium thiourea complex
FIG. 3 XRD pattern of synthesized gallium thiourea complex
FIG. 4 illustrates CuIn (Se, S) prepared from metal complex2XRD pattern of
FIG. 5 illustrates CuIn (Se, S) prepared from a metal complex2XRD pattern of (pressure selenization)
FIG. 6 is a cross-sectional SEM image of a CIS solar cell prepared from a metal complex as a raw material
FIG. 7 is a SEM image (pressurized selenization) of a cross section of a CIS solar cell prepared from a metal complex as a raw material
FIG. 8 is a J-V curve of a CIS solar cell prepared from a metal complex
FIG. 9J-V curves for CIGS and CIS solar cells prepared from metal complexes.
Detailed Description
The main method of the invention is as follows: thiourea complexes of copper and indium or gallium are synthesized in advance, then precursor solution is prepared by taking the synthesized complexes as raw materials, and the precursor solution is used for preparing a light absorption layer of a CIS or CIGS thin-film solar cell. The method comprises the following specific steps:
the method comprises the following steps: and (3) synthesizing a metal thiourea complex.
(1) Synthesis of copper thiourea complexes (CuTU)3Cl)
Weighing a proper amount of thiourea, adding the thiourea into hot water at 60 ℃ to enable the thiourea to be just saturated, and adding a certain amount of copper powder into the thiourea after the thiourea is completely dissolved to enable the molar ratio of the thiourea to the copper to be 4: 1. the mixture was then oil-bathed at 100 ℃ and stirred, an appropriate amount of concentrated hydrochloric acid was added to dissolve the copper powder, and the oil bath and stirring were continued until the solution became clear and transparent. And then carrying out suction filtration while the solution is hot, slowly cooling the filtrate to precipitate a white slender columnar solid, and carrying out suction filtration on the obtained solid and washing the solid with acetone. And recrystallizing the obtained solid product, and drying the recrystallized product in an oven.
(2) Synthesis of indium thiourea complexes (InTU)3Cl3)
Weighing appropriate amount of thiourea, adding into ultrapure water at room temperature to completely dissolve thiourea and form saturated solution, adding certain amount of InCl3·4H2O, the molar ratio of thiourea to indium is 3: 1-4: 1, stirring to enable the solution to become clear and transparent, heating the solution at 80 ℃ to evaporate water from 3/5-4/5, and standing for a period of time at room temperature to enable solids to be precipitated. And recrystallizing the obtained solid product, and drying the recrystallized product in an oven.
(3) Synthesis of gallium thiourea complexes (GaTU)6Cl3)
Weighing appropriate amount of thiourea, adding the thiourea into ultrapure water at room temperature to enable the thiourea to be just saturated, and adding a certain amount of GaCl into the thiourea after the thiourea is completely dissolved3And enabling the molar ratio of thiourea to gallium to be 3: 1-4: 1, stirring to enable the solution to become clear and transparent, heating the solution at 60 ℃ to evaporate part of water until solids are separated out, stopping heating, and standing to enable more solids to be separated out. And recrystallizing the obtained solid product, and drying the recrystallized product in an oven.
Step two: preparation of precursor solution
Dissolving the complex of copper and indium (or copper, indium and gallium) and thiourea in DMF solvent according to a certain proportion, and stirring to completely dissolve the complex to generate precursor solution.
Step three: preparation of copper indium sulfide and copper indium gallium sulfide thin film
Spin-coating the precursor solution prepared in the step two on molybdenum glass and heating to generate CuInS2(CIS) or Cu (In, Ga) S2(CIGS) thin films. The spin-coating speed can be set to 600-8000 rpm, and the spin-coating time can be set to 0s &300s, the heating temperature interval is 150-600 ℃, and the heating time is 1-100 min.
Step four: preparation of copper indium selenide and copper indium gallium selenide thin films
Heating the CIS or CIGS thin film generated in the third step in the Se atmosphere to partially replace S atoms with Se and respectively generate CuIn (S, Se)2，Cu(In,Ga)(S,Se)2The selenization process simultaneously improves the crystallinity and the optoelectronic properties of the formed film. Before selenization, air in the quartz tube must be exhausted and argon gas must be filled in the quartz tube to ensure that the selenization reaction is carried out in an oxygen-free environment. The heating temperature is 300-600 ℃, and the heating time is 5-300 minutes.
