CN110323293B - 一种铜铟镓硒薄膜太阳能电池 - Google Patents

一种铜铟镓硒薄膜太阳能电池 Download PDF

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CN110323293B
CN110323293B CN201910372257.2A CN201910372257A CN110323293B CN 110323293 B CN110323293 B CN 110323293B CN 201910372257 A CN201910372257 A CN 201910372257A CN 110323293 B CN110323293 B CN 110323293B
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彭寿
马立云
李刚
姚婷婷
王天齐
彭塞奥
金克武
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China Building Materials Glass New Materials Research Institute Group Co Ltd
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Abstract

本发明公开一种铜铟镓硒薄膜太阳能电池，包括基板，基板表面由内向外依次层叠背电极层、吸收层、缓冲层、窗口层、透明电极层以及金属栅电极层，其特征在于，所述吸收层包括m组相层叠的基础吸收层，每组基础吸收层均包含由下至上层叠的铜铟镓膜层与硒膜层，2≤m≤5；吸收层厚度为1～2.5μm；背电极层背电极层厚度为0.3～2μm的；缓冲层厚度为20～200nm；窗口层厚度为20～200nm；透明电极层厚度为0.3～2μm；金属栅电极层厚度为2～10μm；本发明镓的梯度沿吸收层背面和吸收层表面两个方向，从而促进镓元素在铜铟镓硒吸收层中深度分布及吸收层带隙宽度的增大，进而提高薄膜太阳能电池的开路电压及光电转换效率。

