Decoding Polymeric Additive‐Driven Self‐Healing Processes in Perovskite Solar Cells from Chemical and Physical Bonding Perspectives

Abstract This review addresses the self‐healing effects in perovskite solar cells (PSCs), emphasizing the significance of chemical and physical bonding as core mechanisms. Polymeric additives play a vital role in inducing self‐healing phenomena along with the intrinsic properties of perovskite materials, both of which are discussed herein. As a relatively underexplored area, the self‐healing effect induced by polymeric additives in PSCs is reviewed from a chemical perspective. The chemical bonds involved in self‐healing include isocyanate, disulfide, and carboxylic acid groups. The physical bonds related to self‐healing effects are primarily hydrogen bonding and chelation. Self‐healing in flexible perovskite devices extends their lifespan and improves their mechanical robustness against environmental and mechanical stressors. This discussion delves into the initiation methods for self‐healing, the conditions required, and the recovery‐rate profiles. This review not only catalogs various approaches to self‐healing, but also considers the fundamental limitations and potential of this phenomenon in PSCs. In addition, insights and an outlook on self‐healing in perovskite‐based optoelectronics are provided, offering guidance for future research and applications.