CN105118883A - 一种低镉cigs基薄膜太阳能电池及其制备方法 - Google Patents
一种低镉cigs基薄膜太阳能电池及其制备方法 Download PDFInfo
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Abstract
本发明提供一种低镉CIGS基薄膜太阳能电池及其制备方法，该薄膜太阳能电池由下至上依次包括衬底、背电极、CIGS吸收层、CdS层和上电极，所述CIGS吸收层表面的Cu原子被Cd原子部分置换形成表面改性层，所述CdS层的厚度为20-35nm。制备方法包括如下工序：a，在衬底上沉积背电极；b，在背电极上沉积CIGS吸收层；c，在CIGS吸收层上沉积CdS层；d，在CdS层表面沉积上电极；所述步骤c在沉积CdS层之前，还包括对CIGS表面进行改性处理的工序。本发明在维持CIGS电池整体高转化效率的同时，大大降低了CdS层厚度，大幅度降低了整个电池组件的Cd含量。
Description
技术领域
本发明涉及薄膜太阳能电池技术领域，具体涉及一种低镉CIGS基薄膜太阳能电池及其制备方法。
背景技术
铜铟镓硒（Cu(In，Ga)Se2，简称CIGS）薄膜太阳能电池以其光电转化效率高，材料用量少，重量轻，可柔性化等特点受到广泛关注，并被认为是很有商业化前景的第二代太阳能电池。
通常CIGS薄膜太阳能电池的制备工序包括：a，在衬底上沉积背电极；b，在背电极上沉积CIGS吸收层；c，在CIGS吸收层上沉积CdS层；d，在CdS层表面沉积上电极。在CIGS薄膜太阳能电池制备过程中，需要用到具有一定环境污染性的CdS层，其采用化学水浴沉积（CBD）工艺制备的膜层厚度一般约为40-60nm左右，综合到整个电池体系中，造成电池Cd含量较高，引起人们对镉污染的担心，也影响了其应用前景。虽然技术上可以通过降低CdS厚度来降低整个组件的Cd含量，但CdS厚度的降低，也大大降低了整个电池组件的光电转化效率。故实际上，目前商业化的CIGS电池CdS层厚度一般控制在50nm左右，工艺窗口较窄，工艺控制难度较大。
发明内容
发明目的：为了解决上述现有技术的不足，本发明提供一种低镉CIGS基薄膜太阳能电池及其制备方法，该薄膜太阳能电池整体Cd含量低、工艺控制窗口较宽。
本发明的技术方案：
一种低镉CIGS基薄膜太阳能电池，由下至上依次包括衬底、背电极、CIGS吸收层、CdS层和上电极，所述CIGS吸收层表面的Cu原子被Cd原子部分置换形成表面改性层，所述CdS层的厚度为20-35nm。
优选地，所述CdS层的厚度为20-25nm。
所述衬底为玻璃、金属、陶瓷以及聚合物衬底中的任意一种；所述背电极为Mo电极；所述上电极为ZnO/AZO电极、ZnO/ITO电极、AZO电极、ITO电极中的任意一种。
一种低镉CIGS基薄膜太阳能电池的制备方法，包括如下工序：
a，在衬底上沉积背电极；
b，在背电极上沉积CIGS吸收层；
c，在CIGS吸收层上沉积CdS层；
d，在CdS层表面沉积上电极；
所述步骤c之前，对CIGS表面进行改性处理，具体步骤为：
（1）制备反应溶液A：配制镉盐的水溶液，向该溶液中加入氨水，用碱溶液调节pH值为10.5-12，搅拌均匀，即得反应溶液A，常温保存备用；
（2）制备反应溶液B：配制硫脲的水溶液，将该溶液与反应溶液A按体积比为1：1~2的比例混合，用碱溶液调节pH值为10.5-12，搅拌均匀，即得反应溶液B，常温保存备用；
（3）将工序b制得的沉积有CIGS吸收层的衬底置于化学表面沉积（CSD）工艺设备的加热台上加热，当衬底温度达到85-100℃时，将步骤（1）制备得到的新鲜的反应溶液A立刻滴到加热的衬底表面，并控制衬底表面不出现干涸，反应5-10min，立马取出并清除衬底表面多余反应溶液A，形成表面改性层；
（4）将步骤（3）制得的沉积有表面改性层的衬底置于CSD工艺设备的另一加热台上继续加热，当衬底温度达到65-75℃，将步骤（2）制得的新鲜的反应溶液B立刻滴到加热的衬底表面，并控制衬底表面不出现干涸，反应2-8min，形成CdS膜层，立刻取出衬底，用去离子水冲洗干净，再用高压气体吹干衬底表面，进入下一道上电极沉积工艺。
