CN114188442A - Preparation method of antimony-doped electrochemical deposition copper-zinc-tin-sulfur solar cell absorption layer - Google Patents
Preparation method of antimony-doped electrochemical deposition copper-zinc-tin-sulfur solar cell absorption layer Download PDFInfo
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- CN114188442A CN114188442A CN202111499816.XA CN202111499816A CN114188442A CN 114188442 A CN114188442 A CN 114188442A CN 202111499816 A CN202111499816 A CN 202111499816A CN 114188442 A CN114188442 A CN 114188442A
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- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 33
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 30
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010409 thin film Substances 0.000 claims abstract description 29
- 238000000137 annealing Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- 239000011733 molybdenum Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000004073 vulcanization Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 6
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 claims abstract description 6
- 229940111695 potassium tartrate Drugs 0.000 claims abstract description 6
- 239000001509 sodium citrate Substances 0.000 claims abstract description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract description 6
- 235000019345 sodium thiosulphate Nutrition 0.000 claims abstract description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 6
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 6
- 235000011083 sodium citrates Nutrition 0.000 claims abstract description 5
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims abstract description 5
- 239000001476 sodium potassium tartrate Substances 0.000 claims abstract description 4
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims abstract description 3
- 239000010408 film Substances 0.000 claims description 28
- 238000000151 deposition Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000009713 electroplating Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims 1
- 230000002745 absorbent Effects 0.000 claims 1
- 239000002250 absorbent Substances 0.000 claims 1
- 239000006096 absorbing agent Substances 0.000 claims 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 230000001681 protective effect Effects 0.000 claims 1
- MUYUEDVRJJRNOO-UHFFFAOYSA-N selanylidene(sulfanylidene)antimony Chemical compound S=[Sb]=[Se] MUYUEDVRJJRNOO-UHFFFAOYSA-N 0.000 claims 1
- OQRNKLRIQBVZHK-UHFFFAOYSA-N selanylideneantimony Chemical compound [Sb]=[Se] OQRNKLRIQBVZHK-UHFFFAOYSA-N 0.000 claims 1
- 238000005486 sulfidation Methods 0.000 claims 1
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 description 2
- 238000000861 blow drying Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001472 potassium tartrate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PDYXSJSAMVACOH-UHFFFAOYSA-N [Cu].[Zn].[Sn] Chemical compound [Cu].[Zn].[Sn] PDYXSJSAMVACOH-UHFFFAOYSA-N 0.000 description 1
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical compound [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- -1 copper zinc tin selenium selenide Chemical compound 0.000 description 1
- 230000005516 deep trap Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011005 potassium tartrates Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0328—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032
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- H01L31/1864—Annealing
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Abstract
The invention discloses a preparation method of an antimony-doped electrochemical deposition copper-zinc-tin-sulfur solar cell absorbing layer, which is characterized by comprising the following steps: dissolving copper sulfate, zinc sulfate, stannous sulfate, sodium thiosulfate, sodium citrate, potassium tartrate and other chemical reagents in a deionized water solution according to a certain molar ratio; then, a quaternary copper-zinc-tin-sulfur prefabricated layer is electrochemically deposited on the metal molybdenum back electrode; then carrying out vulcanization annealing on the prefabricated layer and antimony source powder; finally obtaining the material of the absorbing layer of the stibium doped electrochemical deposition copper zinc tin sulfide thin film solar cell. Compared with the prior art, the preparation method has the advantages of greatly improving photoelectric performance and the like, well solves the technical problem of doping of the solar absorption layer of the electrochemical deposition copper-zinc-tin-sulfur thin film, can accurately control antimony element in the copper-zinc-tin-sulfur thin film by regulating and controlling the amount of an antimony source in the vulcanization annealing process, has simple preparation process, good repeatability and low cost, and has good research, popularization and utilization values.
Description
Technical Field
The invention relates to the technical field of semiconductor materials and solar energy, in particular to a preparation method of an antimony-doped electrochemical deposition copper-zinc-tin-sulfur solar cell absorbing layer.
Background
Global economic development and population growth have driven huge energy demands together. Traditional resources such as petroleum, natural gas and coal are gradually exhausted, and meanwhile, the gas discharged after the combustion of fossil energy causes environmental pollution and complex change of climate, so that people face double challenges of energy shortage and global climate warming. As one of the important forms of renewable energy utilization, solar photovoltaic power generation has very obvious advantages, and the solar photovoltaic power generation has rich and inexhaustible power generation resources, is clean and environment-friendly, has no fuel, no noise, no emission, stable performance, long service life, simple operation and maintenance and reliable use of renewable energy, and is an important material basis for social development.
