Homologous Fluorination Enables Asymmetric Dynamic Interfacial Coupling for Efficient and Sustainable Blade‐Coated Perovskite Solar Cells

Self‐assembled monolayers (SAMs) are indispensable hole‐transport interfaces in inverted perovskite solar cells (PSCs), yet conventional co‐assembly strategies based on symmetric strong interactions often suffer from excessive aggregation, limited adaptability, and insufficient interfacial robustness. Here, we developed a homologous fluorination‐enabled asymmetric interfacial interaction strategy by integrating fluorinated SAM molecule [2‐(3,6‐difluoro‐9 H ‐carbazol‐9‐yl)ethyl]phosphonic acid (F‐2PACz) with perfluorooctanoic acid (PFOA) as a dynamic co‐assembly modulator. Unlike conventional symmetric systems, PFOA formed weak fluorine‐mediated interactions with F‐2PACz to regulate SAM assembly and improve interfacial coverage, while establishing stronger hydrogen‐bonding and coordination interactions with the perovskite layer for defect suppression and Pb 2 + immobilization. This asymmetric interaction hierarchy optimized buried interface quality, promoted charge extraction, and enhanced device stability. Consequently, blade‐coated inverted PSCs achieved a champion efficiency of 24.72% and retain 97.7% of their initial efficiency after 1140 h maximum power point tracking under ISOS‐L‐1I conditions. The strategy was compatible with perovskites of different bandgaps, enabling four‐terminal all‐perovskite tandems with 27.10% efficiency. Moreover, the fluorinated interface achieved a lead sequestration efficiency of 97.4%, mitigating lead leakage. This work establishes asymmetric fluorine‐mediated interfacial coupling as a molecular design strategy for efficient, stable, and sustainable inverted PSCs.