Step four: copper indium selenium and copper indium gallium selenium solar cell device assembly
Depositing a CdS buffer layer on the selenized absorption layer through Chemical Bath Deposition (CBD), then performing radio frequency sputtering on a window layer containing 30nm i-ZnO and 200nm ITO, and finally performing thermal evaporation on a layer of Ni/Al top electrode.
The invention is further described with reference to the following figures and examples.
The present invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the specific material ratios, process conditions and results thereof described in the examples are illustrative only and should not be taken as limiting the invention as detailed in the claims.
Example 1: and preparing a precursor solution by using the synthesized thiourea complex of copper and indium as a raw material, and preparing the CIS solar cell by using the solution.
Synthesis of copper thiourea complexes (CuTU)3Cl): 50mL of ultrapure water was measured and added to a 250mL beaker, heated to 60 ℃ and then 10.05g of thiourea was added thereto and stirred until it was clear. Weighing 2.008g of copper powder, adding the copper powder into the solution, carrying out oil bath at 100 ℃, adding 30mL of concentrated hydrochloric acid after the temperature rises to 100 ℃, observing that the red copper powder disappears, a white solid appears, the white solid continuously increases and is flocculent, and supplementing 30mL of ultrapure water to dissolve the solid. Then, the solution is filtered while the solution is hot, the filtrate is kept stand and cooled, and a large amount of white slender columnar solid appears at the bottom of the beaker after a period of time. The obtained solidThe solid was filtered and washed with acetone, and then recrystallized by adding 60mL of ultrapure water to obtain a regular square pyramid-shaped solid, which was then placed in a vacuum oven and dried at 60 ℃.
Synthesis of indium thiourea complexes (InTU)3Cl3): 5.8002g of thiourea was weighed into a 250mL beaker, 50mL of ultrapure water was added thereto, and stirring was carried out to completely dissolve the thiourea, and 7.5347g of InCl was weighed3·4H2O was added thereto, and stirred for one night. The solution was heated at 80 ℃ to evaporate three fifths of the water, the heating was stopped and a white solid appeared at the bottom of the beaker after standing for a period of time. Recrystallizing the obtained solid, putting the recrystallized solid into a vacuum oven, and drying for 5 hours at 60 ℃.
Synthesis of gallium thiourea complexes (GaTU)6Cl3): 1.4217g of thiourea was weighed into a 50mL beaker, 14mL of ultrapure water was added thereto, stirring was carried out to completely dissolve the thiourea, and 0.98g of GaCl was weighed3Upon addition, a white smoke was observed and the solution was clear by stirring. Heating the solution at 60 ℃ to evaporate part of the water until solids are precipitated, stopping heating, and standing to precipitate more solids. The obtained solid was recrystallized by adding 20mL of ultrapure water, and the recrystallized solid was put into a vacuum oven and dried at 60 ℃ for 5 hours.
Preparing a precursor solution: weighing 2.187g of synthesized InTU3Cl3Adding into a 20mL sample bottle, adding DMF8mL and stirring magneton, stirring at room temperature until InTU is ready3Cl3Weighing CuTU after completely dissolving31.365g of Cl was added to the solution, and stirred at room temperature until it was completely dissolved, to obtain a colorless transparent mixed solution.
Preparation of Copper Indium Sulfide (CIS) thin film: fixing the molybdenum glass cleaned in advance on a sucker of a spin coater, setting parameters (the spin coating speed is 4000 rpm, and the spin coating time is 60s), taking out the precursor solution by using a needle tube, filtering by using a 0.2-micrometer filter membrane, dropwise adding the solution on the molybdenum glass, enabling the solution to be fully paved on the surface of the molybdenum glass, and starting spin coating. After the spin coating was completed, the sample was heated (annealed) on a hot stage previously heated to 340 ℃ for 1 min. After the sample is cooled, repeating the spin coating-heating process for 7 times to obtain the required thickness, and ending the spin coating.