In order to find cheap, green and environment-friendly and stable semiconductor absorbing materials, the copper-zinc-tin-sulfur quaternary semiconductor material attracts more and more attention of global scientists. The material contains rich, low-cost and non-toxic elements, and has the advantages that the band gap of the material is very close to the optimal band gap of the absorption layer of the single-junction solar cell, and the like, so that the material becomes one of the photovoltaic absorption layer materials with the greatest development prospect. Through continuous efforts in recent years, the highest photoelectric conversion efficiency of the pure copper zinc tin sulfide, pure copper zinc tin selenium selenide and sulfur selenium mixed copper zinc tin sulfide selenium thin-film solar cell respectively reaches 11%, 11.6% and 12.6%, which shows that the copper zinc tin sulfide thin-film solar cell has great application prospect in the photovoltaic field.
At present, the main problem of the copper zinc tin sulfur system is that the open circuit voltage is very low, which is closely related to the structural disorder, and the structural disorder is represented by a band tail and a deep trap state. The defects of the copper-zinc inverted acceptor are the main factors causing band tail defects, and the disorder of tin elements generates deep energy level defects in band gaps. These defects limit the performance of copper zinc tin sulfide solar cell devices, but their effect on open circuit voltage is poorly understood. And doping agents such as sodium, potassium, silver, antimony, cadmium, germanium and the like are introduced into the prefabricated layer film, and post-sulfuration or selenization annealing is beneficial to crystallization of the copper-zinc-tin-sulfur film, so that disorder of metal elements is reduced, and the conversion efficiency of the battery is further improved.
Compared with other preparation methods, the electrochemical deposition technology has perfect theory and mature technology, and is an industrial large-scale production technology suitable for preparing metal film materials. The standard potential difference between elements of the electro-codeposition multielement film is required to be within 0.2V. However, the standard potential difference of four elements of copper, zinc, tin and sulfur is large, and particularly the standard potentials of zinc and copper are-0.76V and + 0.342V respectively, so that the technical problem of co-depositing the copper-zinc-tin-sulfur film exists. Therefore, compared with other processes, the electrochemical deposition of the doped copper zinc tin sulfide thin film has the technical problem. In order to improve the conversion efficiency of the copper zinc tin sulfide solar cell, how to dope trace elements on an absorption layer of the electrochemical deposition copper zinc tin sulfide thin-film solar cell is adopted. So far, no literature report related to doping of the copper-zinc-tin-sulfur film for electrochemical deposition exists.
Disclosure of Invention
The invention aims to provide a preparation method of an antimony-doped electrochemical deposition copper-zinc-tin-sulfur solar cell absorbing layer, which aims at overcoming the defects of the prior art, adopts a method for electrochemically depositing a quaternary copper-zinc-tin-sulfur prefabricated layer on a metal molybdenum back electrode, carries out vulcanization annealing on the prefabricated layer and antimony source powder, can accurately control antimony elements in a copper-zinc-tin-sulfur film by regulating and controlling the amount of an antimony source in the vulcanization annealing process, obtains an absorbing layer material of an antimony-doped electrochemical deposition copper-zinc-tin-sulfur solar cell, greatly improves the photoelectric property of the absorbing layer material, effectively solves the technical problem of doping of the solar absorbing layer of the electrochemical deposition copper-zinc-tin-sulfur film, and has the advantages of simple preparation process, good repeatability, low cost and good research, popularization and utilization values.
The purpose of the invention is realized as follows: the preparation method of the antimony-doped electrochemical deposition copper-zinc-tin-sulfur solar cell absorption layer is characterized by comprising the following steps of:
preparation of copper-zinc-tin-sulfur prefabricated layer
Mixing copper sulfate, zinc sulfate, stannous sulfate, sodium thiosulfate, sodium citrate, potassium tartrate and other chemical reagents according to a certain molar ratio, and dissolving the mixture in a deionized water solution to obtain an electrochemical deposition electroplating solution; the method comprises the steps of taking a metal molybdenum back electrode as a working electrode, taking silver-silver chloride as a reference electrode and taking a platinum sheet as a counter electrode, and codepositing a quaternary copper-zinc-tin-sulfur prefabricated layer by adopting a three-electrode potentiostatic method.
Preparation of the (II) absorbing layer
And (3) placing the copper-zinc-tin-sulfur prefabricated layer obtained in the step (I) under a vacuum condition containing antimony source powder for vulcanization annealing to obtain an antimony-doped copper-zinc-tin-sulfur thin film solar cell material, namely an antimony-doped copper-zinc-tin-sulfur absorption layer thin film.
