CN104064626B - 一种循环浸渍制备Cu2ZnSn(S1‑x,Sex)4纳米晶薄膜的方法 - Google Patents
一种循环浸渍制备Cu2ZnSn(S1‑x,Sex)4纳米晶薄膜的方法 Download PDFInfo
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- 239000002159 nanocrystal Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 18
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- 239000010408 film Substances 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 150000001768 cations Chemical class 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 150000001450 anions Chemical class 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 15
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- 238000005470 impregnation Methods 0.000 claims abstract description 5
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- 239000005864 Sulphur Substances 0.000 claims description 13
- 230000008020 evaporation Effects 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
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- 239000000203 mixture Substances 0.000 claims description 4
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- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
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- 150000002500 ions Chemical class 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 2
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- 229910052711 selenium Inorganic materials 0.000 description 14
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
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- 150000004820 halides Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- 238000004519 manufacturing process Methods 0.000 description 4
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- 239000011593 sulfur Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 150000003752 zinc compounds Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- -1 compound Halide Chemical class 0.000 description 2
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明属于纳米晶体薄膜制备技术领域,涉及一种循环浸渍制备Cu2ZnSn(S1‑x,Sex)4纳米晶薄膜的方法,先配制阳离子前驱液和阴离子前驱液;再分别在两个反应容器中加入与阳离子前驱液液面持平的去离子水构成循环浸渍反应体系;用氨水和盐酸分别调节阳、阴离子前驱液的pH值;然后将衬底以阳离子前驱液、去离子水、阴离子前驱液、去离子水为一周期的顺序依次交替循环浸渍后得到前驱体薄膜;最后将制得的前驱体薄膜经退火和冷却后得到Cu2ZnSn(S1‑x,Sex)4纳米晶薄膜;其制备工艺简单,使用设备简单,所需原料储量丰富,操作简便,成本低,所得产物的薄膜厚度可控性强,适合制备大面积薄膜,发展空间大。
Description
技术领域:
本发明属于纳米晶体薄膜制备技术领域,涉及一种新型Cu2ZnSn(S1-x,Sex)4太阳能电池光吸收层的制备方法,特别是一种循环浸渍制备Cu2ZnSn(S1-x,Sex)4纳米晶薄膜的方法。
背景技术:
随着环境污染问题日益严重以及不可再生资源的枯竭,寻求清洁无污染的替代能源,实现可持续发展,已经成为世界各国共同面临的问题。太阳能作为一种储量丰富并且可无限再生的清洁能源,吸引了越来越多的注意力。伴随着光伏组件的广泛使用,如何提高电池光电转换效率、降低成本是目前光伏发电的研究热点。目前,太阳能电池产业化占主导地位的是硅基太阳能电池和铜铟镓硒(Cu2InGa(S1-x,Sex)4,简称CIGSSe)薄膜太阳能电池,这两类太阳能电池的显著优势在于都具有较高的光电转换效率,但是硅基太阳能电池的生产成本过高导致其大范围推广使用受到一定的制约;而铜铟镓硒薄膜太阳能电池所应用的In和Ga元素在地球上的储存量有限,属于稀有元素,并且在其制备过程中会产生对环境的污染,这些因素无形中提高了生产成本,使得基于CIGSSe薄膜的光伏电池的发展空间非常有限。在CIGSSe薄膜的基础上,研究人员发现可以用Zn和Sn取代In和Ga元素从而制备出Cu2ZnSn(S1-x,Sex)4(简称CZTSSe)薄膜,其禁带宽度约为1.5eV,与半导体太阳能电池所要求的最佳禁带宽度十分接近,并且具有较大的光吸收系数(>104cm-1)。CZTSSe材料不含有有毒成分,对环境友好,不会造成任何污染,目前已经成为了替代CIGSSe光电吸收层的最佳候选材料。据最新报道,CZTSSe薄膜太阳能电池的光电转化效率已经达到了12.6%,而其理论值高达32.2%,因此CZTSSe薄膜电池是一种非常具有应用潜力的太阳能电池。
目前,Cu2ZnSn(S1-x,Sex)4薄膜的制备方法主要分为真空法和非真空法,真空法主要包括溅射法、气相沉积法和蒸镀法等,但是真空法设备昂贵,操作复杂,难以大面积成膜,并且原材料利用率低,重复性差,直接制约了其大规模生产;而非真空法主要包括电化学沉积法、溶胶-凝胶法和丝网印刷法等,相对真空法而言,非真空法无需昂贵的真空设备,因此更具发展潜力。最近有采用连续离子层吸附反应的方法制备Cu2ZnSx薄膜和ZnS薄膜叠层预制层结构或者Cu2S薄膜和ZnSnSx薄膜叠层预制层结构,然后进行退火处理得到铜锌锡硫薄膜的专利(申请号201110189391.2),但是该技术工艺复杂,材料制备的时间长。因此,寻求设计一种改进的连续离子层吸附反应的方法直接在衬底上制备前躯体薄膜,再通过在含硫/硒气氛中退火获得均匀的Cu2ZnSn(S1-x,Sex)4纳米晶薄膜,其中硫和硒的比例可以通过气氛中硫和硒的比例调节来实现。
发明内容:
本发明的目的在于克服现有技术存在的缺点,寻求设计提供一种循环浸渍制备Cu2ZnSn(S1-x,Sex)4纳米晶薄膜的方法,采用改进的连续离子层吸附反应的方法直接在衬底上制备前躯体薄膜,再通过在含硫/硒气氛中退火获得均匀的Cu2ZnSn(S1-x,Sex)4纳米晶薄膜,其中硫和硒的比例可以通过气氛中硫和硒的比例调节来实现。
为了实现上述目的,本发明的具体制备工艺包括以下步骤:
