Chen Shulin, Zhang Ying, Zhao Jinjin, Mi Zhou, Zhang Jingmin, Cao Jian, Feng Jicai, Zhang Guanglei, Qi Junlei, Li Jiangyu, Gao Peng
Electron Microscopy Laboratory, School of Physics, Peking University, Beijing 100871, China; State Key Laboratory of Advanced Welding and Joining, Harbin Institute of Technology, Harbin 150001, China.
School of Materials Science and Engineering, School of Mechanical Engineering, Shijiazhuang Tiedao University, Shijiazhuang 050043, China.
Sci Bull (Beijing). 2020 Oct 15;65(19):1643-1649. doi: 10.1016/j.scib.2020.05.020. Epub 2020 May 23.
Organic-inorganic hybrid perovskites (OIHPs) have attracted extensive research interest as a promising candidate for efficient and inexpensive solar cells. Transmission electron microscopy (TEM) characterizations that can benefit the fundamental understanding and the degradation mechanism are widely used for these materials. However, their sensitivity to the electron beam illumination and hence structural instabilities usually prevent us from obtaining the intrinsic information or even lead to significant artifacts. Here, we systematically investigate the structural degradation behaviors under different experimental factors to reveal the optimized conditions for TEM characterizations of OIHPs by using low-dose electron diffraction and imaging techniques. We find that a low temperature (-180 °C) does not slow down the beam damage but instead induces a rapid amorphization for OIHPs. Moreover, a less severe damage is observed at a higher accelerating voltage. The beam-sensitivity is found to be facet-dependent that a (1 0 0) exposed CHNHPbI (MAPbI) surface is more stable than a (0 0 1) surface. With these guidance, we successfully acquire the atomic structure of pristine MAPbI and identify the characterization window that is very narrow. These findings are helpful to guide future electron microscopy characterizations of these beam-sensitive materials, which are also useful for finding strategies to improve the stability and performance of the perovskite solar cells.
有机-无机杂化钙钛矿(OIHPs)作为高效且廉价太阳能电池的一个有前景的候选材料,已引起了广泛的研究兴趣。能够有助于深入理解其基本性质和降解机制的透射电子显微镜(TEM)表征方法被广泛应用于这些材料。然而,它们对电子束照射的敏感性以及由此导致的结构不稳定性,通常使我们无法获得其内在信息,甚至会产生明显的假象。在此,我们通过使用低剂量电子衍射和成像技术,系统地研究了不同实验因素下的结构降解行为,以揭示OIHPs进行TEM表征的优化条件。我们发现低温(-180°C)并不会减缓束流损伤,反而会导致OIHPs快速非晶化。此外,在较高加速电压下观察到的损伤较轻。发现束流敏感性与晶面有关,即暴露的(1 0 0)面的CHNHPbI(MAPbI)表面比(0 0 1)表面更稳定。基于这些指导,我们成功获得了原始MAPbI的原子结构,并确定了非常狭窄的表征窗口。这些发现有助于指导未来对这些束流敏感材料的电子显微镜表征,也有助于找到提高钙钛矿太阳能电池稳定性和性能的策略。