Acid‐Base Complexation Induced Dipole Engineering for Durable Inverted Perovskite Photovoltaics

ABSTRACT Thermally unstable buried interfaces hinder the commercialization of inverted perovskite solar cells (PSCs). Although self‐assembled monolayers (SAMs) serve as promising hole‐selective contacts, their inadequate coverage and weak thermal anchoring cause energy loss and structural degradation. Here, we introduce a dipole‐engineering strategy by incorporating 4‐aminopyridine (4‐AP) into the Me‐4PACz matrix to form a robust electrostatic complex via acid‐base complexation. This approach suppresses aggregation, ensures uniform coverage, enables a vertical molecular orientation, and enhances the interfacial dipole moment from 1.64 to 8.34 Debye, thereby improving hole extraction. The resulting small‐area (0.09 cm 2 ) inverted PSC achieves a power conversion efficiency (PCE) of 27.06% and an open‐circuit voltage ( V OC ) of 1.194 V. This approach also enables large‐area modules (655.2 cm 2 ) with an efficiency of 20.3% (certified 20.11%) and a fill factor of 79.9%. Additionally, the devices demonstrate exceptional thermal stability, retaining 90.1% and 89.3% of their initial PCE after 1000 h at 85°C and 200 thermal cycles, respectively. This work provides a generalizable pathway toward durable and high‐performance perovskite photovoltaics by leveraging supramolecular interactions for interfacial dipole engineering.