<i>Meso</i> ‐Crowned Porphyrin as a Dual Cavity Hybrid Macrocycle for Improving the Efficiency and Stability of Perovskite Solar Cells

ABSTRACT Perovskite solar cells (PSCs) have achieved remarkable power conversion efficiencies (PCEs) and cost‐effective fabrication processes. However, defects in the bulk and interfaces of perovskite materials, as well as Li + migration (especially in n–i–p regular architecture), which are used to enhance the conductivity and hole mobility of spiro‐OMeTAD, can significantly impact device performance and stability. Herein, we report a rationally designed meso ‐crowned porphyrin derivative ( [12]‐C‐4POR ) featuring dual macrocyclic binding sites, i.e., a porphyrin core for undercoordinated Pb 2+ and a crown ether unit selective for Li + to suppress surface defects and mitigate lithium‐ion migration simultaneously. The incorporation of [12]‐C‐4POR into perovskite films significantly reduced the trap‐state density and suppressed non‐radiative recombination, leading to improved charge‐carrier dynamics. Devices treated with [12]‐C‐4POR delivered a champion PCE of 23.14%, surpassing the control device (21.6%), along with enhanced open‐circuit voltage (V OC ) and fill factor (FF). More importantly, the passivated devices retained ∼95% of their initial PCE after 800 h of continuous operation, compared to ∼55% for the control. This study demonstrates a dual‐site host–guest passivation strategy as an effective route to improve both efficiency and operational stability of PSCs.