Description

一种铜铟镓硒薄膜太阳能电池
技术领域
本发明涉及太阳能电池技术领域，具体是一种铜铟镓硒薄膜太阳能电池。
背景技术
太阳能作为一种重要的可再生能源，受到广泛的关注并得到快速发展。随着光伏技术的持续发展和进步，光伏发电成本不断下降，光伏发电竞争力持续增强，可以预见，全球光伏市场在未来很长一段时间内将继续保持高速增长。
与传统晶硅、非晶硅电池相比，铜铟镓硒(CIGS)薄膜太阳能电池作为新一代的薄膜电池，具备弱光发电性能好、成本低、温度系数低、能源回收期短、寿命长、发电稳定、抗辐射能力强、生产工艺无污染等优势，被业界评为“太阳能能源的未来”，市场前景巨大。CIGS是一种直接带隙的P型半导体材料，其吸收系数高达105/cm，2μm厚的CIGS薄膜就可吸收90％以上的太阳光。铜铟镓硒电池转换效率在薄膜太阳能电池中是最高的，2017年12月达到了22.9％的光电转换效率，因此日本、德国等国家都投入巨资进行研究和产业化。
CIGS吸收层的制备是铜铟镓硒薄膜太阳能电池的核心工艺。目前，国际上制备CIGS薄膜的工艺主要有两类，一类是由美国可再生能源国家实验室（NREL）发展出的“共蒸法”，另一类是以Solar Frontier、Avancis等公司为代表使用的“溅射后硒化法”。作为实验室里制备小面积的铜铟镓硒薄膜太阳能电池时，共蒸法沉积的CIGS薄膜质量较好，电池效率较高，但蒸发无法精确控制元素比例、重复性差、材料利用率不高、很难实现大面积均匀稳定成膜，因而限制其在大规模工业化生产中的应用。而溅射后硒化法工艺相对简单，可以在大面积玻璃衬底上溅射金属合金层，可以精确控制铜、铟、镓元素的比例、后硒化材料可以采用气态或固态的硒源，制备的薄膜性能优良，非常适合大面积开发，因此溅射后硒化法被视作更理想的产业化路线。
在溅射后硒化法中，CIGS吸收层的形成是堆叠元素前驱体一系列的硒化过程。然而，CIGS吸收层通常在靠近背电极的底层处显示出明显的Ga元素偏析的现象，这种效应的起因在于含In和Ga化合物的不同反应动力学。由于形成Ga的硒化物相的反应温度比形成Cu和In的硒化物温度高约100℃，所以富Ga相在堆叠层的底部区域中累积，直到在那里形成富Ga的CIGS吸收层。一旦发生形成黄铜矿CIGS吸收层的反应，所建立的梯度只能通过In和Ga的相互扩散来弛豫，而此过程需要较大的热激活能，即使在较高的退火温度下，增加退火时间，也只有很少的相互扩散能够实现。CIGS薄膜中掺Ga的目的是为了增加吸收层材料的带隙宽度，使其在1.04eV到1.67eV范围内连续可调，并实现与太阳光谱的最佳匹配。但是Ga偏析的问题，会降低电池的开路电压，从而影响光电转换效率。
发明内容
本发明的目的在于提供一种铜铟镓硒薄膜太阳能电池，该电池的吸收层解决了现有产品中存在的Ga偏析的问题，提高薄膜太阳能电池的开路电压及光电转换效率。
本发明解决其技术问题所采用的技术方案是：
一种铜铟镓硒薄膜太阳能电池，包括基板，基板表面由内向外依次层叠背电极层、吸收层、缓冲层、窗口层、透明电极层以及金属栅电极层，其特征在于，所述吸收层包括m组相层叠的基础吸收层，每组基础吸收层均包含由下至上层叠的铜铟镓膜层与硒膜层，2≤m≤5；吸收层厚度为1～2.5μm；
所述背电极层为钼膜层，背电极层厚度为0.3～2μm的；
所述缓冲层为硫化镉膜层、硫化铟膜层、硫化锌膜层或氧硫化锌膜层，缓冲层厚度为20～200nm；
所述窗口层为本征氧化锌膜层或氧化锌镁膜层，窗口层厚度为20～200nm；
所述透明电极层为铝掺杂氧化锌膜层，透明电极层厚度为0.3～2μm；
所述金属栅电极层为镍层、铝层或镍铝合金层，金属栅电极层厚度为2～10μm。
进一步的，所述铜铟镓膜层包括n组由铜镓膜层与铟膜层堆叠构成的复合膜层，1≤n≤10。
进一步的，所述铜铟镓膜层包括n组由铜铟膜层与镓膜层堆叠构成的复合膜层，1≤n≤10。
进一步的，所述铜铟镓膜层包括n组由铜镓膜层与铜铟膜层堆叠构成的复合膜层，1≤n≤10。
本发明的有益效果是，在吸收层中通过在铜铟镓膜层中插入硒膜层，解决了铜铟镓硒吸收层中镓元素分布不均的问题，由于前驱体叠层中硒层两侧与铜铟镓膜层均接触，硒化反应往前驱体两侧进行，使得镓的梯度沿吸收层背面和吸收层表面两个方向，从而促进镓元素在铜铟镓硒吸收层中深度分布及吸收层带隙宽度的增大，进而提高薄膜太阳能电池的开路电压及光电转换效率。
附图说明
下面结合附图和实施例对本发明进一步说明：
图1是本发明的结构示意图；
图2是本发明吸收层的示意图；
图3是本发明实施例一铜铟镓膜层的示意图；
图4是本发明实施例二铜铟镓膜层的示意图；
图5是本发明实施例三铜铟镓膜层的示意图。
具体实施方式
实施例一
如图1所示，本发明提供一种吸收层中镓元素均匀分布的铜铟镓硒薄膜太阳能电池，包括基板1，基板1表面由内向外依次层叠背电极层2、吸收层3、缓冲层4、窗口层5、透明电极层6以及金属栅电极层7。
背电极层2为钼膜层，背电极层2的厚度为0.3～2μm的；
缓冲层4为硫化镉膜层、硫化铟膜层、硫化锌膜层或氧硫化锌膜层，缓冲层4的厚度为20～200nm；
窗口层5为本征氧化锌膜层或氧化锌镁膜层，窗口层5的厚度为20～200nm；
透明电极层6为铝掺杂氧化锌膜层，透明电极层6的厚度为0.3～2μm；
金属栅电极层7为镍层、铝层或镍铝合金层，金属栅电极层7的厚度为2～10μm。
结合图2所示，所述吸收层3包括m组相层叠的基础吸收层，每组基础吸收层均包含由下至上层叠的铜铟镓膜层A与硒膜层B，2≤m≤5，吸收层3的厚度为1～2.5μm。
结合图3所示，所述铜铟镓膜层A包括n组由铜镓膜层8与铟膜层9堆叠构成的复合膜层，1≤n≤10。堆叠顺序由下至上可以为铜镓膜层8/铟膜层9/铜镓膜层8/铟膜层9/……/铜镓膜层8/铟膜层9，也可以为铟膜层9/铜镓膜层8/铟膜层9/铜镓膜层8/……/铟膜层9/铜镓膜层8。
实施例二
如图1所示，本发明提供一种吸收层中镓元素均匀分布的铜铟镓硒薄膜太阳能电池，包括基板1，基板1表面由内向外依次层叠背电极层2、吸收层3、缓冲层4、窗口层5、透明电极层6以及金属栅电极层7。
背电极层2为钼膜层，背电极层2的厚度为0.3～2μm的；
缓冲层4为硫化镉膜层、硫化铟膜层、硫化锌膜层或氧硫化锌膜层，缓冲层4的厚度为20～200nm；
窗口层5为本征氧化锌膜层或氧化锌镁膜层，窗口层5的厚度为20～200nm；
透明电极层6为铝掺杂氧化锌膜层，透明电极层6的厚度为0.3～2μm；
金属栅电极层7为镍层、铝层或镍铝合金层，金属栅电极层7的厚度为2～10μm。
结合图2所示，所述吸收层3包括m组相层叠的基础吸收层，每组基础吸收层均包含由下至上层叠的铜铟镓膜层A与硒膜层B，2≤m≤5，吸收层3的厚度为1～2.5μm。
结合图4所示，所述铜铟镓膜层A包括n组由铜铟膜层10与镓膜层11堆叠构成的复合膜层，1≤n≤10。堆叠顺序由下至上可以为铜铟膜层10/镓膜层11/铜铟膜层10/镓膜层11/……/铜铟膜层10/镓膜层11，也可以为镓膜层11/铜铟膜层10/镓膜层11/铜铟膜层10/……/镓膜层11/铜铟膜层10。
实施例三
如图1所示，本发明提供一种吸收层中镓元素均匀分布的铜铟镓硒薄膜太阳能电池，包括基板1，基板1表面由内向外依次层叠背电极层2、吸收层3、缓冲层4、窗口层5、透明电极层6以及金属栅电极层7。
背电极层2为钼膜层，背电极层2的厚度为0.3～2μm的；
缓冲层4为硫化镉膜层、硫化铟膜层、硫化锌膜层或氧硫化锌膜层，缓冲层4的厚度为20～200nm；
窗口层5为本征氧化锌膜层或氧化锌镁膜层，窗口层5的厚度为20～200nm；
透明电极层6为铝掺杂氧化锌膜层，透明电极层6的厚度为0.3～2μm；
金属栅电极层7为镍层、铝层或镍铝合金层，金属栅电极层7的厚度为2～10μm。
结合图2所示，所述吸收层3包括m组相层叠的基础吸收层，每组基础吸收层均包含由下至上层叠的铜铟镓膜层A与硒膜层B，2≤m≤5，吸收层3的厚度为1～2.5μm。
结合图5所示，所述铜铟镓膜层A包括n组由铜镓膜层8与铜铟膜层10堆叠构成的复合膜层，1≤n≤10。堆叠顺序由下至上可以为铜镓膜层8/铜铟膜层10/铜镓膜层8/铜铟膜层10/……/铜镓膜层8/铜铟膜层10；也可以为铜铟膜层10/铜镓膜层8/铜铟膜层10/铜镓膜层8/……/铜铟膜层10/铜镓膜层8。
本发明可以有效地解决现有产品中存在的CIGS吸收层中Ga偏析的问题，提高薄膜太阳能电池的开路电压及光电转换效率。
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制；任何熟悉本领域的技术人员，在不脱离本发明技术方案范围情况下，都可利用上述揭示的方法和技术内容对本发明技术方案做出许多可能的变动和修饰，或修改为等同变化的等效实施例。因此，凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所做的任何简单修改、等同替换、等效变化及修饰，均仍属于本发明技术方案保护的范围内。

