CN113421934B - 一种钙钛矿吸光层材料的制备方法 - Google Patents

一种钙钛矿吸光层材料的制备方法 Download PDF

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CN113421934B
CN113421934B CN202110663796.9A CN202110663796A CN113421934B CN 113421934 B CN113421934 B CN 113421934B CN 202110663796 A CN202110663796 A CN 202110663796A CN 113421934 B CN113421934 B CN 113421934B
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宗迎夏
刘玉梅
宗成中
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Qingdao University of Science and Technology
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Abstract

本发明提供一种钙钛矿吸光层材料及方法，其包括CsSnI3钙钛矿材料，并且还包含有增强材料，增强材料为石墨烯和SnF2的掺杂物。在制备方法中，在石墨烯片上通过浸渍法负载得到有SnF2的石墨烯片；通过真空热蒸发沉积的方式制得负载CsI薄膜的二次基片，然后以CsI薄膜为基础再次沉积得到SnI2薄膜负载的结构；以得到具有掺杂SnF2石墨烯片的CsSnI3钙钛矿薄膜材料通过石墨烯和SnF2的掺杂物的加入，使得CsSnI3钙钛矿材料转换效率得到了明显的提升，并且这种转换效率高于单独的CsSnI3钙钛矿材料和掺杂SnF2的CsSnI3钙钛矿材料；另外，这种材料中不使用对于环境具有破坏作用的铅元素，极大地提高了这种材料的安全性和环境保护作用，具有很好的应用价值。

