Atomic Imaging of the Pb Precipitation in Lead-Halide Perovskites

The lead iodide (PbI2) in lead-halide perovskite (LHP) is both a positive additive for material properties and a site for the formation of device defects. Therefore, atomic-level detection of PbI2 and its derived Pb structures are crucial for understanding the performance and stability of the LHP material. In this work, the atomic imaging of the LHP, PbI2, and Pb lattices is achieved using low-dose integrated differential phase contrast (iDPC) scanning transmission electron microscopy (STEM). Combining it with the traditional high-angle annular dark field (HAADF)-STEM, the Pb precipitation in different LHPs (CsPbI3, CsPbBr3, and FAPbI3) and under different conditions (light, air, and heat) can be investigated in real space. Then, the features of Pb precipitation (positions and sizes) are visually revealed under different conditions and the stabilities of different LHPs. Meanwhile, the pathway of Pb precipitation is directly imaged and confirmed by the iDPC-STEM during an in situ heating process, supporting the detailed mechanism of Pb precipitation. These results provide the visual evidence for analyzing atomic Pb precipitation in LHPs, which helps better understand the structure-property relation induced by Pb impurity. Combining different imaging modes in electron microscopy, the bulk and local features of the mixed structures are investigated during the Pb precipitation in different lead-halide perovskites. Different effects of external conditions on this process are revealed by in situ and ex situ methods. These results can help us better understand the structure-property relation to improve the stability of perovskite materials and devices. image