CN109671787B - 一种无硒化过程非真空法制备的铜铟镓硒吸收层 - Google Patents

一种无硒化过程非真空法制备的铜铟镓硒吸收层 Download PDF

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CN109671787B
CN109671787B CN201910013617.XA CN201910013617A CN109671787B CN 109671787 B CN109671787 B CN 109671787B CN 201910013617 A CN201910013617 A CN 201910013617A CN 109671787 B CN109671787 B CN 109671787B
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李丽波
翟墨
杜金田
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Abstract

本发明涉及一种无硒化过程非真空法制备的铜铟镓硒吸收层，其特征在于，所述工艺步骤包括：制备铜铟镓硒胶体、铜铟镓硒前驱体薄膜的制备、退火热处理三个步骤。选用氯化铜、硫酸铟、氯化镓、二氧化硒作为Cu源、In源、Ga源、Se源，按照（Cu:In:Ga:Se=1:1.4:0.6:4）的摩尔比配置，选用乙醇作为溶剂同时加入三乙醇胺作为络合剂与粘结剂，在一定温度下搅拌溶解至白色粘稠状液体，取出后挥发陈化，适量的溶解在乙醇中再刮涂或滴涂在衬底上，经一定温度热处理后得到铜铟镓硒吸收层。本发明的铜铟镓硒吸收层，生产工艺简单，环保，无需任何再投料硒化工艺，即可得到平整，结构完善，禁带宽度为1.39 eV的铜铟镓硒薄膜。

Description

一种无硒化过程非真空法制备的铜铟镓硒吸收层
技术领域
本发明涉及光电材料新能源领域，具体涉及一种无硒化过程非真空法制备的铜铟镓硒吸收层。
背景技术
能源是人类文明存在和发展的重要物质基础。伴随着社会经济的高速发展、环境污染问题的日益严重以及对能源需求的持续增大，以煤、石油和天然气等化石能源为代表的传统能源已经不能够满足社会经济发展的需求。因此，世界各国都将开发新能源以及可循环持续发展的能源作为解决能源与环境问题的重要途径。而光伏发电将太阳能直接转化为电能，为解决日益增长的全球能源需求，提供了实用且可持续的解决方案。
铜铟镓硒薄膜太阳能电池作为第二代太阳能电池，以不具毒性，直接带隙材料，能带宽度在1.0-1.7 eV范围内可调，光吸收效率高，不存在光致衰退等优点，成为了目前最有可能实现低成本高效率制备薄膜光伏的设备之一。
根据太阳能电池工作原理，吸收层材料的质量直接影响着电池的光电转换效率，因此，铜铟镓硒薄膜的制备至关重要。目前铜铟镓硒薄膜按制备工艺主要分为两类：真空法与非真空法。真空方法主流工艺如多源共蒸发法和溅射后硒化法，其中共蒸发法所制备的铜铟镓硒薄膜太阳能电池转换效率最高，但是其需要昂贵的真空设备，不利于太阳能电池成本的降低和大面积产业化。非真空方法主要有电沉积法、喷涂热解法以及液相法等方法，相对来说，非真空制备方法设备简单易于实现，更利于低成本大规模生产。
非真空的液相法为制备高质量的铜铟镓硒薄膜材料提供了新的思路，液相法制备的铜铟镓硒薄膜材料，具有质量高，化学计量比可控，颗粒小，设备要求低等优点。但在液相法制备当中以肼、油胺为代表，存在一定的毒性，同时在后再添加硒源的后硒化过程存在一定的复杂工艺以及危险性，因此，需寻找一个制备工艺简单，环保，无毒的的制备工艺。
发明内容
本发明针对现有的技术不足，提供一种无硒化过程非真空法制备的铜铟镓硒吸收层。
为实现上述目的，本发明的一种无硒化过程非真空法制备的铜铟镓硒吸收层，工艺步骤包括：
一、铜铟镓硒胶体的制备：取氯化铜、硫酸铟、氯化镓、二氧化硒作为Cu源、In源、Ga源、Se源，按照（Cu:In:Ga:Se=1:1.4:0.6:4）的摩尔比配置溶解在乙醇溶剂中，加入三乙醇胺作为络合剂与粘结剂在一定温度下（40-70℃）水浴搅拌至白色溶液，室温下挥发陈化至白色胶状，待用;
二、铜铟镓硒前驱体薄膜的制备：得到胶体取适量溶解在乙醇中，通过刮涂法或滴涂法涂覆在衬底上，通过初步热处理（90-150℃）去除溶剂与杂质，得到前驱体薄膜，待用；
三、退火热处理：得到的前驱体薄膜经管式炉在氮气条件，一定的升温条件下（5-10℃/min）升至一定的温度（400-500℃）后保温一定时间（30-150min）后自然冷却至室温，得到铜铟镓硒薄膜吸收层。
本发明包含以下有益效果在于：制备过程简单，反应温和，成本低，无需真空工艺，无需再添加硒源的任何硒化工艺，得到铜铟镓硒吸收层薄膜结构稳定，表面平整，禁带宽度1.39eV，适合于实际对吸收层的需求。
附图说明
图1是本发明一种无硒化过程非真空法制备的铜铟镓硒吸收层的流程图。
图2是本发明制备得到的铜铟镓硒吸收层薄膜的外观图。
图3是是本发明制备得到的铜铟镓硒吸收层的X射线衍射图。
图4是本发明制备得到的铜铟镓硒吸收层薄膜的紫外可见吸收光谱图。
具体实施方式
下面结合最佳的实施方式对本发明做进一步说明，但本发明的保护范围并不仅限有以下实施例。
具体实施方式一，本发明的一种无硒化过程非真空法制备的铜铟镓硒吸收层是按照以下的步骤进行的：
一、铜铟镓硒胶体的制备：取氯化铜、硫酸铟、氯化镓、二氧化硒作为Cu源、In源、Ga源、Se源，按照（Cu:In:Ga:Se=1:1.4:0.6:4）的摩尔比配置溶解在乙醇溶剂中，加入三乙醇胺作为络合剂与粘结剂在一定温度下（40-70℃）水浴搅拌至白色溶液，室温下挥发陈化至白色胶状，待用；
二、铜铟镓硒前驱体薄膜的制备：得到胶体取适量溶解在乙醇中，通过刮涂法或滴涂法涂覆在衬底上，通过初步热处理（90-150℃）去除溶剂与杂质，得到前驱体薄膜，待用；
三、退火热处理：得到的前驱体薄膜经管式炉在氮气条件，一定的升温条件下（5-10℃/min）升至一定的温度（400-500℃）后保温一定时间（30-150min）后自然冷却至室温，得到铜铟镓硒薄膜吸收层。
具体实施方式二：本实施方式与具体实施方式一不同点在于：步骤二中所述的衬底为掺氟二氧化锡导电玻璃、铜片、钢片。
具体实施方式三：本实施方式与具体实施方式一或二不同点在于：步骤二中所述的铜铟镓硒前驱体薄膜的制备中涂膜的胶体厚度为25-95μm。
具体实施方式四：本实施方式与具体实施方式一至三之一不同点在于：步骤三中所述的退火热处理过程中无需再添加硒源的任何硒化工艺，直接在一定温度热处理即可。
具体实施例
本实施例的一种无硒化过程非真空法制备的铜铟镓硒吸收层，是按照以下步骤进行的：
一、铜铟镓硒胶体的制备：取氯化铜、硫酸铟、氯化镓、二氧化硒作为Cu源、In源、Ga源、Se源，按照（Cu:In:Ga:Se=1:1.4:0.6:4）的摩尔比配置溶解在乙醇溶剂中，加入三乙醇胺作为络合剂与粘结剂在一定温度下（40-70℃）水浴搅拌至白色溶液，室温下挥发陈化至白色胶状，待用；
二、铜铟镓硒前驱体薄膜的制备：得到胶体取适量溶解在乙醇中，通过刮涂法或滴涂法涂覆在衬底上，通过初步热处理（90-150℃）去除溶剂与杂质，得到前驱体薄膜，待用；
三、退火热处理：得到的前驱体薄膜经管式炉在氮气条件，一定的升温条件下（5-10℃/min）升至一定的温度（400-500℃）后保温一定时间（30-150min）后自然冷却至室温，得到铜铟镓硒薄膜吸收层。
本实施例中铜铟镓硒吸收层的制备流程图如图1所示，制备流程简单、制备条件简捷方便、节能环保提供了一种实用的铜铟镓硒吸收层。
本实施例中铜铟镓硒吸收层的紫外可见吸收光谱图如图3所示，由紫外可见光谱图分析得到铜铟镓硒吸收层薄膜的禁带宽度为1.39 eV。
本实施例中铜铟镓硒吸收层的X射线衍射图如图4所示，相比于铜铟镓硒标准卡片，X射线衍射的出峰位置以及峰大小，峰面积都一致，证实了铜铟镓硒晶体的存在。
本实施例中制得的铜铟镓硒吸收层，无需再添加硒源的任何硒化工艺，经退火之后即可得到结构稳定，表面平整的薄膜，禁带宽度可达1.39eV适合于实际铜铟镓硒太阳能电池对吸收层的需求。