And ultrasonically cleaning the metal molybdenum back electrode for 5-30 minutes by sequentially using an alkaline solution, acetone, ethanol and deionized water, then drying the metal molybdenum back electrode by using nitrogen, and putting the metal molybdenum back electrode into a vacuum drying oven for later use.
The molar concentration ratio of the copper sulfate to the zinc sulfate to the tin sulfate to the sodium thiosulfate to the sodium citrate to the potassium tartrate is 1-5: 2-50: 1-3: 1-20: 10-100: 5 to 40.
The deposition temperature is 25 ℃, the deposition potential is-0.5 to-1.5V (vs. Ag/AgCl), and the deposition time is 5 to 60 minutes.
The vulcanization degradation is specifically as follows: firstly, placing an electrochemical deposition copper-zinc-tin-sulfur prefabricated layer and a certain amount of antimony source powder in a graphite boat, then placing the graphite boat in an annealing furnace, vacuumizing, introducing inert gas, setting the initial vulcanization temperature to be 20-25 ℃, heating the annealing furnace at the temperature rising rate of 5-80 ℃/S, keeping the temperature for 10-60 minutes at the termination temperature of 450-650 ℃, and then naturally cooling to room temperature.
The thickness of the antimony doped copper zinc tin sulfur absorption layer film is 0.5-3 mu m.
Compared with the prior art, the method has the advantages of effectively doping the copper-zinc-tin-sulfur thin film, simple preparation process, controllable components, good thin film crystallinity, great improvement on the photoelectric performance of the copper-zinc-tin-sulfur thin film solar cell, effective solving of the technical problem of doping of the electrochemical deposition copper-zinc-tin-sulfur thin film solar absorption layer, good repeatability, low cost and good research, popularization and utilization values.
Drawings
FIG. 1 is an SEM image of an electrochemically deposited copper zinc tin sulfide preform layer prepared in example 1; )
FIG. 2 is an XRD pattern of an antimony doped electrochemically deposited Cu-Zn-Sn-S film prepared in example 1;
FIG. 3 is a Raman plot of an antimony doped electrochemically deposited Cu-Zn-Sn-S film prepared in example 1;
FIG. 4 is an SEM image of an antimony doped electrochemically deposited Cu-Zn-Sn-S thin film prepared in example 1;
FIG. 5 is an SEM image of an electrochemically deposited copper zinc tin sulfide preform layer prepared in example 2;
FIG. 6 is an XRD pattern of an antimony doped electrochemically deposited Cu-Zn-Sn-S film prepared in example 2;
FIG. 7 is a Raman plot of an antimony doped electrochemically deposited Cu-Zn-Sn-S film prepared in example 2;
FIG. 8 is an SEM image of an antimony doped electrochemically deposited Cu-Zn-Sn-S thin film prepared in example 2;
figure 9 is a J-V diagram of an antimony doped electrochemically deposited copper zinc tin solar cell prepared in example 2.
Detailed Description
The embodiment of the invention provides a preparation method of an antimony-doped electrochemical deposition copper zinc tin sulfide thin-film solar cell absorption layer, which is used for solving the technical problem that the existing electrochemical deposition copper zinc tin sulfide thin film is difficult to dope. For a better understanding of the present invention, the present invention will be described in further detail, and the present invention is not limited to the following examples.
Example 1
1) And (3) ultrasonically cleaning the metal molybdenum back electrode for 10 minutes by sequentially using an alkaline solution, acetone, ethanol and deionized water, then blow-drying by using nitrogen, and drying in a vacuum drying oven for later use.
2) And (2) according to molar ratio: 10: 1: 4: 50: 10 weighing copper sulfate, zinc sulfate, tin sulfate, sodium thiosulfate, sodium citrate and potassium tartrate, and sequentially dissolving in 200 ml of deionized water solvent to obtain electrolyte to be plated for later use; and (2) taking the metal molybdenum back electrode cleaned in the step 1) as a working electrode, a platinum sheet as a counter electrode and silver-silver chloride as a reference electrode, and depositing for 20 minutes at a constant potential of-1.0V at the temperature of an electrodeposition solution (electrolyte) of 25 ℃ to obtain the copper-zinc-tin-sulfur prefabricated layer film.
Referring to the attached figure 1, the prepared copper-zinc-tin-sulfur prefabricated layer film is characterized by a scanning electron microscope, and the surface of the prefabricated layer is smooth, compact and uniform in nano size.
