CN107946384B - 一种硅-pedot:pss杂化太阳能电池及其制备方法 - Google Patents
一种硅-pedot:pss杂化太阳能电池及其制备方法 Download PDFInfo
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- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 claims abstract description 24
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Abstract
本发明涉及一种硅‑PEDOT:PSS杂化太阳能电池及其制备方法，用以提高硅‑PEDOT:PSS杂化太阳能电池的光电转换效率。硅‑PEDOT:PSS杂化太阳能电池的制作方法包括：硅基底的清洗；硅基底的表面钝化处理；硅纳米线/PEDOT:PSS复合膜的制备；PEDOT:PSS/硫化亚铜纳米颗粒/氧化石墨烯复合导电层的制备；背面界面层的制备；正面银栅电极的制备；背面电极的制备。
Description
技术领域
本发明涉及太阳能电池技术领域，特别是涉及一种硅-PEDOT:PSS杂化太阳能电池及其制备方法。
背景技术
无机太阳电池因其造价过于昂贵，而无法得到大规模的应用。有机太阳能电池由于其材料便宜、退火温度低、制作过程简单等优势而有希望降低太阳能电池的生产成本，然而有机太阳能电池的效率远低于无机太阳能电池。因此基于无机和有机半导体材料的有机无机杂化太阳能电池越来越受到了人们的青睐，它提供了一种既可以简化制造步骤又可以降低成本的生产技术。无机材料与有机材料相比，它最大的优势为载流子迁移率高，材料的载流子迁移率高则意味着其平均自由程长，可以有效减少电子-空穴对的复合几率。而对于有机材料，电子迁移率一般较低，在电子输运过程损失严重，因而有机光伏电池的光电转化效率较低。有机无机杂化太阳能电池可以结合有机材料和无机材料的优势，避免各自的缺陷，以得到较高的光电转换效率。
发明内容
本发明的目的是克服上述现有技术的不足，提供一种硅-PEDOT:PSS杂化太阳能电池及其制备方法。
为实现上述目的，本发明提出的一种硅-PEDOT:PSS杂化太阳能电池的制备方法，包括以下步骤：(1)硅基底的清洗：将n型硅片依次在丙酮、乙醇、去离子水中超声清洗10-30分钟，并用氮气吹干，接着将吹干的n型硅片置于浓硫酸/双氧水混合溶液中，100-120℃下热处理40-60分钟，接着用去离子水冲洗n型硅片，最后利用氢氟酸去除所述n型硅片的表面的自然氧化硅层；(2)硅基底的表面钝化处理：将步骤1得到n型硅片用氮气吹干，然后浸入饱和五氯化磷的氯苯溶液中，在110℃下热处理40-60分钟，接着将n型硅片从饱和五氯化磷的氯苯溶液中取出并依次在氯苯和四氢呋喃中清洗，接着将n型硅片放置于甲基氯化镁的四氢呋喃溶液中，以在n型硅片表面形成硅-甲基钝化层；(3)硅纳米线/PEDOT:PSS复合膜的制备：在步骤2得到的n型硅片的正面旋涂含有n型硅纳米线的PEDOT:PSS溶液，转速为1000-2000转/分钟，旋涂时间为2-4分钟，然后置于氮气氛围中进行退火处理，退化温度为110-120℃，退火时间为12-20分钟，形成致密的硅纳米线/PEDOT:PSS复合膜；(4)PEDOT:PSS/硫化亚铜纳米颗粒/氧化石墨烯复合导电层的制备：在硅纳米线/PEDOT:PSS复合膜表面旋涂含有硫化亚铜纳米颗粒和氧化石墨烯的PEDOT:PSS溶液；转速为1000-2000转/分钟，旋涂时间为2-4分钟，然后置于氮气氛围中进行退火处理，退化温度为100