Peptide‐Based Ammonium Halide with Inhibited Deprotonation Enabling Effective Interfacial Engineering for Highly Efficient and Stable FAPbI₃ Perovskite Solar Cells

Abstract Ammonium iodides are intensively investigated as effective interfacial passivation agents in perovskite solar cells (PSCs) while facing a major challenge of their high reactivity with perovskites that undermines the operational stability of the PSCs. Exemplified by involving rationally designed/selected peptide into the widely adopted phenethylammonium iodide (PEAI), the present work demonstrates that the bespoke peptide‐PEAI can effectively inhibit the deprotonation of ammonium iodides and thus hinder the formation of 2D perovskite, facilitating the stability enhancement in perovskite films by multi hydrogen bonding. The additional lone pair electrons provided by peptide molecules can also enhance the passivation ability of the modified layer. Attributed to the stable co‐modifier peptide‐PEAI, the small‐area FAPbI₃‐based PSCs yield a high efficiency of 25.02% with robust light and thermal stabilities. Moreover, the peptide‐PEAI‐based minimodules with an efficiency of 19.06% for a total area of 36 cm² manifested the great application potential of this co‐modification strategy in the perovskite photovoltaics.