Intermolecular π–π Conjugation Self‐Assembly to Stabilize Surface Passivation of Highly Efficient Perovskite Solar Cells

Surface passivation is an effective approach to eliminate defects and thus to achieve efficient perovskite solar cells, while the stability of the passivation effect is a new concern for device stability engineering. Herein, tribenzylphosphine oxide (TBPO) is introduced to stably passivate the perovskite surface. A high efficiency exceeding 22%, with steady‐state efficiency of 21.6%, is achieved, which is among the highest performances for TiO2 planar cells, and the hysteresis is significantly suppressed. Further density functional theory (DFT) calculation reveals that the surface molecule superstructure induced by TBPO intermolecular π–π conjugation, such as the periodic interconnected structure, results in a high stability of TBPO–perovskite coordination and passivation. The passivated cell exhibits significantly improved stability, with sustaining 92% of initial efficiency after 250 h maximum‐power‐point tracking. Therefore, the construction of a stabilized surface passivation in this work represents great progress in the stability engineering of perovskite solar cells. Sufficient and stable surface passivation of perovskite solar cells is realized using a novel tribenzylphosphine oxide molecule, with high cell efficiency of >22% and excellent operation stability being obtained. These achievements benefit from the strong molecule–perovskite Coulomb interaction and the formation of superstructure self‐assembly on the perovskite surface, enabled by intermolecular π–π conjugation.