-120℃，退火时间为5-15分钟，形成致密的PEDOT:PSS/硫化亚铜纳米颗粒/氧化石墨烯复合导电层；(5)背面界面层的制备：在所述n型硅片背面沉积氟化锂薄膜，接着旋涂聚乙烯亚胺溶液，然后置于氮气氛围中进行退火处理，退化温度为100-110℃，退火时间为10-20分钟，以形成氟化锂/聚乙烯亚胺复合背面界面层；(6)正面银栅电极的制备：在真空环境下利用热蒸镀法，在n型硅片正面蒸镀正面银栅电极；(7)背面电极的制备：在真空环境下利用热蒸镀法，在n型硅片背面蒸镀背面铝电极。
作为优选，在所述步骤3中，在所述步骤3中，所述n型硅纳米线的长度为200-400nm，所述n型硅纳米线的直径为10-40nm，所述硅纳米线/PEDOT:PSS复合膜的厚度为50-90纳米。
作为优选，所述含有n型硅纳米线的PEDOT:PSS溶液的制备方法为：采用金属离子辅助化学刻蚀法在n型硅基底的上表面制备n型硅纳米线阵列，然后利用刀片将n型硅纳米线阵列刮入PEDOT:PSS溶液中，以形成所述含有n型硅纳米线的PEDOT:PSS溶液。
作为优选，在所述步骤4中，所述硫化亚铜纳米颗粒的粒径为10-30nm，所述PEDOT:PSS/硫化亚铜纳米颗粒/氧化石墨烯复合导电层的厚度为20-40nm。
作为优选，在所述步骤5中，所述氟化锂薄膜的厚度为0.5-2纳米，旋涂聚乙烯亚胺溶液的转速为1000-3000转/分钟，旋涂时间为2-5分钟，所述聚乙烯亚胺溶液的质量浓度为0.2-0.4mg/ml。
作为优选，所述正面银栅电极的厚度为100-200纳米，所述正面银栅电极中的主栅线的宽度为0.3-0.7mm，副栅线的宽度为0.05mm，相邻副栅线之间的间隔为0.95mm。
作为优选，所述背面铝电极的厚度为200-300nm。
本发明还提供了一种硅-PEDOT:PSS杂化太阳能电池，所述硅-PEDOT:PSS杂化太阳能电池为采用上述方法制备形成的硅-PEDOT:PSS杂化太阳能电池。
本发明与现有技术相比具有下列优点：
(1)本发明通过对n型硅片的表面缺陷态进行最大限度的修复，以得到高质量的异质结，以提高硅-PEDOT:PSS杂化太阳能电池的光电转换效率。
(2)本发明的n型硅片表面具有硅纳米线/PEDOT:PSS复合膜，一部分PEDOT：PSS形成异质结的同时，另一部分PEDOT：PSS与n型硅纳米线形成高质量的异质结，有效提高了硅与PEDOT:PSS的接触面积，同时由于n型硅纳米线的随机排列，可以将电子有效传输至n型硅片，进而提高其光电转换效率。
(3)本发明的硅纳米线/PEDOT:PSS复合膜表面具有PEDOT:PSS/硫化亚铜纳米颗粒/氧化石墨烯复合导电层，通过添加氧化石墨烯和硫化亚铜纳米颗粒，从而提高复合导电层的导电率，并通过优化硫化亚铜纳米颗粒的粒径，使得复合导电层保持优异导电率的同时也具有优异的透光率，而氧化石墨烯的存在提高了PEDOT:PSS的功函，有利于电池中载流子的分离与传输，进而提高太阳能电池的开路电压和填充因子。
(4)本发明在背面铝电极与N型硅片之间设置了氟化锂/聚乙烯亚胺复合背面界面层，氟化锂与聚乙烯亚胺的配合作用，有效降低接触电阻，增强内建电势，改善背接触以抑制电荷复合。
(5)本发明使用简单的、低温的过程制备硅-PEDOT:PSS杂化太阳能电池，有效降低生产成本的同时得到一高光电转换效率的硅-PEDOT:PSS杂化太阳能电池。
附图说明
图1为本发明的硅-PEDOT:PSS杂化太阳能电池的结构示意图；
图中：1、n型硅片；2、硅-甲基钝化层；3、硅纳米线/PEDOT:PSS复合膜；4、PEDOT:PSS/硫化亚铜纳米颗粒/氧化石墨烯复合导电层；5、氟化锂/聚乙烯亚胺复合背面界面层；6、正面银栅电极；7、背面铝电极。