Preparing Cu-in-Se-S (CISSe) film by placing spin-coated and heat-treated CIS sample in a graphite box, weighing 0.35g selenium particles, symmetrically placing around the sample, placing the graphite box in a tube furnace, closing the valve, and vacuumizing to make the vacuum degree in the tube reach 3 × 10-1And (3) Torr, introducing argon into the tube, repeating the operation for 3 times to exhaust the air in the tube, and ensuring that the selenization reaction is carried out in an oxygen-free environment. Setting heating parameters (the heating temperature is 570 ℃, the heating time is 20min), adjusting the sizes of the air inlet valve and the air outlet valve to enable the pressure in the quartz tube to be one atmosphere, starting the tube furnace after the time is reached, and continuing introducing argon gas until the selenization reaction is finished and cooling to the normal temperature to take out a sample.
Preparing a device: and soaking the selenized sample in an ammonium sulfide solution for 15min to remove CuSe on the surface, taking out the sample, washing the sample with deionized water, and depositing a CdS buffer layer by Chemical Bath Deposition (CBD). The chemical bath deposition process comprises the following steps: a water bath beaker was charged with 150mL of ultrapure water, 22mL of 18.46mmol/L CdSO4And 28mL of ammonia water, introducing preheated 65 ℃ hot water into the interlayer of the water bath beaker, continuously stirring by a magnetic stirrer, adding 22mL of 0.75mol/L thiourea after 1min, and continuously heating and stirring for 11 min. The CdS layer has a thickness of about 30 nm. Then a window layer containing 30nm i-ZnO and 200nm ITO is sputtered in a radio frequency mode, and finally a layer of Ni/Al top electrode is evaporated in a thermal evaporation mode.
Example 2: and preparing a precursor solution by using the synthesized thiourea complex of copper and indium as a raw material, and preparing the CIS solar cell by using the solution.
Preparing a precursor solution: the complex used in this example was synthesized as in example 1. 1.018g of synthesized InTU was weighed3Cl3Adding into a 20mL sample bottle, adding DMF 3.8mL and stirring magneton, stirring at room temperature until InTU is ready3Cl3Weighing CuTU after completely dissolving30.63g of Cl was added to the solution, and the mixture was stirred at room temperature until it was completely dissolved to obtain a colorless transparent mixed solution.
Preparation of Copper Indium Sulfide (CIS) thin film: and (3) fixing the washed molybdenum glass on a sucker of a spin coater, and setting parameters (the spin coating speed is 4000 rpm/sec, and the spin coating time is 60 s). And taking out the precursor solution by using a needle tube, replacing a needle head with a filter tip, filtering, dripping the solution on the molybdenum glass to enable the solution to be fully paved on the surface of the molybdenum glass, and turning on a switch to carry out spin coating. After the spin coating is finished, the sample is placed on a hot bench, parameters are adjusted (the heating temperature is 340 ℃, the heating time is 1min), a switch is turned on, and heat treatment is carried out. And (4) finishing heating. And after the sample is cooled, carrying out spin coating again, carrying out heat treatment, repeating the steps for 7 times to obtain the required thickness, and finishing the spin coating.
Preparing Cu-in-Se-S (CISSe) film by selenizing at 0.155MPa, putting rotary coated and heat treated CIS sample in a graphite box, weighing 0.35g selenium particles, symmetrically placing around the sample, putting the graphite box in a tube furnace, closing the valve, and vacuumizing to make the vacuum degree in the tube reach 3 × 10-1And (3) Torr, introducing argon into the tube, repeating the operation for 3 times to exhaust the air in the tube, and ensuring that the selenization reaction is carried out in an oxygen-free environment. Heating parameters are set (the heating temperature is 570 ℃, the heating time is 20min), and the air inlet valve and the air outlet valve are adjusted to keep the pressure in the quartz tube at 0.155 MPa. And starting the tube furnace after the heating time is reached, and continuously introducing argon after the selenization reaction is finished until the temperature is cooled to the normal temperature, and taking out the sample.
Preparing a device: and soaking the selenized sample in an ammonium sulfide solution for 15min to remove CuSe on the surface, taking out the sample, washing the sample with deionized water, and depositing a CdS buffer layer by Chemical Bath Deposition (CBD). The chemical bath deposition process comprises the following steps: a water bath beaker was charged with 150mL of ultrapure water, 22mL of 18.46mmol/L CdSO4And 28mL of ammonia water, introducing preheated 65 ℃ hot water into the interlayer of the water bath beaker, continuously stirring by a magnetic stirrer, adding 22mL of 0.75mol/L thiourea after 1min, and continuously heating and stirring for 11 min. The thickness of the CdS layer is 30-50 nm. Then a window layer containing 30nm i-ZnO and 200nm ITO is sputtered in a radio frequency mode, and finally a layer of Ni/Al top electrode is evaporated in a thermal evaporation mode.