Description

一种钙钛矿吸光层材料的制备方法
技术领域
本发明涉及一种钙钛矿吸光层材料，具体涉及一种CsSnI3钙钛矿材料。
背景技术
为了应对能源危机，太阳能电池在近些年来得到了广泛和深度的发展，在一些生活和工业领域，已经逐渐地开始普遍地、规模化地使用太阳能电池。在太阳能电池技术的发展中，其吸光层材料属于研究的热点之一，目前，太阳能电池的吸光层材料的理论基础主要为钙钛矿材料，这种钙钛矿材料的分子式为ABX3型的结构，其中A可以为CH3NH3 +，B可以为Pb2 +，X为卤素离子。然而，这种基于铅元素（Pb）的钙钛矿材料虽然吸光性能稳定，但是其具有较强的环境破坏力，在本领域中一直寻求替代铅元素的吸光层材料。
目前在现有技术中出现了CsSnI3钙钛矿的材料，这种材料完全地避免了对于铅元素的依赖，具有很好地环境友好性，为本领域的新兴热点材料之一。然而，这种材料也存在一个较为突出的问题，Sn空缺产生高浓度的受主缺陷使得材料表现为强的p型电导，这样深能级缺陷态形成电子和空穴的复合中心，导致这种材料的工作转换效率不高。经过研究后表明，添加了Sn元素进入到钙钛矿材料之后则能够提高吸光层的转换效率。基于此，当把氟化亚锡加入到钙钛矿材料之中进行改良，其吸光层性能确实有提升，但是提升的幅度有限，其远低于传统的铅类的钙钛矿吸光层材料的电池性能。因此，这种材料的吸光层材料仍然有进一步提升的空间。
发明内容
为解决上述技术中存在的问题，本发明提供一种环保友好性且吸光层性能得到保证的钙钛矿材料和方法。
本发明提供的一种钙钛矿吸光层材料，其包括CsSnI3钙钛矿材料，并且还包含有增强材料，所述增强材料为石墨烯和SnF2的掺杂物。
上述方案的有益效果为：通过石墨烯和SnF2的掺杂物的加入，使得CsSnI3钙钛矿材料转换效率得到了明显的提升，并且这种转换效率高于单独的CsSnI3钙钛矿材料和掺杂SnF2的CsSnI3钙钛矿材料；另外，这种材料中不使用对于环境具有破坏作用的铅元素，极大地提高了这种材料的安全性和环境保护作用，具有很好的应用价值。
一个优选的方案是，所述石墨烯和SnF2的掺杂物中的SnF2与CsSnI3的摩尔比为0.1:1至0.3：1。经过在不同含量的SnF2的使用情况下对于吸光层的转换效率进行测试，发现在达到0.1:1以上的时候则会使得转换效率得到明显提升，而对于超过0.3：1的成分，则转换效率不会有显著变化，因此在这个范围内的实施例是比较合适的。
一个优选的方案是，所述石墨烯和SnF2的掺杂物中的SnF2与CsSnI3的摩尔比为0.2：1。经过测试，发现这个摩尔比的时候吸光层的转换效率达到了最优化状态。
一个优选的方案是，包括两层薄膜结构，下层薄膜结构为掺杂SnF2的石墨烯片，上层薄膜结构为CsSnI3薄膜。
本发明提供的钙钛矿吸光层材料的制备方法，其包括下面的步骤：
S1：获得石墨烯片，在所述石墨烯片上通过浸渍法负载得到有SnF2的石墨烯片；
S2：以掺杂有SnF2的石墨烯片为基片，通过真空热蒸发沉积的方式制得负载CsI薄膜的二次基片，然后以所述CsI薄膜为基础再次沉积得到SnI2薄膜负载的结构；
S3：迅速在退火炉中以保护气体的氛围下在180℃至320℃范围内的不同温度下进行退火步骤，随后自然冷却，以得到具有掺杂SnF2石墨烯片的CsSnI3钙钛矿薄膜材料。
具体实施方式
本发明提供的一种钙钛矿吸光层材料，其包括CsSnI3钙钛矿材料，并且还包含有增强材料，所述增强材料为石墨烯和SnF2的掺杂物。
本发明通过石墨烯和SnF2的掺杂物的加入，使得CsSnI3钙钛矿材料转换效率得到了明显的提升，并且这种转换效率高于单独的CsSnI3钙钛矿材料和掺杂SnF2的CsSnI3钙钛矿材料；另外，这种材料中不使用对于环境具有破坏作用的铅元素，极大地提高了这种材料的安全性和环境保护作用，具有很好的应用价值。
所述石墨烯和SnF2的掺杂物中的SnF2与CsSnI3的摩尔比为0.1:1至0.3：1。经过在不同含量的SnF2的使用情况下对于吸光层的转换效率进行测试，发现在达到0.1:1以上的时候则会使得转换效率得到明显提升，而对于超过0.3：1的成分，则转换效率不会有显著变化，因此在这个范围内的实施例是比较合适的。所述石墨烯和SnF2的掺杂物中的SnF2与CsSnI3的摩尔比为0.2：1。经过测试，发现这个摩尔比的时候吸光层的转换效率达到了最优化状态。
在具体的实验对照中，分别测试了CsSnI3钙钛矿材料（简称为CsSnI3材料）、掺杂SnF2的CsSnI3钙钛矿材料（简称为SnF2-CsSnI3材料）、石墨烯和SnF2的掺杂物的CsSnI3钙钛矿材料（简称为C-SnF2-CsSnI3材料）。具体见下面的表1。
表1：不同材料类型的电转换效率的性能测试。
组别 材料类型 变化量 转换效率
1 CsSnI<sub>3</sub>材料 - 5%以下
2 SnF<sub>2</sub>-CsSnI<sub>3</sub>材料 SnF<sub>2</sub>摩尔比10% 14%
3 SnF<sub>2</sub>-CsSnI<sub>3</sub>材料 SnF<sub>2</sub>摩尔比20% 18%
4 C-SnF<sub>2</sub>-CsSnI<sub>3</sub>材料 SnF<sub>2</sub>摩尔比5% 6%
5 C-SnF<sub>2</sub>-CsSnI<sub>3</sub>材料 SnF<sub>2</sub>摩尔比10% 17%
6 C-SnF<sub>2</sub>-CsSnI<sub>3</sub>材料 SnF<sub>2</sub>摩尔比15% 20%
7 C-SnF<sub>2</sub>-CsSnI<sub>3</sub>材料 SnF<sub>2</sub>摩尔比20% 25%
8 C-SnF<sub>2</sub>-CsSnI<sub>3</sub>材料 SnF<sub>2</sub>摩尔比25% 22%
9 C-SnF<sub>2</sub>-CsSnI<sub>3</sub>材料 SnF<sub>2</sub>摩尔比30% 21%
本发明提供的钙钛矿吸光层材料包括两层薄膜结构，下层薄膜结构为掺杂SnF2的石墨烯片，上层薄膜结构为CsSnI3薄膜。
本发明提供的钙钛矿吸光层材料的制备方法，其包括下面的步骤：
S1：获得石墨烯片，在所述石墨烯片上通过浸渍法负载得到有SnF2的石墨烯片；另外还可以通过现有的其它的方式把SnF2掺杂到石墨烯片上。
S2：以掺杂有SnF2的石墨烯片为基片，通过真空热蒸发沉积的方式制得负载CsI薄膜的二次基片，然后以所述CsI薄膜为基础再次沉积得到SnI2薄膜负载的结构；
S3：迅速在退火炉中以保护气体的氛围下在180℃至320℃范围内的不同温度下进行退火步骤，随后自然冷却，以得到具有掺杂SnF2石墨烯片的CsSnI3钙钛矿薄膜材料。以上制备方法为优选实施例。

Claims (3)

1.钙钛矿吸光层材料的制备方法，其特征在于，包括下面的步骤：
S1：获得石墨烯片，在所述石墨烯片上通过浸渍法负载得到有SnF2的石墨烯片；
S2：以掺杂有SnF2的石墨烯片为基片，通过真空热蒸发沉积的方式制得负载CsI薄膜的二次基片，然后以所述CsI薄膜为基础再次沉积得到SnI2薄膜负载的结构；
S3：迅速在退火炉中以保护气体的氛围下在180℃至320℃范围内的温度下进行退火步骤，随后自然冷却，以得到具有掺杂SnF2石墨烯片的CsSnI3钙钛矿薄膜材料。
2.根据权利要求1所述的钙钛矿吸光层材料的制备方法，其特征在于，具有掺杂SnF2石墨烯片的CsSnI3钙钛矿薄膜材料中的SnF2与CsSnI3的摩尔比为0.1:1至0.3：1。
3.根据权利要求2所述的钙钛矿吸光层材料的制备方法，其特征在于，具有掺杂SnF2石墨烯片的CsSnI3钙钛矿薄膜材料中的SnF2与CsSnI3的摩尔比为0.2：1。
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