CN108807560A - 一种用硫粉辅助制备铜铁硫光电薄膜的方法 - Google Patents
一种用硫粉辅助制备铜铁硫光电薄膜的方法 Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 22
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000010949 copper Substances 0.000 title claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000005864 Sulphur Substances 0.000 title claims abstract description 19
- 230000005693 optoelectronics Effects 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000010408 film Substances 0.000 claims abstract description 37
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000010409 thin film Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 19
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 15
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000005357 flat glass Substances 0.000 claims abstract description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000004528 spin coating Methods 0.000 claims abstract description 5
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000008236 heating water Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 238000004506 ultrasonic cleaning Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract description 4
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 abstract description 4
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 4
- 229910052951 chalcopyrite Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 102000005298 Iron-Sulfur Proteins Human genes 0.000 description 1
- 108010081409 Iron-Sulfur Proteins Proteins 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- YNBADRVTZLEFNH-UHFFFAOYSA-N methyl nicotinate Chemical compound COC(=O)C1=CC=CN=C1 YNBADRVTZLEFNH-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
一种用硫粉辅助制备铜铁硫光电薄膜的制备方法，属于光电薄膜制备技术领域，本发明通过如下步骤得到，首先清洗玻璃基片，然后将CuCl2.2H2O、FeCl3.6H2O和Na2S2O3.5H2O依次放入溶剂水中，配制澄清透明溶液，用旋涂法在玻璃片上得到前驱体薄膜，自然晾干，放入反应釜内胆的中间层中，同时在涂有前驱体溶液的玻璃片旁边放入硫粉，反应釜内胆的下层放入水合联氨溶液，使前驱体薄膜样品不与联氨直接接触，将装有前驱体薄膜样品的密闭容器进行加热后取出样品进行干燥，可通过增加反应次数和热处理工艺改善薄膜质量，得到铜铁硫光电薄膜。本发明不需要高温高真空条件，对仪器设备要求低，生产成本低，生产效率高，易于操作。所得铜铁硫光电薄膜较不加硫粉制得的薄膜均匀性和结晶都要好，这种新工艺为制备高性能的铜铁硫光电薄膜提供了一种成本低、可实现工业化的生产方法。
Description
技术领域
本发明属于太阳能电池用光电薄膜制备技术领域，尤其涉及一种用硫粉辅助制备铜铁硫光电薄膜的制备方法。
背景技术
铜铁硫作为光电材料，是一种三元Ⅰ–Ⅲ–Ⅵ2族化合物半导体，具有黄铜矿和闪锌矿的晶体结构，同时具有高的光吸收系数、为直接能隙半导体、热稳定性好、无光致衰退效应等优点，又因铜铁硫材料的价格低廉、储量丰富且无毒等优势受到了科学家的广泛关注。
目前铜铁硫薄膜的制备方法有很多，主要有电化学沉积法、溅射法、热蒸发法、热喷涂法等。由于原料在地球上的储量丰富、价格低廉且无毒，因此是一种非常有发展前途的光电薄膜材料，但现有工艺路线复杂、制备成本高，因而需要探索低成本的制备工艺。
如前面所述方法一样，其它方法也有不同的缺陷。与本发明相关的还有如下文献：
[1] Xie H, X Su, et al. Thermoelectric performance of CuFeS2+2x compositesprepared by rapid thermal explosion. NPG ASIA Materials, 2017.
主要研究了利用快速热爆法制备CuFeS2+2x复合材料，研究了TE过程中发生的相变以及微观结构与输运性能之间的关系。
[2] Gaspari R, G Della Valle, et al. Quasi-Static Resonances in theVisible Spectrum from All-Dielectric Intermediate Band SemiconductorNanocrystals. Nano Letters, 2017.
主要研究了黄铜矿CuFeS2作为中间带半导体纳米晶替代等离子材料的技术。
[3] Tsujii N, T Mori. Development of thermoelectric materials basedon iron sulfide minerals. Funtai Oyobi Fummatsu Yakin/Journal of the JapanSociety of Powder and Powder Metallurgy, 2017.
主要研究了n型掺杂CuFeS2材料，发现Zn掺杂CuFeS2的热电性能主要取决于合成方法。
[4] Wang Y, X Li, et al. Ether based electrolyte improves theperformance of CuFeS2 spike-like nanorods as a novel anode for lithiumstorage. Electrochimica Acta, 2015.
主要研究了一种简单的水热法制备CuFeS2尖晶石纳米棒材料，研究表明CuFeS2可以成为用于高倍率锂电池的负极材料。
[5] Zhang Z, D Li, et al. Synthesis and photoelectric properties ofhigh quality CuFeS2 nanocrystals with tunable sizes. Gaodeng Xuexiao HuaxueXuebao/ Chemical Journal of Chinese Universities, 2014.