Example 3: and preparing a precursor solution by using the synthesized thiourea complex of copper, indium and gallium as a raw material, and preparing the CIGS and CIS solar cell by using the solution.
Preparing a precursor solution: the complex used in this example was synthesized as in example 1.
(1) CIGS precursor solution: 0.45g of synthesized InTU was weighed3Cl3Adding into a 20mL sample bottle, adding DMF3mL, stirring at room temperature until InTU is ready3Cl3Weighing CatU after complete dissolution6Cl30.16g of the solution was added to the solution so that the atomic ratio of gallium to indium, Ga/(In + Ga), became 0.2, and the mixture was stirred at room temperature until completely dissolved, and finally CuTU was added30.35g of Cl was dissolved by stirring to obtain a colorless transparent mixed solution.
(2) CIS precursor solution: 0.75g of synthesized InTU was weighed out3Cl3Adding into a 20mL sample bottle, adding DMF3mL and stirring magneton, stirring at room temperature until InTU is ready3Cl3Weighing CuTU after completely dissolving30.47g of Cl was added to the solution, and the mixture was stirred at room temperature until it was completely dissolved to obtain a colorless transparent mixed solution.
Preparation of Copper Indium Gallium Sulfide (CIGS) film: fixing the molybdenum glass cleaned in advance on a sucker of a spin coater, setting parameters (the spin coating speed is 3600 r/min, the spin coating time is 60s), taking out the precursor solution by using a needle tube, filtering by using a 0.2-micrometer filter membrane, dropwise adding the solution on the molybdenum glass, enabling the solution to be fully paved on the surface of the molybdenum glass, and starting spin coating. After the spin coating was completed, the sample was heated (annealed) on a hot stage previously heated to 340 ℃ for 1 min). After the sample is cooled, repeating the spin coating-heating process for 8 times to obtain the required thickness, and ending the spin coating.
Preparing CIGS-Se-S (CIGSSe) film by placing a CIGS sample which is coated in a spinning mode and is subjected to heat treatment into a graphite box, weighing 0.35g of selenium grains, symmetrically placing the selenium grains around the sample, then placing the graphite box into a tube furnace, closing a valve, vacuumizing to enable the vacuum degree in the tube to reach 3 × 10-1And (3) Torr, introducing argon into the tube, repeating the operation for 3 times to exhaust the air in the tube, and ensuring that the selenization reaction is carried out in an oxygen-free environment. Setting heating parameters (heating temperature is 570 ℃, heating for 20min), adjusting the sizes of the air inlet valve and the air outlet valve to enable the pressure in the quartz tube to be one atmosphere, starting the tube furnace after the pressure reaches the atmospheric pressure, and ending the selenization reactionAnd continuously introducing argon until the temperature is cooled to the normal temperature, and taking out the sample.
Preparing a device: and soaking the selenized sample in an ammonium sulfide solution for 15min to remove CuSe on the surface, taking out the sample, washing the sample with deionized water, and depositing a CdS buffer layer by Chemical Bath Deposition (CBD). The chemical bath deposition process comprises the following steps: a water bath beaker was charged with 150mL of ultrapure water, 22mL of 18.46mmol/L CdSO4And 28mL of ammonia water, introducing preheated 65 ℃ hot water into the interlayer of the water bath beaker, continuously stirring by a magnetic stirrer, adding 22mL of 0.75mol/L thiourea after 1min, and continuously heating and stirring for 11 min. The thickness of the CdS layer is 30-50 nm. Then a window layer containing 30nmi-ZnO and 200nm ITO is sputtered by radio frequency, and finally a layer of Ni/Al top electrode is evaporated by heat.
TABLE 1 results of elemental analysis of the synthesized complexes
The mass fractions of the respective elements are shown in Table 1, and the mass fractions calculated in accordance with the target chemical formula are shown in parentheses.
As shown in FIG. 1, the synthesized copper thiourea complex has CuTU3Crystal structure of Cl.
