Surface Defect Dynamics in Organic–Inorganic Hybrid Perovskites: From Mechanism to Interfacial Properties

Organic-inorganic hybrid perovskites (OHPs) have garnered much attention among the photovoltaic and light-emitting diode research community due to their excellent optoelectronic properties and low-cost fabrication. Defects in perovskites have been proposed to affect device efficiency and stability and to have a potential role in enabling ion migration. In this study, the dynamic behavior and electronic properties of intrinsic defects in CH₃NH₃PbBr₃ (MAPbBr₃) were explored at the atomic scale. We use scanning tunneling microscopy to show unambiguously the occurrence of vacancy-assisted transport of individual ions as well as the existence of vacancy defect clusters at the OHP surface. We combine these observations with density functional theory (DFT) calculations to identify the mechanisms for this ion motion and show that ion transport energy barriers, as well as transport mechanisms, at the surface depend on crystal direction. DFT calculations also reveal that vacancy defect clusters can significantly modify the local work function of the perovskite surface, which is then expected to alter interfacial charge transport in a device. Our work provides a microscopic insight into the mechanism of ion migration in OHPs and also delivers the useful information for device improvement from the perspective of interface engineering.