Interface Chelation Induced by Pyridine‐Based Polymer for Efficient and Durable Air‐Processed Perovskite Solar Cells

Polymer doping is a significant approach to precisely control nucleation and crystal growth of perovskites and enhance electronic quality in perovskite solar cells (PSC) prepared in air. Here, a brand‐new self‐healing polysiloxane (SHP) with dynamic 2,6‐pyridinedicarboxamide (PDCA) coordination units and plenty of hydrogen bonds was designed and incorporated into perovskite films. PDCA units, showing strong intermolecular Pb2+‐Namido, I−‐Npyridyl, and Pb2+‐Oamido coordination interactions, were expected to enhance crystallinity and passivate the grain boundary. In addition, abundant hydrogen bonds in SHP afforded the self‐healing of cracks at grain boundaries for fatigue PSCs. Significantly, the doped device demonstrated a champion efficiency of 19.50 % with inconspicuous hysteresis, almost rivaling those achieved in control atmosphere. This strategy of heterocyclic‐based macromolecular doping in PSCs will pave a way for realizing efficient and durable crystalline semiconductors. The perovskite solar cell (PSC) has emerged rapidly in the field of flexible photovoltaics. A self‐healing polysiloxane (SHP) polymer with pyridine‐based heterocyclic structures and plenty of dynamic hydrogen bonds was utilized to passivate and heal the cracks at grain boundaries. A champion efficiency of 19.50 % was achieved and the PSC with SHP recovered 80 % of original efficiency after self‐healing for 2 h in ambient atmosphere.