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

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 Pb²⁺ 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.