具体实施方式
本发明具体实施例提出的一种硅-PEDOT:PSS杂化太阳能电池的制备方法，包括以下步骤：(1)硅基底的清洗：将n型硅片依次在丙酮、乙醇、去离子水中超声清洗10-30分钟，并用氮气吹干，接着将吹干的n型硅片置于浓硫酸/双氧水混合溶液中，100-120℃下热处理40-60分钟，接着用去离子水冲洗n型硅片，最后利用氢氟酸去除所述n型硅片的表面的自然氧化硅层；(2)硅基底的表面钝化处理：将步骤1得到n型硅片用氮气吹干，然后浸入饱和五氯化磷的氯苯溶液中，在110℃下热处理40-60分钟，接着将n型硅片从饱和五氯化磷的氯苯溶液中取出并依次在氯苯和四氢呋喃中清洗，接着将n型硅片放置于甲基氯化镁的四氢呋喃溶液中，以在n型硅片表面形成硅-甲基钝化层；(3)硅纳米线/PEDOT:PSS复合膜的制备：在步骤2得到的n型硅片的正面旋涂含有n型硅纳米线的PEDOT:PSS溶液，转速为1000-2000转/分钟，旋涂时间为2-4分钟，然后置于氮气氛围中进行退火处理，退化温度为110-120℃，退火时间为12-20分钟，形成致密的硅纳米线/PEDOT:PSS复合膜；(4)PEDOT:PSS/硫化亚铜纳米颗粒/氧化石墨烯复合导电层的制备：在硅纳米线/PEDOT:PSS复合膜表面旋涂含有硫化亚铜纳米颗粒和氧化石墨烯的PEDOT:PSS溶液；转速为1000-2000转/分钟，旋涂时间为2-4分钟，然后置于氮气氛围中进行退火处理，退化温度为100-120℃，退火时间为5-15分钟，形成致密的PEDOT:PSS/硫化亚铜纳米颗粒/氧化石墨烯复合导电层；(5)背面界面层的制备：在所述n型硅片背面沉积氟化锂薄膜，接着旋涂聚乙烯亚胺溶液，然后置于氮气氛围中进行退火处理，退化温度为100-110℃，退火时间为10-20分钟，以形成氟化锂/聚乙烯亚胺复合背面界面层；(6)正面银栅电极的制备：在真空环境下利用热蒸镀法，在n型硅片正面蒸镀正面银栅电极；(7)背面电极的制备：在真空环境下利用热蒸镀法，在n型硅片背面蒸镀背面铝电极。
其中，在所述步骤3中，在所述步骤3中，所述n型硅纳米线的长度为200-400nm，所述n型硅纳米线的直径为10-40nm，所述硅纳米线/PEDOT:PSS复合膜的厚度为50-90纳米。所述含有n型硅纳米线的PEDOT:PSS溶液的制备方法为：采用金属离子辅助化学刻蚀法在n型硅基底的上表面制备n型硅纳米线阵列，然后利用刀片将n型硅纳米线阵列刮入PEDOT:PSS溶液中，以形成所述含有n型硅纳米线的PEDOT:PSS溶液。在所述步骤4中，所述硫化亚铜纳米颗粒的粒径为10-30nm，所述PEDOT:PSS/硫化亚铜纳米颗粒/氧化石墨烯复合导电层的厚度为20-40nm。在所述步骤5中，所述氟化锂薄膜的厚度为0.5-2纳米，旋涂聚乙烯亚胺溶液的转速为1000-3000转/分钟，旋涂时间为2-5分钟，所述聚乙烯亚胺溶液的质量浓度为0.2-0.4mg/ml。所述正面银栅电极的厚度为100-200纳米，所述正面银栅电极中的主栅线的宽度为0.3-0.7mm，副栅线的宽度为0.05mm，相邻副栅线之间的间隔为0.95mm。所述背面铝电极的厚度为200-300nm。
如图1所示，本发明根据上述方法制备的硅-PEDOT:PSS杂化太阳能电池，所述硅-PEDOT:PSS杂化太阳能电池从下至上背面铝电极7、氟化锂/聚乙烯亚胺复合背面界面层5、n型硅片1、硅-甲基钝化层2、硅纳米线/PEDOT:PSS复合膜3、PEDOT:PSS/硫化亚铜纳米颗粒/氧化石墨烯复合导电层4以及正面银栅电极6。
实施例1：
