Bifunctional OMe‐PEAI Synchronizes Carrier Extraction Dynamics and Loss Mitigation toward High‐Performance Perovskite Solar Cells and Modules

Comprehensive Summary Perovskite solar cells (pero‐SCs) face inherent challenges due to the presence of numerous defects on the solution‐processed perovskite surfaces. Conventional passivation strategies cannot address its detrimental effects on interfacial charge extraction efficiency and long‐term device stability. In this study, we introduce methoxy‐functionalized derivative‐PEAI (OMe‐PEAI) as a bifunctional interfacial mediator for the post‐treatment of perovskite surfaces in n‐i‐p structured organic‐inorganic hybrid pero‐SCs. The methoxy group in OMe‐PEAI, acting as a Lewis base with available lone‐pair electrons, effectively interacts with uncoordinated Pb 2+ to mitigate interfacial defects. More importantly, the strong dipole moment inherent to OMe‐PEAI induces a reduction in perovskite work function, achieving optimized energy level alignment at the perovskite/Spiro‐OMeTAD interface and enabling strong interfacial electronic coupling. These synergistic effects collectively enhance interfacial charge carrier extraction while suppressing non‐radiative recombination losses. The optimized small‐area devices (0.062 cm 2 ) demonstrated a high‐power conversion efficiency (PCE) of 25.38% with minimized voltage deficits while corresponding perovskite modules (13.93 cm 2 ) achieved a notable PCE of 21.57%. Furthermore, OMe‐PEAI‐modified devices exhibited remarkable stabilities, retaining 89% and 92% of initial efficiencies after thermal stress testing (85 °C for 512 h) and maximum power point tracking (500 h), respectively.