S_N2−Reaction− Bonding‐Heterointerface Strengthens Buried Adhesion and Orientation for Advanced Perovskite Solar Cells

Traditionally weak buried interaction without customized chemical bonding always goes against the formation of high--quality perovskite film that highly determines the efficiency and stability of perovskite solar cells. To address this issue, herein, we propose a bimolecular nucleophilic substitution reaction (S_N2) driving strategy to idealize the robust buried interface by simultaneously decorating underlying substrate and functionalizing [PbX₆]^4- octahedral framework with iodoacetamide and thiol molecules, respectively. Theoretical and experimental results demonstrate that a strong S_N2 reaction between exposed halogen and thiol group in two molecules occurs, which not only benefits the reinforcement of buried adhesion, but also triggers target-point-oriented crystallization, synergistically upgrading the upper perovskite film quality and accelerating interfacial charge extraction-transfer behavior. Benefiting from the suppressed nonradiative recombination, as a result, an all-air-processed carbon-based all-inorganic CsPbI₂Br device achieves an enhanced efficiency of 15.14 %, more importantly, with significantly prolonged long-term stability under harsh conditions. This unique reaction-driven buried interface provides a new path for manipulating perovskite growth and obtaining advanced perovskite photovoltaics.