CN106591914B - 一种电沉积法制备的铜铟硒硫薄膜太阳能电池吸收层 - Google Patents
一种电沉积法制备的铜铟硒硫薄膜太阳能电池吸收层 Download PDFInfo
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- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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Abstract
本发明涉及一种电沉积法制备的铜铟硒硫薄膜太阳能电池吸收层，其特征在于，所述工艺步骤包括：电沉积前驱体薄膜、热处理两个步骤。选用硫酸铜、硫酸铟、二氧化硒、硫代硫酸钠分别作为Cu源、In源、Se源、S源，按照Cu:In:Se:S=8:20:5:10的摩尔比制备前驱体溶液，以石墨为阳极，待沉积衬底为阴极，进行电沉积形成前驱体薄膜，400℃氮气气氛下热处理，即得到铜铟硒硫薄膜太阳能电池吸收层。本发明涉及的制备方法简单，反应条件温和，成本低。本发明制备的铜铟硒硫薄膜太阳能电池吸收层结构致密，表面平整，其禁带宽度为1.49eV，满足实际应用需要。
Description
技术领域
本发明涉及光电材料新能源领域，具体涉及一种电沉积法制备的铜铟硒硫薄膜太阳能电池吸收层。
背景技术
随着人类社会的发展，能源的需求量增长迅猛，化石能源已无法满足需求，因此人们将眼光投向了可再生的能源。太阳能、生物能、风能、和海洋能等新兴的清洁可再生能源在世界各地迅速崛起，开始逐渐代替了传统能源。在这些清洁能源中，太阳能因其覆盖范围广泛、利用价值高，蕴含的能量目前来说可以远远超过我们的需求，因此倍受世界各国能源科学家青睐，最近几年来，太阳能光伏材料的利用也已被提高到了战略高度。其中，化合物半导体薄膜比硅基薄膜的效率高，弱光条件的发电性能较好，稳定性好，无光致衰退以及可以在柔性基地上沉积等特点，将成为太阳能电池以后发展研究的重要方向。
目前研究较多的薄膜太阳能电池是碲化镉，硒化镉，铜铟镓硒等，从原料角度讲，镉有毒，镓为稀有元素，这将限制这类薄膜材料的发展；从制备方法上讲，目前通常采用电子束蒸发法、真空热蒸发法、溅射法等真空制备方法，真空热蒸发法、溅射等方法采用的设备复杂、实验过程成本极高等缺点。所以伴随着能源和环境问题日益成为世界发展主题的背景下，探索一种工艺要求不高、能控制成本、能耗更低、对环境友好的合成方法和薄膜材料来制备太阳能电池具有很强的科研价值和实用价值。电沉积法因其简单，反应条件温和，成本低，能大面积成膜而备受关注。有关电沉积法制备薄膜的研究较多，以下给出部分文献：
发明专利授权公开号：CN 104795456A，2015.07.22
发明专利授权公开号：CN 104681658A，2015.06.03
发明专利授权公开号：CN 105489672A，2016.04.13。
发明内容
本发明针对现有技术的不足，提供一种电沉积法制备的铜铟硒硫薄膜太阳能电池吸收层。
为实现上述目的，本发明的一种电沉积法制备的铜铟硒硫薄膜太阳能电池吸收层，工艺步骤包括：电沉积前驱体薄膜、热处理两个步骤。选用硫酸铜、硫酸铟、二氧化硒、硫代硫酸钠分别作为Cu源、In源、Se源、S源，按照Cu : In : Se : S=8 : 20: 5 : 10的摩尔比制备前驱体溶液，以石墨为阳极，待沉积衬底为阴极，进行电沉积形成前驱体薄膜，400℃氮气气氛下热处理，即得到铜铟硒硫薄膜太阳能电池吸收层。具体步骤如下：
步骤一：将待沉积衬底依次用洗衣粉水、去离子水、丙酮、无水乙醇、去离子水超声清洗15~60 min，吹风机吹干，备用；
步骤二：取8mmol/L硫酸铜、10mmol/L硫酸铟、5mmol/L二氧化硒、5mmol/L硫代硫酸钠和40mmol/L柠檬酸钠配置成电解液，溶剂为去离子水，用稀盐酸将溶液的pH值调至1.7，搅拌1h，将溶液密封好，放置于50 ℃的恒温水浴之中4~5h；
步骤三：将步骤一吹干后的待沉积衬底置于装有电解液的双电极电解槽中，以石墨为阳极，待沉积衬底为阴极，电沉积在室温下进行，过程中不需要搅拌，1.3~1.7V沉积电位范围内进行电沉积处理40~80min，取出电沉积前驱体薄膜，去离子水冲洗，吹干；
步骤四：将步骤三的电沉积前驱体薄膜置于管式电阻炉，氮气气氛下，400℃热处理80min后，自然降至室温，即得铜铟硒硫薄膜太阳能电池吸收层。