3) Placing the electrochemical deposition copper-zinc-tin-sulfur prefabricated layer obtained in the step 2) and 0.2g of antimony sulfide powder in a graphite boat, then placing the graphite boat in an annealing furnace, vacuumizing, introducing high-purity nitrogen, setting the initial vulcanization temperature to be 25 ℃, heating the annealing furnace at the heating rate of 50 ℃/S, keeping the temperature at 550 ℃, and naturally cooling the system to room temperature after keeping the temperature for 15 minutes to obtain the antimony-doped electrochemical deposition copper-zinc-tin-sulfur absorption layer film.
Referring to fig. 2 to fig. 3, the thin copper zinc tin sulfide absorption layer prepared above is characterized by XRD and Raman spectroscopy, and it can be seen that peaks at 2q =18.21, 28.53, 32.98, 47.33 and 56.18 ° respectively correspond to diffraction peaks of (101), (112), (200), (220) and (312) crystal planes of copper zinc tin sulfide [ JCPDS 26-0575] of kesterite structure, and XRD diffraction peaks and Raman spectroscopy characteristic peaks of antimony and antimony related compounds do not appear, indicating that the prepared thin film is pure phase copper zinc tin sulfide and antimony element is doped into the electrochemically deposited copper zinc tin sulfide thin film.
Referring to the attached figure 4, the prepared copper zinc tin sulfur absorption layer film is characterized by a scanning electron microscope, which shows that the prepared antimony doped copper zinc tin sulfur absorption layer film has smooth surface, compact surface, less crystal boundary and good crystallinity.
Example 2
1) And (3) ultrasonically cleaning the metal molybdenum back electrode for 10 minutes by sequentially using an alkaline solution, acetone, ethanol and deionized water, then blow-drying by using nitrogen, and drying in a vacuum drying oven for later use.
2) According to the mol ratio of 1: 20: 1: 4: 50: 10 weighing copper sulfate, zinc sulfate, tin sulfate, sodium citrate, sodium thiosulfate and potassium tartrate, and sequentially dissolving in 200 ml of deionized water solvent to obtain electrolyte to be plated; and (2) taking the metal molybdenum back electrode cleaned in the step 1) as a working electrode, a platinum sheet as a counter electrode and silver-silver chloride as a reference electrode, and depositing for 20 minutes at a constant potential of-1.15V at the temperature of an electrodeposition solution (electrolyte) of 25 ℃ to obtain the copper-zinc-tin-sulfur prefabricated layer film.
Referring to fig. 5, the cu-zn-sn-s prefabricated layer film prepared above was characterized by using a scanning electron microscope, which indicated that the surface of the prefabricated layer was smooth, dense, and uniform in nano-size.
3) Placing the electrochemical deposition copper-zinc-tin-sulfur prefabricated layer prepared in the step 2) and 0.5g of antimony sulfide powder in a graphite boat, then placing the graphite boat in an annealing furnace, vacuumizing, introducing high-purity argon, setting the initial temperature of the vulcanization temperature to be 25 ℃, heating the annealing furnace at the heating rate of 50 ℃/S, setting the final temperature to be 550 ℃, preserving the temperature for 15 minutes, and naturally cooling the system to the room temperature to obtain the antimony-doped electrochemical deposition copper-zinc-tin-sulfur film.
Referring to fig. 6 to 7, the thin copper zinc tin sulfide absorption layer prepared above is characterized by XRD and raman spectroscopy, and it can be seen that peaks at 2q =18.21, 28.53, 32.98, 47.33 and 56.18 ° correspond to diffraction peaks of (101), (112), (200), (220) and (312) crystal planes of copper zinc tin sulfide [ JCPDS 26-0575] of kesterite structure, and XRD diffraction peaks and raman spectroscopy characteristic peaks of antimony and antimony related compounds do not appear, indicating that the prepared thin film is pure phase copper zinc tin sulfide and antimony element is doped into the electrochemically deposited copper zinc tin sulfide thin film.
Referring to the attached figure 8, the prepared copper zinc tin sulfur absorption layer film is characterized by a scanning electron microscope, which shows that the prepared antimony doped copper zinc tin sulfur absorption layer film has smooth surface, compact surface, less crystal boundary and good crystallinity.
In other embodiments of the present invention, antimony sulfide powder of 1.0g, 1.5g, 2.0g or 2.5g was placed in a graphite boat, and the other operations were the same as in embodiment 2, and the obtained antimony doped copper zinc tin sulfide absorption layer thin film was the same as the product of embodiment 2.