Claims (3)

1.一种铜铟镓硒薄膜太阳能电池，其特征在于，包括基板，基板表面由内向外依次层叠背电极层、吸收层、缓冲层、窗口层、透明电极层以及金属栅电极层，其特征在于，所述吸收层包括m组相层叠的基础吸收层，每组基础吸收层均包含由下至上层叠的铜铟镓膜层与硒膜层，2≤m≤5；吸收层厚度为1～2.5μm；
所述背电极层为钼膜层，背电极层厚度为0.3～2μm的；
所述缓冲层为硫化镉膜层、硫化铟膜层、硫化锌膜层或氧硫化锌膜层，缓冲层厚度为20～200nm；
所述窗口层为本征氧化锌膜层或氧化锌镁膜层，窗口层厚度为20～200nm；
所述透明电极层为铝掺杂氧化锌膜层，透明电极层厚度为0.3～2μm；
所述金属栅电极层为镍层、铝层或镍铝合金层，金属栅电极层厚度为2～10μm；
所述铜铟镓膜层包括n组由铜镓膜层与铟膜层堆叠构成的复合膜层，1≤n≤10。
2.根据权利要求1所述的一种铜铟镓硒薄膜太阳能电池，其特征在于，所述n组由铜镓膜层与铟膜层堆叠构成的复合膜层，替换为n组铜铟膜层与镓膜层堆叠构成的复合膜层，1≤n≤10。
3.根据权利要求1所述的一种铜铟镓硒薄膜太阳能电池，其特征在于，所述n组由铜镓膜层与铟膜层堆叠构成的复合膜层，替换为铜镓膜层与铜铟膜层堆叠构成的复合膜层，1≤n≤10。
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