Atomic-scale imaging of CH3NH3PbI3 structure and its decomposition pathway

• Published in: Nature communications 2021-09, Vol.12 (1), p.5516-5516, Article 5516
• Main Authors: Chen, Shulin, Wu, Changwei, Han, Bo, Liu, Zhetong, Mi, Zhou, Hao, Weizhong, Zhao, Jinjin, Wang, Xiao, Zhang, Qing, Liu, Kaihui, Qi, Junlei, Cao, Jian, Feng, Jicai, Yu, Dapeng, Li, Jiangyu, Gao, Peng
• Format: Article
• Language: English
• Subjects: 119/118; 147/135; 147/137; 147/143; 639/301/299/946; 639/4077/909/4101/4096; Ammonia; Atomic structure; Collapse; Decomposition; Failure mechanisms; Humanities and Social Sciences; Imaging; Imaging techniques; Irradiation; multidisciplinary; Optimization; Perovskite structure; Perovskites; Photoelectric effect; Photoelectric properties; Photoelectricity; Radiation; Science; Science (multidisciplinary); Structural stability
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-021-25832-9

Understanding the atomic structure and structural instability of organic-inorganic hybrid perovskites is the key to appreciate their remarkable photoelectric properties and understand failure mechanism. Here, using low-dose imaging technique by direct-detection electron-counting camera in a transmission electron microscope, we investigate the atomic structure and decomposition pathway of CH 3 NH 3 PbI 3 (MAPbI 3 ) at the atomic scale. We successfully image the atomic structure of perovskite in real space under ultra-low electron dose condition, and observe a two-step decomposition process, i.e., initial loss of MA + followed by the collapse of perovskite structure into 6H-PbI 2 with their critical threshold doses also determined. Interestingly, an intermediate phase (MA 0.5 PbI 3 ) with locally ordered vacancies can robustly exist before perovskite collapses, enlightening strategies for prevention and recovery of perovskite structure during the degradation. Associated with the structure evolution, the bandgap gradually increases from ~1.6 eV to ~2.1 eV. In addition, it is found that C-N bonds can be readily destroyed under irradiation, releasing NH 3 and HI and leaving hydrocarbons. These findings enhance our understanding of the photoelectric properties and failure mechanism of MAPbI 3 , providing potential strategies into material optimization. The knowledge of atomic structure and structural instability of hybrid perovskites is crucial to understand their photoelectric properties and failure mechanism. Here, the authors utilise low-dose TEM imaging technique to investigate the atomic structure and decomposition pathway of MAPbI 3 at the atomic scale.