Claims (3)

1.一种无硒化过程非真空法制备铜铟镓硒吸收层的方法，其特征在于一种无硒化过程非真空法制备的铜铟镓硒吸收层的方法步骤是按以下进行的：
一、铜铟镓硒胶体的制备：取氯化铜、硫酸铟、氯化镓、二氧化硒作为Cu源、In源、Ga源、Se源，按照Cu:In:Ga:Se＝1:1.4:0.6:4的摩尔比配置溶解在乙醇溶剂中，加入三乙醇胺作为络合剂与粘结剂在40-70℃温度下水浴搅拌至白色溶液，室温下挥发陈化至白色胶状，待用；
二、铜铟镓硒前驱体薄膜的制备：得到胶体取适量溶解在乙醇中，通过刮涂法或滴涂法涂覆在衬底上，通过在90-150℃下初步热处理去除溶剂与杂质，得到前驱体薄膜，待用；
三、退火热处理：得到的前驱体薄膜经管式炉在氮气条件，以5-10℃/min升温条件下升至400-500℃温度后保温30-150min后自然冷却至室温，得到铜铟镓硒薄膜吸收层；所述的退火热处理过程中无需再添加硒源的任何硒化工艺，直接在一定温度热处理即可。
2.根据权利要求1所述的一种无硒化过程非真空法制备铜铟镓硒吸收层的方法，其特征在于：所述衬底为掺氟二氧化锡导电玻璃、铜片或钢片。
3.根据权利要求1所述的一种无硒化过程非真空法制备铜铟镓硒吸收层的方法，其特征在于：所述的铜铟镓硒前驱体薄膜的制备中涂膜的溶胶厚度为25-95μm。
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