主要研究了具有可调尺寸的单分散CuFeS2纳米晶体（NCs），进一步揭示了CuFeS2NCs的光响应特性作为光电器件的光学活性元件的适用性。
[6] Aliyev YI, TM Ilyasli, et al. The structural and vibrationalproperties of Ni-doped chalcopyrite CuFeS2. Journal of Ovonic Research, 2018.
主要研究了镍掺杂黄铜矿CuFeS2的结构和振动性质，并分析了掺杂镍CuFe0.99Ni0.01S2对CuFeS2晶体结构的影响。
[7] Rouchdi M, E Salmani, et al. Spray pyrolysis synthesis of CuxFe1- xS2 and their structural, electronic and optical properties: Experimental andfirst-principles study. Materials Science and Engineering B-advancedFunctional Solid-state Materials, 2018.
主要采用化学喷雾热解(CSP)技术合成黄铁矿、FeS2(FS)和黄铜矿铜铁硫化物CuxFe1- xS2(CFS)薄膜，主要研究了Cu浓度对薄膜生长的影响。
[8] Xiong X, X Hua, et al. Oxidation mechanism of chalcopyriterevealed by X-ray photoelectron spectroscopy and first principles studies.Applied Surface Science, 2018.
主要研究了黄铜矿（CuFeS2）表面的氧化机理和第一性原理计算。
发明内容
本发明为了解决现有制备技术的不足，发明了一种与现有制备方法完全不同的铜铁硫薄膜的制备工艺。
本发明采用旋涂-化学共还原法制备铜铁硫薄膜材料，采用玻璃片或硅片为基片，以CuCl2.2H2O、FeCl3.6H2O、Na2S2O3.5H2O为原料，以水为溶剂，依次加入CuCl2.2H2O、FeCl3.6H2O、Na2S2O3.5H2O，使其充分反应。先以旋涂法制备一定厚度的铜铁硫前驱体薄膜，放入反应釜内胆的中间层中，同时在涂有前驱体溶液的玻璃片旁边放入硫粉，反应釜内胆的下层放入水合联氨溶液，使前驱体薄膜样品不与联氨直接接触，以水合联氨为还原剂，在密闭容器内在较低温度下加热，使前驱体薄膜还原并发生合成反应，可通过增加反应次数和反应后热处理改善所制备薄膜质量，得到目标产物。
本发明的具体制备方法包括如下顺序的步骤：
a. 进行基片的清洗，本实验选择玻璃片或硅片作为基片，首先将玻璃片或硅片切至20mm×20mm×2mm大小作为薄膜基片，然后用去离子水清洗2~3次，随后经过稀硫酸煮沸30~40min、水浴加热40~50min、去离子水超声清洗20min，这三个重要清洗步骤后，用双氧水浸泡保存备用即可。
b. 将CuCl2.2H2O、FeCl3.6H2O和Na2S2O3.5H2O依次放入溶剂中，使溶液中的物质均匀混合。具体地说，将0.1705g的CuCl2.2H2O在玻璃瓶中加入1mL的水使其充分溶解，再依次往玻璃瓶内加入0.2702g的FeCl3.6H2O和0.2481g的Na2S2O3.5H2O使其充分均匀混合溶解，其中加入的CuCl2.2H2O、FeCl3.6H2O、Na2S2O3.5H2O和溶剂水的量可根据涂膜的多少成比例变化。
c. 制作外部均匀如步骤b所述溶液的基片，并烘干，得到前驱体薄膜样品。可以将上述溶液滴到放置在匀胶机上的基片上，再启动匀胶机以200~3500转/分旋转一定时间，使滴上的溶液涂布均匀后，并对基片进行自然晾干后，再次重复滴上前述溶液和旋涂后再自然晾干，如此重复2~8次，于是在基片上得到了一定厚度的前驱体薄膜样品。
d. 将步骤c所得前驱体薄膜样品置于反应釜内胆的中层，并在薄膜样品的旁边放入0.032g的硫粉，反应釜内胆的下层放入水合联氨溶液，使前驱体薄膜样品不与水合联氨接触；水合联氨放入量为0.5mL。将上述装有前驱体薄膜样品的密闭容器放入烘箱中，加热至160~220℃之间，保温时间2~40小时，然后冷却到室温取出。
e. 取出自然干燥后，重复b、c和d步骤2~6次，以增加所制备薄膜的厚度，减少薄膜缺陷。
f. 将步骤e所得物，使其常温自然干燥后，增加热处理工艺，在管式加热炉中加热至200~400℃，保温5~15小时，即得到铜铁硫光电薄膜。
本发明不需要高真空条件，对仪器设备要求低，生产成本低，生产效率高，易于操作。所得铜铁硫光电薄膜较不加硫粉制得的薄膜均匀性和结晶都要好，主相为CuFeS2相，可以实现低成本大规模的工业化生产。