As can be seen from the above examples 1-2, the half height width of XRD of the copper zinc tin sulfide thin film grown by placing 0.5g of antimony sulfide powder in a graphite boat is small, the crystallinity thereof is high, the SEM morphology of the copper zinc tin sulfide thin film is very dense, and the further prepared copper zinc tin sulfide thin film solar cell has higher efficiency. The half height width of XRD of the copper zinc tin sulfide film grown by 0.2g of antimony sulfide powder placed in the graphite boat is larger, and the grain size of the copper zinc tin sulfide film is relatively smaller.
Referring to fig. 9, a graph comparing J-V curves for antimony doped and undoped copper zinc tin sulfide thin film solar cells prepared in example 2 shows that: the antimony is doped into the electrochemical deposition copper zinc tin sulfur absorption layer, so that the electrical performance of the copper zinc tin sulfur thin-film solar cell is remarkably improved, and the current density is 19.65mA/cm2Increased to 21.34mA/cm2The open circuit voltage increased from 0.6723V to 0.710V, the fill factor increased from 61.7% to 64.3%, and the conversion efficiency increased from 8.15% to 9.76%.
According to the invention, by adjusting the content of the antimony source powder, the components of the antimony-doped electrochemical deposition copper-zinc-tin-sulfur can be accurately controlled, and further, the solar cell device which has high crystallization quality and good appearance, is formed by the antimony-doped electrochemical deposition copper-zinc-tin-sulfur-selenium film and has the conversion efficiency close to 10% is obtained. 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 improvements can be made in the present invention without departing from the scope of the invention, and such modifications and improvements should be considered as within the scope of the invention.
Claims (3)
1. A preparation method of an antimony-doped electrochemical deposition copper-zinc-tin-sulfur solar cell absorbing layer is characterized in that a method of electrochemically depositing a quaternary copper-zinc-tin-sulfur prefabricated layer on a metal molybdenum back electrode is adopted, the prefabricated layer and antimony source powder are subjected to vulcanization annealing, and the antimony-doped electrochemical deposition copper-zinc-tin-sulfur thin film solar cell absorbing layer is obtained, and the preparation method specifically comprises the following steps:
preparation of the prefabricated layer
Copper sulfate, zinc sulfate, stannous sulfate, sodium thiosulfate, sodium citrate and potassium tartrate are mixed according to the weight ratio of 1-5: 2-50: 1-3: 1-20: 10-100: the mixed solution with the molar ratio of 5-40 is put into deionized water to obtain an electrochemical deposition electroplating solution; depositing a quaternary copper-zinc-tin-sulfur prefabricated layer by using a three-electrode potentiostatic method by using a metal molybdenum back electrode as a working electrode, silver-silver chloride as a reference electrode and a platinum sheet as a counter electrode, wherein the deposition temperature is 20-30 ℃, the deposition potential is-0.5-1.5V, and the deposition time is 5-60 minutes;
(2) preparation of the absorbent layer
Placing the prepared copper-zinc-tin-sulfur prefabricated layer under a vacuum condition containing an antimony source and a sulfur source for vulcanization annealing to prepare an antimony-doped copper-zinc-tin-sulfur absorption layer with a film thickness of 0.5-3 mu m, namely an antimony-doped copper-zinc-tin-sulfur thin-film solar cell material, wherein the antimony source is one or a mixture of more than two of antimony selenide powder, antimony sulfide powder and selenium antimony sulfide powder; the sulfur source is sulfur powder or hydrogen sulfide.
2. The method for preparing the absorbing layer of the Sb-doped electrochemical deposition Cu-Zn-Sn-S solar cell according to claim 1, wherein the step of sulfurizing annealing is to place the prefabricated Cu-Zn-Sn-S layer, the Sb source and the S source in a graphite boat of an annealing furnace for vacuumizing, and control the amount of the Sb source to accurately control the Sb element in the Cu-Zn-Sn-S film so as to obtain the absorbing layer material of the Sb-doped electrochemical deposition Cu-Zn-Sn-S solar cell, wherein the initial sulfurizing temperature is 20-25 ℃, the absorbing layer material is heated to 450-650 ℃ at the heating rate of 5-80 ℃/S, and the absorbing layer material is naturally cooled to room temperature after the temperature is maintained for 10-50 minutes.
3. The method for preparing an antimony doped electrochemically deposited copper zinc tin sulfide solar cell absorber layer according to claim 1 or claim 2, wherein the protective gas for the sulfidation annealing is high purity nitrogen or argon.
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