一种硅-PEDOT:PSS杂化太阳能电池的制备方法，包括以下步骤：(1)硅基底的清洗：将n型硅片依次在丙酮、乙醇、去离子水中超声清洗20分钟，并用氮气吹干，接着将吹干的n型硅片置于浓硫酸/双氧水混合溶液中，110℃下热处理50分钟，接着用去离子水冲洗n型硅片，最后利用氢氟酸去除所述n型硅片的表面的自然氧化硅层；(2)硅基底的表面钝化处理：将步骤1得到n型硅片用氮气吹干，然后浸入饱和五氯化磷的氯苯溶液中，在110℃下热处理60分钟，接着将n型硅片从饱和五氯化磷的氯苯溶液中取出并依次在氯苯和四氢呋喃中清洗，接着将n型硅片放置于甲基氯化镁的四氢呋喃溶液中，以在n型硅片表面形成硅-甲基钝化层；(3)硅纳米线/PEDOT:PSS复合膜的制备：在步骤2得到的n型硅片的正面旋涂含有n型硅纳米线的PEDOT:PSS溶液，转速为2000转/分钟，旋涂时间为2分钟，然后置于氮气氛围中进行退火处理，退化温度为115℃，退火时间为15分钟，形成致密的硅纳米线/PEDOT:PSS复合膜；(4)PEDOT:PSS/硫化亚铜纳米颗粒/氧化石墨烯复合导电层的制备：在硅纳米线/PEDOT:PSS复合膜表面旋涂含有硫化亚铜纳米颗粒和氧化石墨烯的PEDOT:PSS溶液；转速为1500转/分钟，旋涂时间为3分钟，然后置于氮气氛围中进行退火处理，退化温度为110℃，退火时间为12分钟，形成致密的PEDOT:PSS/硫化亚铜纳米颗粒/氧化石墨烯复合导电层；(5)背面界面层的制备：在所述n型硅片背面沉积氟化锂薄膜，接着旋涂聚乙烯亚胺溶液，然后置于氮气氛围中进行退火处理，退化温度为110℃，退火时间为15分钟，以形成氟化锂/聚乙烯亚胺复合背面界面层；(6)正面银栅电极的制备：在真空环境下利用热蒸镀法，在n型硅片正面蒸镀正面银栅电极；(7)背面电极的制备：在真空环境下利用热蒸镀法，在n型硅片背面蒸镀背面铝电极。
其中，在所述步骤3中，在所述步骤3中，所述n型硅纳米线的长度为300nm，所述n型硅纳米线的直径为20nm，所述硅纳米线/PEDOT:PSS复合膜的厚度为60纳米。所述含有n型硅纳米线的PEDOT:PSS溶液的制备方法为：采用金属离子辅助化学刻蚀法在n型硅基底的上表面制备n型硅纳米线阵列，然后利用刀片将n型硅纳米线阵列刮入PEDOT:PSS溶液中，以形成所述含有n型硅纳米线的PEDOT:PSS溶液。在所述步骤4中，所述硫化亚铜纳米颗粒的粒径为20nm，所述PEDOT:PSS/硫化亚铜纳米颗粒/氧化石墨烯复合导电层的厚度为30nm。在所述步骤5中，所述氟化锂薄膜的厚度为1纳米，旋涂聚乙烯亚胺溶液的转速为2000转/分钟，旋涂时间为4分钟，所述聚乙烯亚胺溶液的质量浓度为0.2mg/ml。所述正面银栅电极的厚度为120纳米，所述正面银栅电极中的主栅线的宽度为0.5mm，副栅线的宽度为0.05mm，相邻副栅线之间的间隔为0.95mm。所述背面铝电极的厚度为260nm。
将上述方法制备的硅-PEDOT:PSS杂化太阳能电池，通过各层之间的配合作用，该硅-PEDOT:PSS杂化太阳能电池的开路电压为0.59V，短路电流为29.5mA/cm2，填充因子为0.75，光电转换效率为13.1％。
以上所述是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明的保护范围。
Claims (8)
1.一种硅-PEDOT:PSS杂化太阳能电池的制备方法，其特征在于：包括以下步骤：
（1）硅基底的清洗：将n型硅片依次在丙酮、乙醇、去离子水中超声清洗10-30分钟，并用氮气吹干，接着将吹干的n型硅片置于浓硫酸/双氧水混合溶液中，100-120℃下热处理40-60分钟，接着用去离子水冲洗n型硅片，最后利用氢氟酸去除所述n型硅片的表面的自然氧化硅层；
