CN104752552A - 泡沫金属负载的铜铟硫半导体光伏材料制备方法 - Google Patents

泡沫金属负载的铜铟硫半导体光伏材料制备方法 Download PDF

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CN104752552A
CN104752552A CN201310732089.6A CN201310732089A CN104752552A CN 104752552 A CN104752552 A CN 104752552A CN 201310732089 A CN201310732089 A CN 201310732089A CN 104752552 A CN104752552 A CN 104752552A
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copper
indium
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元炯亮
路辉
王培城
李旺
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Beijing University of Chemical Technology
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    • 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
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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
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Abstract

本发明涉及一种铜铟硫半导体光伏材料制备方法，属于材料领域。其特征在于：采用电化学方法在泡沫金属基体上均匀连续负载3纳米至1微米的铜铟硫半导体层。该材料具有很高的光电转换效率。

Description

泡沫金属负载的铜铟硫半导体光伏材料制备方法
技术领域
本发明涉及一种铜铟硫半导体光伏材料的制备方法，属于材料领域。
背景技术
黄铜矿型I-III-VI2族半导体具有良好的光电转换性能，Cu(In,Ga)Se2薄膜太阳能电池的光电转换效率高达20.3%；但是，由于硒元素有毒，因而限制了其应用。尽管CuInS2薄膜太阳能电池的光电转换效率目前只有13%，但是CuInS2是直接禁带半导体，带隙能约1.5eV，与太阳光谱十分匹配，而且吸收系数高（105cm-1）；更重要的是，CuInS2中不使用有毒元素，具有环境友好的特征。因此，CuInS2是最具发展前途的光伏材料之一。
由于高比表面积低维纳米结构可以有效促进光吸收和电荷分离，因而CuInS2半导体纳米晶、纳米线、纳米棒、纳米管等具有较高的光电转换效率。但是，半导体晶粒间界面阻力导致光生电子不能有效传输到外电路，因而限制了CuInS2光电转换效率的进一步提高。
泡沫金属不仅具有高比表面积，而且具有高的导电性。为此，本发明提出在泡沫金属上负载均匀连续的CuInS2半导体光伏材料，形成以三维互通金属线为芯的半导体管状结构，从而提高收集和传输光生电子的能力。
发明内容
本发明提供一种泡沫金属负载的铜铟硫半导体光伏材料制备方法，其特征在于：采用电化学方法在泡沫金属基体上均匀连续负载3nm~1μm的铜铟硫半导体层。
泡沫金属基体包括单一金属和金属合金，例如泡沫铜、泡沫铝、泡沫镍、泡沫铁、泡沫黄铜、泡沫铁镍铬。
在泡沫金属基体上首先通过电化学方法制备铜铟硫半导体层。可以采用一步电沉积法制备铜铟硫半导体层，也可以采用分步法制备铜铟硫半导体层。采用一步法时，可在含有Cu2+、In3+、S2O3 2 −的电解液中进行。采用分步法时，可先沉积铜金属层，再沉积铟金属层，然后再硫化；也可以先沉积铜铟合金层，然后再硫化。
在泡沫金属基体上通过恒电位共沉积的方法制备铜铟合金膜时，电解液中铜盐和铟盐的浓度均为2~20mM，铜盐和铟盐的摩尔比为2:1~1:2，铜盐和铟盐可采用氯化物、硫酸盐、硝酸盐、乙酸盐，但不局限于这些种类的盐。电解液中络合剂三乙醇胺的加入量为0~0.5M；也可以采用邻苯二甲酸氢钾做络合剂，加入量为0~0.1M。电解液中柠檬酸钠的加入量为0~0.1M。电解液pH值控制在2.0~5.0，沉积电位为-800~ -1100mV（相对于饱和甘汞电极），沉积时间为10~60min，电解液温度为20~50℃。
铜铟合金膜的硫化退火过程中，以升华硫为硫源，退火温度控制在300-500℃之间；退火时间为15-120min。
该发明提供的泡沫金属负载铜铟硫半导体光伏材料，形成以三维互通金属线为芯的半导体管状结构，而不是半导体量子点。与传统导电基体上制备的半导体光伏材料相比，泡沫金属负载铜铟硫半导体光伏材料的光电转换性能显著提高。
附图说明
图1是在铟锡氧化物（ITO）导电玻璃上沉积的铜铟硫薄膜电极的电流-电位曲线。
图2是泡沫镍负载的铜铟硫半导体电极的电流-电位曲线。
具体实施方式
对比例
在50mL 5mM氯化铜溶液中加入0.2M的三乙醇胺作为络合剂，0.01M柠檬酸钠作为缓冲剂，用浓硫酸将电解液pH值调至5.0左右，然后加入5mM氯化铟，用氢氧化钠溶液将溶液pH值调至4.00。
以1cm×1cm铟锡氧化物（ITO）导电玻璃作为工作电极，铂网为对电极，饱和甘汞电极（SCE）为参比电极，室温下在-1000mV恒电位沉积30min。
待薄膜干燥后对其进行硫化热处理，将薄膜置于管式炉的石英管中，称取2g硫粉放在石英管的进气口方向，以5℃/min的升温速率将温度升至400℃煅烧90min，得到铜铟硫半导体薄膜。
以CuInS2薄膜作为工作电极，碳棒作为辅助电极，SCE作为参比电极，在0.1M Na2SO4水溶液中测量暗态和光照（100mW/cm2）条件下电流-电位曲线。测量结果见图1。
实施例
以0.5mm厚的1cm×1cm泡沫镍作为工作电极，电解液组成、电沉积条件、硫化热处理条件同对比例，得到泡沫镍负载的铜铟硫半导体光伏材料。
以泡沫镍负载的铜铟硫半导体材料作为工作电极，碳棒作为辅助电极，SCE作为参比电极，在0.1M Na2SO4水溶液中测量暗态和光照（100mW/cm2）条件下电流-电位曲线。测量结果见图2。