附图说明
图1是180℃反应10h制备CuFeS2的XRD图。其中上曲线为加硫粉硫化前的样品，下曲线为加硫粉硫化后的样品。
具体实施方式
实施例1
a. 玻璃基片或硅基片的清洗：如前所述进行清洗基片，大小为20mm×20mm×2mm。
b. 可以先将0.1705g的CuCl2.2H2O在玻璃瓶中加入1mL的水使其充分溶解，再依次往玻璃瓶内加入0.2702g的FeCl3.6H2O和0.2481g的Na2S2O3.5H2O使其充分均匀混合溶解。
c. 将上述溶液滴到放置在匀胶机上的玻璃基片上，再启动匀胶机，匀胶机以200转/分转动5秒，以3000转/分旋转15秒，使滴上的溶液涂布均匀后，对基片进行烘干后，再次重复滴上前述溶液和旋涂后再烘干，如此重复6次，于是在基片上得到了一定厚度的前驱体薄膜样品。
d. 将步骤c所得前驱体薄膜样品置于反应釜内胆的中层，并在薄膜样品的旁边放入0.032g的硫粉，反应釜内胆的下层放入水合联氨溶液，使前驱体薄膜样品不与水合联氨接触；水合联氨放入量为0.5mL。将上述装有前驱体薄膜样品的密闭容器放入烘箱中，加热至180℃，保温时间10小时，然后冷却到室温取出。
e. 取出自然干燥后，重复b、c和d步骤4次，以增加所制备薄膜的厚度，减少薄膜缺陷。
f. 将步骤e所得物，使其常温自然干燥后，增加热处理工艺，在管式加热炉中加热至300℃，保温10小时，即得到铜铁硫光电薄膜。
Claims (5)
1.一种用硫粉辅助制备铜铁硫光电薄膜的方法，包括如下顺序的步骤：
a.玻璃基片或硅基片的清洗；
b.将0.1705g的CuCl2.2H2O在玻璃瓶中加入1mL的水使其充分溶解，再依次往玻璃瓶内加入0.2702g的FeCl3.6H2O和0.2481g的Na2S2O3.5H2O使其充分均匀混合溶解；
c.制作表面均匀涂布步骤b所述溶液的基片，自然晾干，得到前驱体薄膜样品；
d.将步骤c所得前驱体薄膜样品置于反应釜内胆的中层，并在薄膜样品的旁边放入0.032g的硫粉，反应釜内胆的下层放入水合联氨溶液，使前驱体薄膜样品不与水合联氨接触；水合联氨放入量为0.5mL；将上述装有前驱体薄膜样品的密闭容器放入烘箱中，加热至160~220℃之间，保温时间2~40小时，然后冷却到室温取出；
e.取出自然干燥后，重复上述步骤2~6次，以增加所制备薄膜的厚度；
f.将步骤e所得物，使其常温自然干燥后，增加热处理工艺，在管式加热炉中加热至200~400℃，保温5~15小时，即得到铜铁硫光电薄膜。
2.如权利要求1所述的一种用硫粉辅助制备铜铁硫光电薄膜的方法，其特征在于，步骤a所述清洗，将玻璃片或硅片切至20mm×20mm×2mm大小作为薄膜基片，然后用去离子水清洗2~3次，随后经过稀硫酸煮沸30~40min、水浴加热40~50min、去离子水超声清洗20min，这三个重要清洗步骤后，用双氧水浸泡保存备用即可。
3.如权利要求1所述的一种用硫粉辅助制备铜铁硫光电薄膜的制备方法，其特征在于，步骤b所述溶剂为水溶液，且其中加入的CuCl2.2H2O、FeCl3.6H2O、Na2S2O3.5H2O和溶剂水的量可根据涂膜的多少成比例变化。
4.如权利要求1所述的一种用硫粉辅助制备铜铁硫光电薄膜的制备方法，其特征在于，步骤c所述均匀涂抹的基片，是通过匀胶机旋涂，匀胶机以200~3500转/分旋转，然后对基片进行烘干后，再次如此重复2~8次，得到了一定厚度的前驱体薄膜样品。
5.如权利要求1所述的一种用硫粉辅助制备铜铁硫光电薄膜的制备方法，其特征在于，步骤d所述在薄膜样品的旁边放入0.032g的硫粉，反应釜内胆的下层放入水合联氨溶液，使前驱体薄膜样品不与水合联氨接触；水合联氨放入量为0.5mL。
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| WO2015004666A1 (en) * | 2013-07-11 | 2015-01-15 | Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. | Thermal doping by vacancy formation in nanocrystals |
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| CN116272424B (zh) * | 2023-04-20 | 2024-04-26 | 中国长江三峡集团有限公司 | 一种CuFeS2改性催化陶瓷膜及其制备方法和应用 |
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