Surface Characterization of the Solution‐Processed Organic–Inorganic Hybrid Perovskite Thin Films

Abstract The surface properties of organic–inorganic hybrid perovskites can strongly affect the efficiency and stability of corresponding devices. Even though different surface passivation methods are developed, the microscopic structures of solution‐processed perovskite film surfaces are not systematically studied. This study uses low‐temperature scanning tunneling microscopy to study the organic–inorganic hybrid perovskite thin films, MA_0.4FA_0.6PbI₃ and MAPbI₃, synthesized by the spin‐coating method. Flat surface structures, atomic steps, and crystal grain boundaries are resolved at an atomic resolution. The surface imperfections are also characterized, as well as the dominant defects. Simulations on different types of iodine vacancy configurations are performed by density functional theory calculations. In addition, it is observed that the surface iodine lattice structure is unstable during scanning. Tip scanning can also cause the vertical migration of surface iodine ions. The measurements provide the direct visualizations of the surface imperfections of the solution‐processed perovskite films. They are essential for understanding the surface‐related optoelectronic effects and rationally designing more efficient surface passivation methods.