Modulating the Dipole Moment of Secondary Ammonium Spacers for Efficient 2D Ruddlesden‐Popper Perovskite Solar Cells

Abstract Layered two‐dimensional (2D) perovskites are emerging as promising optoelectronic materials owing to their excellent environmental stability. Regulating the dipole moment of organic spacers has the potential to reduce the exciton binding energy ( E b ) of 2D perovskites and improve their photovoltaic performance. Here, we developed two azetidine‐based secondary ammonium spacers with different electron‐withdrawing groups, namely 3‐hydroxyazatidine (3‐OHAz) and 3,3‐difluoroazetidine (3,3‐DFAz) spacers, for 2D Ruddlesden‐Popper (RP) perovskites. It was found that the large dipole moment of the fluorinated dipole spacer could effectively enhance the interaction between organic spacers and inorganic layers, leading to improved charge dissociation in 2D RP perovskite. In contrast to 3‐OHAz spacer, the 2D perovskite using 3,3‐DFAz as spacer also shows improved film quality, optimized energy level alignment, and reduced exciton binding energy. As a result, the 2D perovskite ( n =4) device based on 3,3‐DFAz yields an outstanding efficiency of 19.28 %, surpassing that of the 3‐OHAz‐Pb device (PCE=11.35 %). The efficiency was further improved to 19.85 % when using mixed A‐site cation of MA 0.95 FA 0.05 . This work provides an effective strategy for modulating the energy level alignment and reducing the E b by regulating the dipole moment of organic spacers, ultimately enabling the development of high‐performance 2D perovskite solar cells.