Interlocked Self‐Assembled Monolayers Enabled by Porphyrin Derivative for Efficient and Stable Organic Solar Cells

ABSTRACT Although the prevailing self‐assembly monolayers (SAMs) have been proved effective in improving device performance, e.g., power conversion efficiency (PCE) exceeding 20% in organic photovoltaics (OPVs), their unstable chemical structures and/or insufficient anode coverage lead to severe efficacy issues. Herein, we introduce a fluorinated porphyrin derivative with amine groups (F‐Por) as to control the packing of SAMs via interlocking the adjacent molecules to form laterally constrained and vertically ordered topology. Consequently, the device efficiency, operation stability, and environmental adaptivity are simultaneously reinforced, due to the improved work function, molecular arrangement, and charge transport of SAMs. In particular, the optimized devices comprising composite SAM and F‐Por delivers a PCE of 20.25% and a T ₈₀ lifetime of 585 h under continuous operation. Therefore, this work provides a valuable design paradigm for the development of high‐performance, operational stable and environmentally adaptive organic optoelectronic devices toward practical applications.