CN104078521A - 基于cigs太阳能电池吸收层的表面修饰及复合缓冲层的太阳能电池制备方法 - Google Patents
基于cigs太阳能电池吸收层的表面修饰及复合缓冲层的太阳能电池制备方法 Download PDFInfo
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Abstract
本发明的目的在于提供一种CIGS太阳能电池吸收层的修饰和缓冲层的优化方法，将修饰层CuInS2引入吸收层表面作为过渡层，降低吸收层和缓冲层之间的带宽层间差距，提高匹配性；同时用CdS/ZnS双缓冲层代替传统的CdS缓冲层，减少Cd的用量提高生产过程的环保性；同时CdS/ZnS的引入有利于获得蓝光区的光谱响应，提高电池的短路电流；减小电子亲和势，提高开路电压；提高吸收层和缓冲层之间的晶格匹配性，进而进一步提高太阳能电池的转换效率。
Description
技术领域
本发明属于太阳能电池领域，涉及到一种采用吸收层表面修饰+复合缓冲层制备太阳能电池的方法。
背景技术
近年来，铜铟镓硒(CIGS)薄膜太阳电池取得了很高的光电转换效率。在这种电池中大多采用化学水浴法(CBD)沉积的硫化镉(CdS)薄膜作为缓冲层。但由于Cd属于重金属，在沉积过程中产生的含Cd废水，会对环境产生较大的污染。同时CdS薄膜的禁带宽度只有2.4eV，对电池吸收层短波响应有一定的影响；同时与吸收层的CIGS的禁带宽度(1.02ev)有较大层间的差距，不利于晶格匹配。
因此，CIGS太阳电池的光吸收系数在短波区的提高以及无镉缓冲层CIGS太阳电池的开发成为全球CIGS太阳电池研究的热点。在这些无镉缓冲层中，主要有两类：第一类是In基缓冲层,包括In的硫化物、硒化物和氧化物,主要包括In2S3和In(0H)3两种薄膜材料；第二类是Zn基缓冲层,包括Zn基的硫化物、硒化物和氧化物,如ZnS,Zn(1-x)MgxO,ZnSe,ZnO等。
其中应用最广和效果最好的材料是ZnS：具有如下特点：1.ZnS无毒，环保。2.ZnS(3.66ev)的禁带宽度比CdS(2.4ev)宽的多，不仅可以提高电池的短路电流，还有利于获得蓝光区的光谱响应。3.ZnS可以减小电子亲和势，提高开路电压。4.以CBD法制出的ZnS缓冲层的太阳能电池的转换效率与CdS接近。
目前的2种缓冲层材料在应用上各有利弊：
CdS，优点：较高载流子迁移率；缺点：Cd是重金属,属于有毒物质；与窗口层的匹配性较差。
ZnS，优点：获得较高的短路电流和开路电压；缺点：与CIGS层的晶型匹配性差，电池效率较低。
所以目前，缓冲层材料的环保性以及缓冲层与吸收层和窗口层之间的匹配度对太阳能电池有较大的影响，目前对缓冲层材料和晶格匹配度的研究都很多，但专注与次两方面结合的研究较少，而且效果不理想。
发明内容
本发明的目的在于提供一种CIGS太阳能电池吸收层的修饰和缓冲层的优化方法，将修饰层CuInS2引入吸收层表面作为过渡层，降低吸收层和缓冲层之间的带宽层间差距，提高匹配性；同时用CdS/ZnS双缓冲层代替传统的CdS缓冲层，减少Cd的用量提高生产过程的环保性；同时CdS/ZnS的引入有利于获得蓝光区的光谱响应，提高电池的短路电流；减小电子亲和势，提高开路电压；提高吸收层和缓冲层之间的晶格匹配性，进而进一步提高太阳能电池的转换效率。
本发明是一种基于吸收层表面修饰和缓冲层的优化改进技术，其特征在于，其中包括：
—吸收层表面修饰层(1)，该修饰层制备于吸收层的表面，一方面有利于改善表面的平整度，更重要的一方面是降低吸收层和缓冲层之间的带宽层间差距，提高匹配性
—缓冲层CdS(2)，该缓冲层制作于吸收层修饰层上，降低修饰层和ZnS层之间的带宽层间差距，提高匹配性。
—缓冲层ZnS(3)，该缓冲层制作于缓冲层CdS上，一方面有利于获得蓝光区的光谱响应，提高电池的短路电流；减小电子亲和势，提高开路电压；另一方面可以提高缓冲层与窗口层之间的匹配度。
本发明的积极效果是：使各层间的匹配性进一步加强，器件的转换效率较改进前有进一步的提高。
附图说明
为进一步说明本发明的内容以及特点，以下结合附图对本发明作详细的描述，其中：图1是本发明的示意图；
具体实施方式
为使本发明的目的、技术方案以及优点更加清楚明白，以下结合具体的实施例并结合参照附图进行具体说明。
如图1所示，图1为本发明提供的本发明是一种基于吸收层表面修饰和缓冲层的优化改进技术的结构示意图。该发明包括－吸收层表面修饰层(1)；－缓冲层CdS(2)；该缓冲层CdS(2)是制作在吸收层表面修饰层(1)上的；－缓冲层ZnS(3)，该缓冲层ZnS(3)是制作在缓冲层CdS(2)上的。.
