Synergistic Buried and Bulk Engineering by Pre‐Crystallized 2D Seeds Enables High Performance Inverted Perovskite Solar Cells

ABSTRACT The pursuit of high‐performance perovskite photovoltaics necessitates precise control over crystal growth. While surface defects have been extensively investigated, the regulation of buried interface and crystal orientation in three‐dimensional (3D) perovskites is equally critical for high‐performance inverted perovskite solar cells (PSCs). Herein, we report a synergistic strategy that enhances buried interface contact and directs bulk crystallization by incorporating DFBP 2 PbI 4 two‐dimensional (2D) perovskite crystal seeds. It is revealed that the molecularly tailored 2D seeds not only promote bottom‐up epitaxial growth of perovskite films with a favored crystallization direction but also form hydrogen bonds with the self‐assembled monolayer (SAM), thereby accelerating interfacial carrier transfer. Consequently, the optimized inverted PSCs achieve a champion power conversion efficiency of 25.40% and exhibit remarkable operational stability, retaining 91.7% of their initial efficiency after 800 h of continuous operation at the maximum power point tracking. Our findings underscore the importance of co‐optimizing buried interfaces and bulk crystallographic order to advance the performance of PSCs.