步骤（1）中，所述镉盐的水溶液中Cd2-浓度为3-6mmol/L，氨水浓度为10-20wt%，Cd2-与NH4OH的摩尔比为1：10~300。
步骤（2）中，所述硫脲的水溶液中硫脲的浓度为0.1-0.5mol/L。
步骤（1）和步骤（2）中，所述镉盐为可溶性镉盐，具体选自CdSO4、CdCl2、CdI2和（CH3COO）2Cd·2H20中的任意一种或多种的组合物，所述碱溶液为3-10mol/LNaOH溶液。
本发明对CIGS吸收层表面进行改性处理，涉及的反应是溶液中的Cd原子和CIGS吸收层表面的Cu原子发生离子交换，改变了表面改性层的导电特性，Cd原子在表面层起到施主掺杂的效果，表面改性层与基底CIGS吸收层一起形成一浅埋的同质PN结，从而在整个CIGS薄膜电池中形成质量优良的PN结，维持电池高转化效率。在表面改性层上制备极薄的CdS膜层，能够解决整体电池的能带和晶格匹配，同时由于CdS膜层折射率值处于上电极与CIGS吸收层之间，起到减反射效果。极薄的CdS膜层能显著降低此膜层对光的吸收，从而增加进入CIGS吸收层的入射光，增加短路电流，并大幅度降低整个膜层的Cd含量。
有益效果：
1．在维持CIGS电池整体高转化效率的同时，大大降低了CdS层厚度，大幅度降低了整个电池组件的Cd含量。
2．拓宽了CdS层工艺窗口，降低了此膜层工艺控制难度，便于大规模生产应用。
附图说明
图1为本发明的低镉CIGS基薄膜太阳能电池的结构示意图；
其中，1、衬底；2、背电极；3、CIGS吸收层；4、表面改性层；5、CdS层；6、上电极。
具体实施方式
下面以CdSO4作为镉盐为例，通过具体实施例的方式，对本发明技术方案进行详细说明，但是本发明的保护范围不局限于所述实施例。
以范围形式表达的值应当以灵活的方式理解为不仅包括明确列举出的作为范围限值的数值，而且还包括涵盖在该范围内的所有单个数值或子区间，犹如每个数值和子区间被明确列举出。例如，“大约0.1%至约5%”的浓度范围应当理解为不仅包括明确列举出的约0.1%至约5%的浓度，还包括有所指范围内的单个浓度（如，1%、2%、3%和4%）和子区间（例如，0.1%至0.5%、1%至2.2%、3.3%至4.4%）。
实施例1
如图1所示，一种低镉CIGS基薄膜太阳能电池，由下至上依次包括衬底1、背电极2、CIGS吸收层3、CdS层5和上电极6，所述CIGS吸收层3表面的Cu原子被Cd原子部分置换，所述CdS层5的厚度为20nm。
所述低镉CIGS基薄膜太阳能电池的制备方法，包括如下工序：
a，在衬底上沉积背电极；
b，在背电极上沉积CIGS吸收层；
c，在CIGS吸收层上沉积CdS层；
d，在CdS层表面沉积上电极；
所述步骤c之前，对CIGS表面进行改性处理，具体步骤为：称取CdSO4粉末1.6g，溶于1.276L去离子水中，搅拌均匀，向CdSO4溶液中加入224ml浓度为19wt%的氨水，进一步搅拌均匀即可得到反应溶液A。
称取硫脲粉末2.85g，溶于0.375L去离子水中，搅拌均匀，直至硫脲粉末完全溶解，取0.75L反应溶液A，与硫脲溶液混合，用3-10mol/LNaOH溶液调节pH值为10.5-12，搅拌均匀，即得反应溶液B。
将采用共蒸发工艺或者溅射后硒化工艺沉积好的带CIGS吸收层的衬底固定于CSD工艺设备加热台上，加热衬底，当衬底温度达到85℃时，将溶液A立刻滴定到加热的衬底表面（溶液量为0.15ml/cm2），反应7min，取出衬底，清除表面多余反应溶液A，形成表面改性层；
将制得的带表面改性层的衬底放入CSD工艺设备另一加热台，控制温度为75℃；将制得的溶液B立刻滴定到加热的衬底表面（溶液量为0.15ml/cm2），反应3min，取出衬底，并用去离子水冲洗干净，用高压气体吹干衬底表面，得到制备的CdS膜层，进入下一道上电极沉积工艺，并完成整个CIGS薄膜太阳能电池的制备。
实施例2~3所使用原料量、反应条件及所得CdS层5的厚度见表1，其余条件同实施例1。
表1
。
对比例1
与实施例1的不同之处在于，在CIGS吸收层上直接沉积CdS层，所述CdS层的厚度为30nm。
对比例2
与实施例1的不同之处在于，在CIGS吸收层上直接沉积CdS层，所述CdS层的厚度为50nm。
