Multi‐Site Intermolecular Interaction for In Situ Formation of Vertically Orientated 2D Passivation Layer in Highly Efficient Perovskite Solar Cells

Abstract Surface passivation via 2D perovskite is critical for perovskite solar cells (PSCs) to achieve remarkable performances, in which the applied spacer cations play an important role on structural templating. However, the random orientation of 2D perovskite always hinder the carrier transport. Herein, multiple nitrogen sites containing organic spacer molecule (1H‐Pyrazole‐1‐carboxamidine hydrochloride, PAH) is introduced to form 2D passivation layer on the surface of formamidinium based (FAPbI₃) perovskite. Deriving from the interactions between PAH and PbI₂, the defects of FAPbI₃ perovskite are effectively passivated. Interestingly, due to the multiple‐site interactions, the 2D nanosheets are found to grow perpendicularly to the substrate for promotion of charge transfer. Therefore, an impressive power conversion efficiency of 24.6% and outstanding long‐term stability are achieved for the 2D/3D perovskite devices. The findings further provide a perspective in structure design of novel organic halide salts for the fabrication of efficient and stable PSCs.