所述的吸收层表面修饰层(1)为Cu、In、S的化合物薄膜，通过在含有In、S的混合溶液中浸泡获得。吸收层表面修饰层(1)上面是采用化学水浴沉积工艺制备的缓冲层CdS(2),通过改变反应温度和反应时间可以控制缓冲层CdS(2)的厚度，通常情况下该缓冲层的厚度在1-200nm之间。缓冲层CdS(2)上面的缓冲层ZnS(3)也是采用化学水浴沉积工艺制备的。该缓冲层ZnS(3)的厚度也可以通过控制反应温度和反应时间调节，通常情况下所述的缓冲层ZnS(3)厚度在1－200nm之间。
实验例：
1.合成含In、S混合液的工艺如下：
在50ml的烧杯中，依次加入1-20mmol的氯化铟(InCl3)和1-20ml的硫代乙酰胺(CH3CSNH2)，先进行磁力搅拌约20分钟，随后超声20分钟，放置待用。
2.将制备好背电极和CIGS吸收层的玻璃片浸入到上述溶液中30s，取出后在空气中放置1-30分钟。
3.于恒温水浴锅中分别加入1-100mmol CdSO4，1-100mmol氨水和450ml水，把浸泡好的玻璃片置入溶液沉积反应，搅拌速度300rpm，反应温度1-90℃，沉积时间5-30min。取出后，超声清洗1min，清洗后用N2轻轻吹扫表面，除去表面液体。然后放入含有1-100mmol CdSO4，1-100mmol硫脲、1-100mmol氨水和450ml水的混合溶液中，搅拌速度300rpm，反应温度1-90℃，沉积时间5-30min，取出后超声清洗1min*2次，清洗后用N2轻轻吹扫表面，除去表面液体。
4.于恒温水浴锅中分别加入1-100mmol ZnSO4，1-100mmol硫脲、1-100mmol氨水和450ml水的混合溶液中，搅拌速度300rpm，反应温度0-90℃，沉积时间5-30min，取出后超声清洗1min，清洗后用N2轻轻吹扫表面，除去表面液体。
以上所述的具体施例，对本发明的目的、技术方案和积极的效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体施例而已，并不用于限制本发明，凡在本发明的原则之内所做的任何修和改进等，均应包含在本发明的保护范围之内。
Claims (6)
1.一种基于CIGS太阳能电池吸收层的表面修饰及复合缓冲层的太阳能电池制备方法，其特征在于，其中包括：
CIGS吸收层表面的修饰层，该修饰层置于CIGS吸收层的表面，提升其与缓冲层的匹配性。
复合缓冲层，该缓冲层设置在CIGS吸收层表面的修饰层之上，可以减少制备过程中的污染，还可以增强电池对光的吸收，并可以提升此层上下界面的匹配性。
2.如权利要求1所述的基于CIGS太阳能电池吸收层的表面修饰及复合缓冲层的太阳能电池制备方法，其特征在于，其中修饰层是氯化铟(InCl3)和硫代乙酰胺(CH3CSNH2)反应形成的薄膜。
3.如权利要求1所述的基于CIGS太阳能电池吸收层的表面修饰及复合缓冲层的太阳能电池制备方法，其特征在于，修饰层通过浸泡在CIGS表面形成薄膜。
4.如权利要求1所述的基于CIGS太阳能电池吸收层的表面修饰及复合缓冲层的太阳能电池制备方法，其特征在于，缓冲层为CdS/ZnS复合双缓冲层。
5.如权利要求1所述的基于CIGS太阳能电池吸收层的表面修饰及复合缓冲层的太阳能电池制备方法，其特征在于，CdS/ZnS复合双缓冲层的厚度为1～200/1～200nm之间。
6.如权利要求1所述的基于CIGS太阳能电池吸收层的表面修饰及复合缓冲层的太阳能电池制备方法，其特征在于，CdS/ZnS复合双缓冲层通过两段式化学水浴沉积(CBD)的方法形成于修饰层上。
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| CN112054077A (zh) * | 2019-06-06 | 2020-12-08 | 北京铂阳顶荣光伏科技有限公司 | 太阳能电池及其制备方法 |
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