Atomic Structure and Electrical Activity of Grain Boundaries and Ruddlesden–Popper Faults in Cesium Lead Bromide Perovskite

To evaluate the role of planar defects in lead-halide perovskites-cheap, versatile semiconducting materials-it is critical to examine their structure, including defects, at the atomic scale and develop a detailed understanding of their impact on electronic properties. In this study, postsynthesis nanocrystal fusion, aberration-corrected scanning transmission electron microscopy, and first-principles calculations are combined to study the nature of different planar defects formed in CsPbBr₃ nanocrystals. Two types of prevalent planar defects from atomic resolution imaging are observed: previously unreported Br-rich [001](210)∑5 grain boundaries (GBs) and Ruddlesden-Popper (RP) planar faults. The first-principles calculations reveal that neither of these planar faults induce deep defect levels, but their Br-deficient counterparts do. It is found that the ∑5 GB repels electrons and attracts holes, similar to an n-p-n junction, and the RP planar defects repel both electrons and holes, similar to a semiconductor-insulator-semiconductor junction. Finally, the potential applications of these findings and their implications to understand the planar defects in organic-inorganic lead-halide perovskites that have led to solar cells with extremely high photoconversion efficiencies are discussed.