Thiocarbonyl‐Based Hole Transport Materials with Enhanced Defect Passivation Ability for Efficient and Stable Perovskite Solar Cells

Abstract Organic hole transporting materials (HTMs) are extensively studied in perovskite solar cells (PSCs). The HTMs directly contact the underlying perovskite material, and they play additional roles apart from hole transporting. Developing organic HTMs with defect passivation function has been proved to be an efficient strategy to construct efficient and stable PSCs. In this work, new organic molecules with thiocarbonyl (C═S) and carbonyl (C═O) functional groups are synthesized and applied as HTMs (named FN‐S and FN‐O). FN‐S with C═S can be facilely obtained from FN‐O containing C═O. Notably, the C═S in FN‐S results in superior defect passivation ability compared to FN‐O. Moreover, FN‐S exhibits excellent hole extraction/transport capability. Conventional PSCs using FN‐S as HTM show an impressive power conversion efficiency (PCE) of 23.25%, with excellent long‐term stability and operational stability. This work indicates that simply converting C═O to C═S is an efficient way to improve the device performance by strengthening the defect passivation functionality.