Ionic Bonding Without Directionality Facilitates Efficient Interfacial Bridging for Perovskite Solar Cells

Abstract Interface passivation through Lewis acid–base coordinate chemistry in perovskite solar cells (PSCs) is a universal strategy to reduce interface defects and hinder ion migration. However, the formation of coordinate covalent bonding demands strict directional alignment of coordinating atoms. Undoubtedly, this limits the selected range of the interface passivation molecules, because a successful molecular bridge between charge transport layer and perovskite bottom interface needs a well‐placed molecular orientation. In this study, it is discovered that potassium ions can migrate to the hollow sites of multiple iodine ions from perovskite to form K‐I x ionic bonding, and the ionic bonds without directionality can support molecular backbone rotation to facilitate polar sites (carboxyl groups) chelating Pb at the bottom perovskite interface, finally forming a closed‐loop bonding structure. The synergy of coordinate and ionic bonding significantly reduces interface defects, changes electric field distribution, and immobilizes iodine at the perovskite bottom interface, resulting in eliminating the hysteresis effect and enhancing the performance of PSCs. As a result, the corresponding devices achieve a high efficiency exceeding 24.5% (0.09 cm 2 ), and a mini‐module with 21% efficiency (12.4 cm 2 ). These findings provide guidelines for designing molecular bridging strategies at the buried interface of PSCs.