（2）硅基底的表面钝化处理：将步骤1得到n型硅片用氮气吹干，然后浸入饱和五氯化磷的氯苯溶液中，在110℃下热处理40-60分钟，接着将n型硅片从饱和五氯化磷的氯苯溶液中取出并依次在氯苯和四氢呋喃中清洗，接着将n型硅片放置于甲基氯化镁的四氢呋喃溶液中，以在n型硅片表面形成硅-甲基钝化层；
（3）硅纳米线/PEDOT:PSS复合膜的制备：在步骤2得到的n型硅片的正面旋涂含有n型硅纳米线的PEDOT:PSS溶液，转速为1000-2000转/分钟，旋涂时间为2-4分钟，然后置于氮气氛围中进行退火处理，退化温度为110-120℃，退火时间为12-20分钟，形成致密的硅纳米线/PEDOT:PSS复合膜；
（4）PEDOT:PSS/硫化亚铜纳米颗粒/氧化石墨烯复合导电层的制备：在硅纳米线/PEDOT:PSS复合膜表面旋涂含有硫化亚铜纳米颗粒和氧化石墨烯的PEDOT:PSS溶液；转速为1000-2000转/分钟，旋涂时间为2-4分钟，然后置于氮气氛围中进行退火处理，退化温度为100-120℃，退火时间为5-15分钟，形成致密的PEDOT:PSS/硫化亚铜纳米颗粒/氧化石墨烯复合导电层；
（5）背面界面层的制备：在所述n型硅片背面沉积氟化锂薄膜，接着旋涂聚乙烯亚胺溶液，然后置于氮气氛围中进行退火处理，退化温度为100-110℃，退火时间为10-20分钟，以形成氟化锂/聚乙烯亚胺复合背面界面层；
（6）正面银栅电极的制备：在真空环境下利用热蒸镀法，在n型硅片正面蒸镀正面银栅电极；
（7）背面电极的制备：在真空环境下利用热蒸镀法，在n型硅片背面蒸镀背面铝电极。
2.根据权利要求1所述的硅-PEDOT:PSS杂化太阳能电池的制备方法，其特征在于：在所述步骤3中，所述n型硅纳米线的长度为200-400 nm，所述n型硅纳米线的直径为10-40nm，所述硅纳米线/PEDOT:PSS复合膜的厚度为50-90纳米。
3.根据权利要求2所述的硅-PEDOT:PSS杂化太阳能电池的制备方法，其特征在于：所述含有n型硅纳米线的PEDOT:PSS溶液的制备方法为：采用金属离子辅助化学刻蚀法在n型硅基底的上表面制备n型硅纳米线阵列，然后利用刀片将n型硅纳米线阵列刮入PEDOT:PSS溶液中，以形成所述含有n型硅纳米线的PEDOT:PSS溶液。
4.根据权利要求1所述的硅-PEDOT:PSS杂化太阳能电池的制备方法，其特征在于：在所述步骤4中，所述硫化亚铜纳米颗粒的粒径为10-30nm，所述PEDOT:PSS/硫化亚铜纳米颗粒/氧化石墨烯复合导电层的厚度为20-40nm。
5.根据权利要求1所述的硅-PEDOT:PSS杂化太阳能电池的制备方法，其特征在于：在所述步骤5中，所述氟化锂薄膜的厚度为0.5-2纳米，旋涂聚乙烯亚胺溶液的转速为1000-3000转/分钟，旋涂时间为2-5分钟，所述聚乙烯亚胺溶液的质量浓度为0.2-0.4 mg/ml。
6.根据权利要求1所述的硅-PEDOT:PSS杂化太阳能电池的制备方法，其特征在于：所述正面银栅电极的厚度为100-200纳米，所述正面银栅电极中的主栅线的宽度为0.3-0.7mm，副栅线的宽度为0.05mm，相邻副栅线之间的间隔为0.95mm。
7.根据权利要求1所述的硅-PEDOT:PSS杂化太阳能电池的制备方法，其特征在于：所述背面铝电极的厚度为200-300nm。
8.一种硅-PEDOT:PSS杂化太阳能电池，其特征在于，所述硅-PEDOT:PSS杂化太阳能电池为采用权利要求1-7任一项所述的方法制备形成的硅-PEDOT:PSS杂化太阳能电池。
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