(1)、将含铜化合物水溶液、含锌化合物水溶液和含锡化合物水溶液按照体积比为1:(0.5~1.5):(0.5~1.5)的比例分别量取并置入反应容器,然后按照缓冲剂与阳离子总摩尔量(10~300):1的配比加入缓冲剂,在室温下搅拌均匀即得到阳离子前驱液;其中含铜化合物水溶液中铜浓度为0.01~1mol/L,含锌化合物水溶液中锌浓度为0.005~1mol/L,含锡化合物水溶液中锡浓度为0.01~1mol/L;
(2)、按照含硫化合物水溶液与阳离子前驱液体积比为1:(0.5~1.5)的比例量取含硫化合物水溶液置入与步骤(1)相同的反应容器中,配制成阴离子前驱液;其中含硫化合物水溶液中硫浓度为 0.08~1mol/L;
(3)、将阴离子前驱液和阳离子前驱液的温度分别调控为20~80℃,选取与步骤(1)相同的两个反应容器,分别在两个反应容器中加入与阳离子前驱液液面持平的去离子水构成循环浸渍反应体系;用氨水和盐酸分别调节阳、阴离子前驱液的pH值到2.0~4.0和5.0~7.0;其中氨水的重量百分比浓度为1%~28%,盐酸的重量百分比浓度为1%~37%;
(4)、将依次经过去离子水、丙酮和乙醇清洗过的衬底以阳离子前驱液、去离子水、阴离子前驱液、去离子水为一周期的顺序依次交替循环浸渍;每次阳、阴离子的浸渍时间为5~30秒,每次去离子水的浸渍时间为10~50秒,浸渍循环次数为20~600次,浸渍完成后即得到前驱体薄膜;
(5)、将制得的前驱体薄膜在400~700℃含硫/硒气氛下退火0.5~4h,再自然冷却到室温,即得到Cu2ZnSn(S1-x,Sex)4纳米晶薄膜,其中x=0-1。
本发明所述的含铜化合物为铜的卤化物、硫酸盐、硝酸盐和醋酸盐中的一种或两种以上;含锌化合物为锌的卤化物、硝酸盐、硫酸盐和醋酸盐中的一种或两种以上;含锡化合物为含锡的卤化物、硝酸盐、硫酸盐和醋酸盐中一种或两种以上;含铜化合物优选含铜的卤化物、硫酸盐;含锌化合物优选含锌的卤化物、硫酸盐;含锡化合物优选含锡的卤化物、硫酸盐。
本发明所述缓冲剂为尿素、酒石酸、柠檬酸、三乙醇胺、氟化铵和乙二胺中的一种或两种以上。
本发明所述反应容器为玻璃器皿、塑料器皿和不锈钢器皿中的一种。
本发明所述含硫化合物为硫代乙酰胺、硫代硫酸钠、硫化钠、硫化钾和硫化铵中的一种。
本发明所述衬底为洁净的玻璃、载玻片、纳米材料薄膜、高分子材料、不锈钢片、铜片、镍片、铝片、钼片和钛片中的一种。
本发明所述含硫/硒气氛为蒸发硫气氛、蒸发硒气氛、蒸发硫/硒混合气氛、Ar+蒸发硫气氛、Ar+蒸发硒气氛、N2+蒸发硫气氛、N2+蒸发硒气氛、Ar+5%H2S气氛和N2+5%H2S气氛中的一种或两种以上。
本发明与现有技术相比,具有以下优点:一是不需要昂贵的实验设备,对原材料的利用率非常高;而且铜锌锡硫硒薄膜的制备方法简单,所用前躯体材料成本低,无污染,适合批量合成;二是制备的铜锌锡硫薄膜均匀致密,具有较好的结晶;材料禁带宽度为1.5eV左右,可以作为太阳能电池器件的光吸收材料;三是有利于降低电池制作成本,减少原材料的浪费,适合制备大面积薄膜,可适用于工业化生产,具有良好的市场应用前景;其制备工艺简单,使用设备简单,所需原料储量丰富,操作简便,成本低,所得产物的薄膜厚度可控性强,适合制备大面积薄膜,发展空间大。
附图说明:
图1为本发明实施例1制备的Cu2ZnSnS4纳米晶薄膜的SEM图。
图2为本发明实施例1制备的Cu2ZnSnS4纳米晶薄膜的XRD图。
图3为本发明实施例2制备的Cu2ZnSn(S1-x,Sex)4纳米晶薄膜的SEM图。
图4为本发明实施例2制备的Cu2ZnSn(S1-x,Sex)4纳米晶薄膜的XRD图。
具体实施方式:
下面通过实施例并结合附图作进一步说明。
本实施例中的原料均为市购产品,纯度为分析纯。
实施例1:
本实施例制备Cu2ZnSnS4纳米晶薄膜的具体工艺过程为:
(1)、分别配制好浓度为0.02mol/L的CuSO4·5H2O溶液、0.01mol/L的ZnSO4·7H2O溶液、0.02mol/L的SnCl2·2H2O溶液和0.16mol/L Na2S·9H2O;
(2)、阳离子前驱液的配制:用量筒分别量取10ml的CuSO4·5H2O溶液、10ml的ZnSO4·7H2O溶液和10ml的SnCl2·2H2O 后混合在一起放置于50ml的烧杯中,加入5.845g的尿素,在室温下搅拌均匀后,转移到50℃的水浴锅内,用稀氨水调节其pH值为3.0,得到阳离子前驱液;
(3)、阴离子前驱液的配制:用量筒分别量取30ml的Na2S·9H2O溶液置于50ml的烧杯内,转移到50℃的水浴锅内,用稀盐酸调节其pH值为6.0,得到阴离子前驱液;
