CN103303970B - 一种带隙可调的镁掺杂铜锌锡硫薄膜的制备方法 - Google Patents

一种带隙可调的镁掺杂铜锌锡硫薄膜的制备方法 Download PDF

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CN103303970B
CN103303970B CN201310259146.3A CN201310259146A CN103303970B CN 103303970 B CN103303970 B CN 103303970B CN 201310259146 A CN201310259146 A CN 201310259146A CN 103303970 B CN103303970 B CN 103303970B
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zinc
tin
copper
magnesium
sulfur
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CN103303970A (zh
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李永峰
肖振宇
姚斌
丁战辉
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Jilin University
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Abstract

本发明涉及一种带隙受镁杂质浓度调控的铜锌锡硫（Cu2ZnSnS4）薄膜的制备方法，其特征是以氯化镁、醋酸铜、醋酸锌、氯化亚锡、硫脲为原料，利用溶胶凝胶技术制备出镁含量不同的铜锌锡硫薄膜，当镁与锌的比例在0到0.8范围内变化时，对应的带隙可在1.54到1.22 eV之间变化，本方法工艺简单，成本低廉，掺杂元素无毒无害，可用于制备具有不同带隙的铜锌锡硫吸收层的叠层太阳电池。

Description

一种带隙可调的镁掺杂铜锌锡硫薄膜的制备方法
技术领域
本发明涉及一种带隙受镁组分调控的铜锌锡硫薄膜的制备方法，以氯化镁、醋酸铜、醋酸锌、氯化亚锡、硫脲为原料，属于薄膜太阳电池材料领域。
背景技术
铜锌锡硫是一种直接带隙化合物半导体，光学带隙为1.5 eV，其吸收边高能侧吸收系数高达104 cm-1，被用于制备薄膜太阳电池的吸收层。铜锌锡硫作为吸收层，其光学带隙是调控薄膜太阳电池光电转换效率的重要参数，尤其是具有不同带隙的叠层太阳电池。目前，铜锌锡硫带隙调节方法是在铜锌锡硫中掺入硒元素，其缺点是：在硒化过程中，所使用的硒化物（如H2Se）为剧毒物质，对环境及人体均存在危害。因此，采用对人体无毒无害、对环境无污染的带隙调节方法具有十分重要的意义。
发明内容
本发明的目的在于克服目前采用硒化的方法调控铜锌锡硫带隙所带来的环境和健康危害。本发明将采用无硒工艺制备带隙可调的铜锌锡硫薄膜。
本发明的目的是这样实施的：将醋酸铜、醋酸锌、氯化锡、硫脲按化学计量比溶于乙二醇甲醚和乙醇胺中，保持在45 ℃条件下，搅拌至完全溶解，再加入硫脲，搅拌至完全溶解，获得铜锌锡硫溶液。在获得的铜锌锡硫溶液中按掺杂比例加入氯化镁，在搅拌至完全溶解，获得带有镁组分的铜锌锡硫溶液。将所配制的溶液滴在放置于旋涂机上的衬底上，使溶液在衬底上均匀铺开。旋涂完毕后，在300 ℃下干燥，使溶剂挥发，然后将旋涂和干燥的过程重复若干次，得到镁掺杂的铜锌锡硫薄膜。光学吸收谱测试表明，镁掺杂的铜锌锡硫薄膜的光学带隙受镁掺杂浓度的调制。
本发明调控铜锌锡硫光学带隙的方法的优点是：
（1）避免了硒化过程给环境和人体健康带来的危害。
（2）光学带隙随镁组分的增加而降低。
附图说明
图1为本发明所述的工艺流程图。
图2为本发明所述的制备的镁掺杂的铜锌锡硫薄膜的X光衍射图。
图3为本发明所述的制备的镁掺杂的铜锌锡硫薄膜的光学吸收谱。
具体实施方式
实施例
将等体积的、浓度分别为0.875 mol/L、0.4375 mol/L、0.4375 mol/L、1.75 mol/L的醋酸铜、醋酸锌、氯化亚锡、硫脲溶于30 ml乙二醇甲醚和3 ml乙醇胺中，在45 ℃度环境下，搅拌至完全溶解，再加入硫脲搅，拌至完全溶解。分别量取此溶液5 ml，在其中加入与锌的比为0、0.1、0.3、0.5、0.8的氯化镁，搅拌至完全溶解，就得到了掺镁的铜锌锡硫溶液。将此溶液滴在置于旋涂机上的衬底上，在800 rpm的低速下旋涂6 s，然后2500 rpm的高速下旋涂20 s。旋涂完毕后，在300 ℃的环境下干燥5 min，然后将旋涂和干燥的过程重复5次，得到厚度为2微米的镁掺杂的铜锌锡硫薄膜。图2为旋涂后获得不同镁组分的铜锌锡硫薄膜的的X光衍射图，其衍射峰均为铜锌锡硫相，未发现与杂质相关的第二相，说明获得镁掺杂的铜锌锡硫为单一相结构。图3为不同镁组分的铜锌锡硫薄膜的光学吸收谱，当镁与锌的比例在0和0.8之间变化时，其光学带隙可在1.54 eV和1.22 eV之间调制。

Claims (3)

1.一种带隙可调的镁掺杂铜锌锡硫薄膜的制备方法，其特征在于以醋酸铜、醋酸锌、氯化亚锡、硫脲为原料，溶解在乙二醇甲醚和乙醇胺中，获得铜锌锡硫溶液，再在获得的铜锌锡硫溶液中加入氯化镁，最后将获得的溶液旋涂于衬底上，干燥后，获得镁掺杂的铜锌锡硫薄膜。
2.按照权利要求1所述的一种带隙可调的镁掺杂铜锌锡硫薄膜的制备方法，其特征在于所制得的含镁的铜锌锡硫溶液中氯化镁与醋酸锌的摩尔比例在0到0.8之间时，所制得的铜锌锡硫薄膜为锌黄锡矿(Kesterite)结构。
3.按照权利要求1所述的一种带隙可调的镁掺杂铜锌锡硫薄膜的制备方法，其特征在于所制得的含镁的铜锌锡硫溶液中氯化镁与醋酸锌的摩尔比例在0到0.8之间时，获得的镁掺杂铜锌锡硫薄膜的光学带隙可在1.54eV和1.22eV之间变化。
CN201310259146.3A 2013-06-26 2013-06-26 一种带隙可调的镁掺杂铜锌锡硫薄膜的制备方法 Expired - Fee Related CN103303970B (zh)

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CN103606591B (zh) * 2013-11-13 2016-02-03 福州大学 一种太阳电池吸收层材料铜锌锡硫薄膜的制备方法
CN105552171B (zh) * 2016-02-01 2018-03-20 上海理工大学 喷涂一步法制备Cu2ZnSnS4极薄太阳光吸收层的方法
CN105742385B (zh) * 2016-03-23 2017-03-01 岭南师范学院 一种铜铁锌锡硫微米单晶颗粒及其制备方法和在制备太阳能电池方面的应用
CN109904259B (zh) * 2019-04-10 2021-05-11 广东工业大学 一种双掺杂铜锌锡硫薄膜及其制备方法
CN112064105B (zh) * 2020-08-28 2022-04-08 盐城工学院 Cu2Zn1-xMgxSnS4纳米晶的制备方法及其用途

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