As shown in FIG. 2, the synthesized indium thiourea complex has InTU3Cl3The crystal structure of (1).
As shown in fig. 3, the synthesized gallium thiourea complex has a crystal structure.
As shown in FIG. 4, CuIn (Se, S) prepared from the metal complex2The absorption layer has a chalcopyrite structure and no secondary phase is found.
As shown in FIG. 5, CuIn (Se, S) prepared by pressure selenization of metal complex as raw material2The absorption layer has a chalcopyrite structure and no secondary phase is found.
As shown in FIG. 6, the thickness of the absorption layer was 1 μm, the absorption layer was dense, and the crystal grain size was close to the film thickness.
As shown in FIG. 7, the thickness of the absorption layer is 1 μm, and the absorption layer has a few holes after pressure selenization, but the absorption layer is still dense.
As shown in FIG. 8, the efficiency of the CIS solar cell prepared from the precursor solution with the copper-indium molar ratio of 0.85 was 7.4%, the open-circuit voltage was 355.1mV, and the short-circuit current was 40.1mA/cm2The filling factor is 0.52, and the battery performance is good. By adjusting the molar ratio of the raw materials of copper and indium or doping gallium, the cell performance has further optimized space.
As shown in fig. 9, which is a J-V curve of CIS and CIGS solar cells prepared using the metal complex in example 3, it can be seen that the open circuit voltage of the cell is significantly increased after gallium is added.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (10)
1. A method for preparing high-efficiency copper indium selenide and copper indium gallium selenide thin-film solar cells is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: synthesis of metal thiourea complexes
(1) Synthesis of copper thiourea Complex CuTU3Cl
Adding copper powder into saturated thiourea aqueous solution at 60 ℃, mixing, carrying out oil bath at 100 ℃, adding concentrated hydrochloric acid to dissolve the copper powder, carrying out suction filtration, cleaning with acetone, recrystallizing, and drying at 60 ℃;
(2) synthesis of indium thiourea complexes InTU3Cl3Or gallium thiourea complex GaTU6Cl3
Adding InCl into saturated thiourea solution at room temperature3·4H2O or GaCl3Mixing, stirring, heating for evaporation, standing at room temperature, precipitating solid, recrystallizing, and drying at 60 deg.C;
step two: preparation of precursor solution
Mixing the CuTU3Cl and InTU3Cl3Or InTU3Cl3/GaTU6Cl3Dissolving the mixture in a DMF solvent to generate a precursor solution;
step three: preparation of copper indium sulfide and copper indium gallium sulfide thin film
Spin-coating the precursor solution on molybdenum glass and heating to generate a CIS or CIGS thin film;
step four: preparation of copper indium selenide and copper indium gallium selenide thin films
Heating the CIS or CIGS thin film in Se atmosphere to generate a CISSe or CIGSSe thin film;
step five: copper indium selenium and copper indium gallium selenium solar cell device assembly
Depositing a CdS buffer layer on the selenized absorption layer, sputtering a window layer by radio frequency, and finally thermally evaporating a Ni/Al top electrode.
2. The method of claim 1 for manufacturing high efficiency copper indium diselenide and copper indium gallium diselenide thin film solar cells, wherein: in the first step, the copper thiourea complex CuTU is synthesized3The specific method of Cl is as follows:
weighing thiourea, adding the thiourea into hot water at 60 ℃ to dissolve the thiourea to saturation, adding copper powder, and mixing until the molar ratio of the thiourea to the copper is 4: 1; performing oil bath at 100 ℃, adding concentrated hydrochloric acid to dissolve the copper powder, continuously performing oil bath and stirring, and supplementing ultrapure water until the solution becomes clear and transparent; and (4) carrying out suction filtration, standing and cooling the filtrate, separating out white long columnar solid, carrying out suction filtration, washing with acetone, recrystallizing, and finally drying in an oven at 60 ℃.
3. The method of claim 1 for manufacturing high efficiency copper indium diselenide and copper indium gallium diselenide thin film solar cells, wherein: in the first step, the indium thiourea complex InTU is synthesized3Cl3The specific method comprises the following steps:
weighing thiourea, adding the thiourea into ultrapure water at room temperature to dissolve the thiourea to saturation, and adding InCl3·4H2O, the molar ratio of thiourea to indium is 3: 1-4: 1, stirring until the solution is clear and transparent; heating the solution at 80 deg.C, evaporatingAnd (3) removing water from 3/5-4/5, stopping heating, standing at room temperature, precipitating a solid, recrystallizing, and finally drying in an oven at 60 ℃.