Claims (10)

1.一种泡沫金属负载的铜铟硫半导体光伏材料制备方法，其特征在于：采用电化学方法在泡沫金属基体上均匀连续负载3nm~1μm的铜铟硫半导体层。
2.根据权利要求1所述的泡沫金属负载的铜铟硫半导体光伏材料制备方法，其特征在于：泡沫金属基体包括泡沫铜、泡沫铝、泡沫镍、泡沫铁、泡沫黄铜、泡沫铁镍铬。
3.根据权利要求1所述的泡沫金属负载的铜铟硫半导体光伏材料制备方法，其特征在于：在泡沫金属基体上首先通过恒电位共沉积制备铜铟合金膜，然后通过硫化退火的方法得到泡沫金属负载的铜铟硫半导体层。
4.根据权利要求3所述的在泡沫金属基体上通过恒电位共沉积制备铜铟合金膜的方法，其特征在于：电解液中铜盐和铟盐的浓度为2~20mM，铜盐和铟盐的摩尔比为2:1~1:2，铜盐和铟盐可采用氯化物、硫酸盐、硝酸盐、乙酸盐。
5.根据权利要求3所述的在泡沫金属基体上通过恒电位共沉积制备铜铟合金膜的方法，其特征在于：电解液中络合剂三乙醇胺的加入量为0~0.5M。
6.根据权利要求3所述的在泡沫金属基体上通过恒电位共沉积制备铜铟合金膜的方法，其特征在于：电解液中柠檬酸钠的加入量为0~0.1M。
7.根据权利要求3所述的在泡沫金属基体上通过恒电位共沉积制备铜铟合金膜的方法，其特征在于：电解液pH值控制在2.0~5.0。
8.根据权利要求3所述的在泡沫金属基体上通过恒电位共沉积制备铜铟合金膜的方法，其特征在于：沉积电位为-800~ -1100mV（相对于饱和甘汞电极），沉积时间10~60min，电解液温度为20~50℃。
9.根据权利要求3所述的通过硫化退火得到泡沫金属负载的铜铟硫半导体层的方法，其特征在于：铜铟合金膜的硫化退火过程中，以升华硫为硫源，退火温度控制在300~500℃之间。
10.根据权利要求3所述的通过硫化退火得到泡沫金属负载的铜铟硫半导体层的方法，其特征在于：铜铟合金膜的硫化退火过程中，退火时间为15~120min。
CN201310732089.6A 2013-12-27 2013-12-27 泡沫金属负载的铜铟硫半导体光伏材料制备方法 Pending CN104752552A (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105428458A (zh) * 2015-12-17 2016-03-23 山东建筑大学 一种硫酸盐体系两步法制备铜铟硫光电薄膜的方法
CN105428459A (zh) * 2015-12-17 2016-03-23 山东建筑大学 一种醋酸盐体系两步法制备铜铟硫光电薄膜的方法

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CN105428458A (zh) * 2015-12-17 2016-03-23 山东建筑大学 一种硫酸盐体系两步法制备铜铟硫光电薄膜的方法
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