所述的待沉积衬底为FTO玻璃、ITO玻璃、溅射钼的钠钙玻璃或铜箔。
本发明的有益效果在于：制备方法简单，反应条件温和，成本低；制备的铜铟硒硫薄膜太阳能电池吸收层结构致密，表面平整，其禁带宽度为1.49eV，满足实际应用需要。
附图说明
图1是本发明制得的铜铟硒硫薄膜的SEM图；
图2是本发明制得的铜铟硒硫薄膜的XRD图，其中，a是热处理前的XRD，b是热处理后的XRD。
具体实施方式
下面通过具体实施例，对本发明做详细的描述。
实施例1
本实施方式的一种电沉积法制备的铜铟硒硫薄膜太阳能电池吸收层是按照以下步骤进行的：
一、将FTO玻璃在洗衣粉水中超声清洗15min，用去离子水冲洗除去洗衣粉，将冲洗后的FTO 玻璃在丙酮中超声清洗15min后，放入无水乙醇中超声清洗15min，再用去离子水超声清洗15min，吹风机吹干，备用；
二、取8mmol/L硫酸铜、10mmol/L硫酸铟、5mmol/L二氧化硒、5mmol/L硫代硫酸钠和40mmol/L柠檬酸钠配置成电解液，溶剂为去离子水，用稀盐酸将溶液的pH值调至1.7，搅拌1h，将溶液密封好，放置于50 ℃的恒温水浴之中4h；
三、将步骤一吹干后的FTO玻璃置于装有电解液的双电极电解槽中，以石墨为阳极，FTO玻璃为阴极，电沉积在室温下进行，过程中不需要搅拌，1.6V沉积电位下进行电沉积处理60min，取出电沉积前驱体薄膜，去离子水冲洗，吹干；
四、将步骤三的电沉积前驱体薄膜置于管式电阻炉，氮气气氛下，400℃热处理80min后，自然降至室温，即得铜铟硒硫薄膜太阳能电池吸收层，其禁带宽度为1.49eV，满足实际应用需要。
从图1可以观察到制得的铜铟硒硫薄膜结构致密，表面平整。
从图2热处理后的峰与标准卡片对比，可以得出图中三个峰分别对应化合物铜铟硒硫的（112）、（220）和（116）晶面的峰，证实了铜铟硒硫的存在。
实施例2
本实施方式的一种电沉积法制备的铜铟硒硫薄膜太阳能电池吸收层是按照以下步骤进行的：
一、将打磨光亮的铜箔在洗衣粉水中超声清洗15min，用去离子水冲洗除去洗衣粉，将冲洗后的铜箔在丙酮中超声清洗15min后，放入无水乙醇中超声清洗15min，再用去离子水超声清洗15min，吹风机吹干，将铜箔的一侧表面用胶带贴好，备用；
二、取8mmol/L硫酸铜、10mmol/L硫酸铟、5mmol/L二氧化硒、5mmol/L硫代硫酸钠和40mmol/L柠檬酸钠配置成电解液，溶剂为去离子水，用稀盐酸将溶液的pH值调至1.7，搅拌1h，将溶液密封好，放置于50 ℃的恒温水浴之中4h；
三、将步骤一处理后的铜箔置于装有电解液的双电极电解槽中，以石墨为阳极，铜箔为阴极，电沉积在室温下进行，过程中不需要搅拌，1.6V沉积电位下进行电沉积处理60min，取出电沉积前驱体薄膜，去离子水冲洗，吹干；
四、将步骤三的电沉积前驱体薄膜置于管式电阻炉，氮气气氛下，400℃热处理80min后，自然降至室温，即得铜铟硒硫薄膜太阳能电池吸收层。
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内作出各种变形或修改，这并不影响本发明的实质内容。
Claims (2)
1.一种电沉积法制备的铜铟硒硫薄膜太阳能电池吸收层，其特征在于：
步骤一：将待沉积衬底依次用洗衣粉水、去离子水、丙酮、无水乙醇、去离子水超声清洗15～30min，吹风机吹干，备用；
步骤二：取8mmol/L硫酸铜、10mmol/L硫酸铟、5mmol/L二氧化硒、5mmol/L硫代硫酸钠和40mmol/L柠檬酸钠配置成电解液，溶剂为去离子水，用稀盐酸将溶液的pH值调至1.7，搅拌1h，将溶液密封好，放置于50℃的恒温水浴之中4～5h；
步骤三：将步骤一吹干后的待沉积衬底置于装有电解液的双电极电解槽中，以石墨为阳极，待沉积衬底为阴极，电沉积在室温下进行，过程中不需要搅拌，在沉积电位1.6V进行电沉积处理60min，取出电沉积前驱体薄膜，去离子水冲洗，吹干；
步骤四：将步骤三的电沉积前驱体薄膜置于管式电阻炉，氮气气氛下，400℃热处理80min后，自然降至室温，即得铜铟硒硫薄膜太阳能电池吸收层。
2.根据权利要求1所述的一种电沉积法制备的铜铟硒硫薄膜太阳能电池吸收层，其特征在于：所述的待沉积衬底为FTO玻璃、ITO玻璃、溅射钼的钠钙玻璃或铜箔。
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