(4)、用量筒分别量取30ml的去离子水置于两个50ml的烧杯中,然后转移到50℃的水浴锅内,与步骤(2)和(3)分别制的阳离子前驱液和阴离子前驱液构成循环浸渍反应体系;
(5)、把经过去离子水、丙酮和乙醇清洗干净的导电玻璃浸入到阳离子前驱液中进行阳离子吸附,时间为15秒,再浸入到去离子水中15秒,接着浸入到阴离子前驱液中15秒,最后把导电玻璃浸入另一杯去离子水中15秒,完成一个连续离子层吸附反应循环;重复以上循环50次,在导电玻璃上得到前驱体薄膜;
(6)、将制备的前驱体薄膜在氩气和蒸发硫的混合气氛中,550℃退火1小时,在导电玻璃上得到Cu2ZnSnS4纳米晶薄膜;制得的Cu2ZnSnS4纳米晶薄膜的电镜照片如图1所示,其XRD谱图如图2所示,由图1和图2可知,薄膜致密均匀,结晶性较好,不存在杂质相。
实施例2:
本实施例的具体制备工艺过程为:
(1)、分别配制好浓度为0.03mol/L的CuCl溶液、0.015mol/L的ZnCl2溶液、0.03mol/L的SnCl4·5H2O溶液和0.24mol/L CH3CSNH2;
(2)、配制阳离子前驱液,用量筒分别量取15ml的CuCl溶液、15ml的ZnCl2溶液和15ml的SnCl4·5H2O,然后混合在一起放置于100ml的烧杯中,加入9.009g的尿素,在室温下搅拌均匀后,转移到60℃的水浴锅内,用稀氨水调节其pH值为3.0,得到阳离子前驱液;
(3)、配制阴离子前驱液,用量筒分别量取45ml的CH3CSNH2溶液置于100ml的烧杯内,转移到60℃的水浴锅内,用稀盐酸调节 其pH值为6.0,得到阴离子前驱液;
(4)、用量筒分别量取45ml的去离子水置于两个100ml的烧杯中,然后转移到60℃的水浴锅内,与上述阳、阴离子前驱液构成四烧杯反应体系;
(5)、把经过去离子水、丙酮和乙醇清洗干净的载玻片浸入到阳离子前驱液中进行阳离子吸附,时间为20秒,再浸入到去离子水中15秒,接着浸入到阴离子前驱液中20秒,最后把导电玻璃浸入另一杯去离子水中20秒,完成一个连续离子层吸附反应循环;重复以上循环100次,在载玻片上得到前驱体薄膜;
(6)、将制备的前驱体薄膜在氩气和蒸发硒的混合气氛中,500℃退火30分钟,在载玻片上得到Cu2ZnSn(S1-x,Sex)4纳米晶薄膜;制得的Cu2ZnSn(S1-x,Sex)4纳米晶薄膜的电镜照片如图3所示,图4为制得的Cu2ZnSn(S1-x,Sex)4薄膜的XRD谱图,实验结果反应制备的薄膜致密均匀,良好的结晶性,硒化程度高。
Claims (1)
1.一种循环浸渍制备Cu2ZnSnS4纳米晶薄膜的方法,其特征在于具体制备工艺包括以下步骤:
(1)、分别配制好浓度为0.02mol/L的CuSO4·5H2O溶液、0.01mol/L的ZnSO4·7H2O溶液、0.02mol/L的SnCl2·2H2O溶液和0.16mol/L Na2S·9H2O;
(2)、阳离子前驱液的配制:用量筒分别量取10ml的CuSO4·5H2O溶液、10ml的ZnSO4·7H2O溶液和10ml的SnCl2·2H2O后混合在一起放置于50ml的烧杯中,加入5.845g的尿素,在室温下搅拌均匀后,转移到50℃的水浴锅内,用稀氨水调节其pH值为3.0,得到阳离子前驱液;
(3)、阴离子前驱液的配制:用量筒分别量取30ml的Na2S·9H2O溶液置于50ml的烧杯内,转移到50℃的水浴锅内,用稀盐酸调节其pH值为6.0,得到阴离子前驱液;
(4)、用量筒分别量取30ml的去离子水置于两个50ml的烧杯中,然后转移到50℃的水浴锅内,与步骤(2)和(3)分别配制的阳离子前驱液和阴离子前驱液构成循环浸渍反应体系;
(5)、把经过去离子水、丙酮和乙醇清洗干净的导电玻璃浸入到阳离子前驱液中进行阳离子吸附,时间为15秒,再浸入到去离子水中15秒,接着浸入到阴离子前驱液中15秒,最后把导电玻璃浸入另一杯去离子水中15秒,完成一个连续离子层吸附反应循环;重复以上循环50次,在导电玻璃上得到前驱体薄膜;
(6)、将制备的前驱体薄膜在氩气和蒸发硫的混合气氛中,550℃退火1小时,在导电玻璃上得到Cu2ZnSnS4纳米晶薄膜。
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