4. The method of claim 1 for manufacturing high efficiency copper indium diselenide and copper indium gallium diselenide thin film solar cells, wherein: in the step one, the gallium thiourea complex GaTU is synthesized6Cl3The specific method comprises the following steps:
weighing thiourea, adding the thiourea into ultrapure water at room temperature to dissolve and saturate the thiourea, and adding GaCl3And enabling the molar ratio of thiourea to gallium to be 3: 1-4: 1, stirring until the solution is clear and transparent; heating the solution at 60 ℃ for evaporation until a solid is separated out, stopping heating, standing at room temperature, separating out the solid, recrystallizing, and finally drying in an oven at 60 ℃.
5. The method of claim 1 for manufacturing high efficiency copper indium diselenide and copper indium gallium diselenide thin film solar cells, wherein: in the second step, the CuTU3Cl and InTU3Cl3Or InTU3Cl3/GaTU6Cl3Dissolving the mixture into DMF solvent according to the molar ratio of Cu, In and Ga (Cu/In is 0.6-1.2) or Cu/(In + Ga) is 0.6-1.2, and Ga/(In + Ga) is 0-0.5); InTU3Cl3The molar concentration in DMF is 0.2-1.0 mol/l.
6. The method of preparing high efficiency copper indium diselenide and copper indium gallium diselenide thin film solar cells as claimed in claim 1 or 5, wherein: the preparation method of the precursor solution comprises the following steps: weighing InTU3Cl3Adding DMF and stirring magneton, stirring at room temperature, standing for InTU3Cl3Weighing CuTU after completely dissolving3Cl was added to the solution, and stirred at room temperature until it was completely dissolved, to obtain a colorless transparent mixed solution.
7. The method of claim 1 for manufacturing high efficiency copper indium diselenide and copper indium gallium diselenide thin film solar cells, wherein: in the third step, the spin-coating speed is 600-8000 rpm, the spin-coating time is not more than 300s, the heating temperature is 150-600 ℃, and the heating time is 1-100 min.
8. The method of claim 1 for manufacturing high efficiency copper indium diselenide and copper indium gallium diselenide thin film solar cells, wherein: in the fourth step, the selenization reaction is carried out in an oxygen-free environment, the pressure in the selenized quartz tube is 0.1 MPa-1.0 MPa, the heating temperature is 300-600 ℃, and the heating time is 5-300 minutes.
9. The method of claim 1 for manufacturing high efficiency copper indium diselenide and copper indium gallium diselenide thin film solar cells, wherein: depositing a CdS buffer layer on the selenized absorption layer through chemical bath deposition, then performing radio frequency sputtering on a window layer containing 30nm i-ZnO and 200nm ITO, and finally performing thermal evaporation on a Ni/Al top electrode.
10. The method of claim 9 for producing high efficiency copper indium diselenide and copper indium gallium diselenide thin film solar cells, wherein: the chemical bath deposition process comprises the following steps: a water bath beaker was charged with 150mL of ultrapure water, 22mL of 18.46mmol/L CdSO4Adding 28mL of ammonia water, introducing preheated 65 ℃ hot water into the interlayer of the water bath beaker, continuously stirring by using a magnetic stirrer, adding 22mL of 0.75mol/L thiourea after 1min, and continuously heating and stirring for 11 min; the thickness of the CdS layer is 15-50 nm.
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| CN110246698B (en) * | 2019-06-21 | 2022-03-15 | 南京邮电大学 | Metal sulfide thin film boiling method based on reusable precursor liquid |
| CN111071997B (en) * | 2019-12-17 | 2021-07-13 | 青海民族大学 | Preparation method of copper indium selenium nanosheet |
| CN111554760B (en) * | 2020-05-15 | 2022-06-17 | 南京邮电大学 | Precursor solution of copper-zinc-tin-sulfur thin film solar cell and preparation method and application thereof |
| CN115557868A (en) * | 2022-09-23 | 2023-01-03 | 南京邮电大学 | Metal thiourea complex based on thiourea and copper acetate, and derivative and application thereof |
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