I-V测试
将实施例1~3及对比例1~2制备的太阳能电池在标准条件（即：温度25℃，光源辐照度1000W/m2，光谱辐照度分布AM1.5）下进行I-V测试，测得的光电转换效率结果如表2所示。
表2
。
由表2可知，本发明在降低了CdS层厚度的同时，能够实现整个电池维持高的光电转换效率。对于本发明的整个CIGS电池组件来说，Cd主要存在于CdS层（占总含量95%以上），因此可以认为整个电池中的Cd含量主要由CdS膜层的厚度决定。而本发明通过将CIGS吸收层表面改性的方式，在维持高的光电转换效率的基础上，大幅降低了CdS膜层厚度，实现了大幅度降低整个电池中Cd含量的目的，其中，当CdS层的厚度在20-25nm时，光电转换效率更高，为优选例。
总之，以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所作的均等变化与修饰，皆应属本发明专利的涵盖范围。
Claims (9)
1.一种低镉CIGS基薄膜太阳能电池，由下至上依次包括衬底（1）、背电极（2）、CIGS吸收层（3）、CdS层（5）和上电极（6），其特征在于，所述CIGS吸收层（3）表面的Cu原子被Cd原子部分置换形成表面改性层（4），所述CdS层（5）的厚度为20-35nm。
2.根据权利要求1所述一种低镉CIGS基薄膜太阳能电池，其特征在于，所述CdS层（5）的厚度为20-25nm。
3.根据权利要求1所述一种低镉CIGS基薄膜太阳能电池，其特征在于，所述衬底为玻璃、金属、陶瓷以及聚合物衬底中的任意一种。
4.根据权利要求1所述一种低镉CIGS基薄膜太阳能电池，其特征在于，所述背电极为Mo电极。
5.根据权利要求1所述一种低镉CIGS基薄膜太阳能电池，其特征在于，所述上电极为ZnO/AZO电极、ZnO/ITO电极、AZO电极、ITO电极中的任意一种。
6.权利要求1~5任一项所述一种低镉CIGS基薄膜太阳能电池的制备方法，包括如下工序：
a，在衬底上沉积背电极；
b，在背电极上沉积CIGS吸收层；
c，在CIGS吸收层上沉积CdS层；
d，在CdS层表面沉积上电极；
其特征在于，所述步骤c之前，对CIGS表面进行改性处理，具体步骤为：
（1）制备反应溶液A：配制镉盐的水溶液，向该溶液中加入氨水，用碱溶液调节pH值为10.5-12，搅拌均匀，即得反应溶液A，常温保存备用；
（2）制备反应溶液B：配制硫脲的水溶液，将该溶液与反应溶液A按体积比为1：1~2的比例混合，用碱溶液调节pH值为10.5-12，搅拌均匀，即得反应溶液B，常温保存备用；
（3）将工序b制得的沉积有CIGS吸收层的衬底置于CSD工艺设备的加热台上加热，当衬底温度达到85-100℃时，将步骤（1）制备得到的新鲜的反应溶液A立刻滴到加热的衬底表面，并控制衬底表面不出现干涸，反应5-10min，立马取出并清除衬底表面多余反应溶液A，形成表面改性层；
（4）将步骤（3）制得的沉积有表面改性层的衬底置于CSD工艺设备的另一加热台上继续加热，当衬底温度达到65-75℃，将步骤（2）制得的新鲜的反应溶液B立刻滴到加热的衬底表面，并控制衬底表面不出现干涸，反应2-8min，形成CdS膜层，立刻取出衬底，用去离子水冲洗干净，再用高压气体吹干衬底表面，进入下一道上电极沉积工艺。
7.根据权利要求6所述一种低镉CIGS基薄膜太阳能电池的制备方法，其特征在于，步骤（1）中，所述镉盐的水溶液中Cd2-浓度为3-6mmol/L，氨水浓度为10-20wt%，Cd2-与NH4OH的摩尔比为1：10~300。
8.根据权利要求6所述一种低镉CIGS基薄膜太阳能电池的制备方法，其特征在于，步骤（2）中，所述硫脲的水溶液中硫脲的浓度为0.1-0.5mol/L。
9.根据权利要求7所述一种低镉CIGS基薄膜太阳能电池的制备方法，其特征在于，步骤（1）和步骤（2）中，所述镉盐为CdSO4、CdCl2、CdI2和(CH3COO)2Cd·2H20中的任意一种或多种的组合物，所述碱溶液为3-10mol/LNaOH溶液。
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