CN108878590A - 一种用硝酸盐制备铜铁硫光电薄膜的方法 - Google Patents

一种用硝酸盐制备铜铁硫光电薄膜的方法 Download PDF

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CN108878590A
CN108878590A CN201810705114.4A CN201810705114A CN108878590A CN 108878590 A CN108878590 A CN 108878590A CN 201810705114 A CN201810705114 A CN 201810705114A CN 108878590 A CN108878590 A CN 108878590A
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刘科高
孙齐磊
荆明星
姬明
石磊
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Abstract

一种用硝酸盐制备铜铁硫光电薄膜的方法，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Cu(NO3)2、Fe(NO3)3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，放入有水合联氨的可密闭容器，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有较好的连续性和均匀性，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

一种用硝酸盐制备铜铁硫光电薄膜的方法
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，尤其涉及一种用硝酸盐制备铜铁硫光电薄膜材料的方法。
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] Xiankuan Meng, Hongmei Deng, Investigate the growth mechanism ofCu2FeSnS4 thin films by sulfurization of metallic precursor. MaterialsLetters, 2017.
主要研究了通过金属前驱体硫化法制备Cu2FeSnS4薄膜，并分析了Cu2FeSnS4薄膜的生长机制。
[2] Erika Dutková, Zdenka Bujnáková , Mechanochemical synthesis,structural, magnetic, optical and electrooptical properties of CuFeS2nanoparticles. Advanced Powder Technology, 2018.
主要研究了通过机械研磨法制备CuFeS2纳米粒子，研究了CuFeS2纳米粒子的结构、磁性、光学和电学性质。
[3] Sugathan A, B Bhattacharyya, et al. Why Does CuFeS2 ResembleGold. Journal of Physical Chemistary Letters, 2018.
主要研究了CuFeS2量子点的物理性质。采用结构和光学表征方法相结合，研究了在类似于500 nm的量子点的光谱中观察到的碰撞现象。
[4] 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。
[5] 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。
[6] Xiong X, X Hua, et al. Oxidation mechanism of chalcopyriterevealed by X-ray photoelectron spectroscopy and first principles studies.Appled 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材料的制备工艺。
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Cu(NO3)2、Fe(NO3)3、Na2S2O3.5H2O为原料，以水为溶剂，依次加入Cu(NO3)2、Fe(NO3)3、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，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Cu(NO3)2、Fe(NO3)3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0.188g的Cu(NO3)2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0.242g的Fe(NO3)3和0.2481g的Na2S2O3.5H2O使其充分均匀混合溶解，其中加入的Cu(NO3)2、Fe(NO3)3、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支架上，放入有水合联氨的可密闭容器，使前驱体薄膜样品不与联氨接触。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有较好的连续性和均匀性，主相为CuFeS2相，可以实现低成本大规模的工业化生产。
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0.188g的Cu(NO3)2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0.242g的Fe(NO3)3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支架上，放入有水合联氨的可密闭容器，使前驱体薄膜样品不与联氨接触。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200℃，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)

1.一种用硝酸盐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0.188g的Cu(NO3)2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0.242g的Fe(NO3)3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支架上，放入有水合联氨的可密闭容器，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所述的一种用硝酸盐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所述的一种用硝酸盐制备铜铁硫光电薄膜材料的方法，其特征在于，步骤b所述溶剂为水溶液，且其中加入的Cu(NO3)2、Fe(NO3)3、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所述的一种用硝酸盐制备铜铁硫光电薄膜的方法，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所述的一种用硝酸盐制备铜铁硫光电薄膜的方法，其特征在于，步骤d所述密闭容器内放入0.5mL水合联氨。
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CN106796962A (zh) * 2014-11-05 2017-05-31 株式会社Lg化学 用于制备太阳能电池的光吸收层的前体及其制备方法
CN105551936A (zh) * 2015-12-17 2016-05-04 山东建筑大学 一种硝酸盐体系两步法制备铜铟硫光电薄膜的方法

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