Phase Distribution and Carrier Dynamics in Multiple-Ring Aromatic Spacer-Based Two-Dimensional Ruddlesden–Popper Perovskite Solar Cells

Two-dimensional (2D) perovskites with natural multi-quantum-well structure have been reported to offer better stability compared to 3D perovskites. However, the understanding of the exciton separation and transport mechanism in 2D perovskites and developing more efficient organic spacers remain considerable challenges, as the 2D perovskites exhibit large exciton binding energy due to quantum confinement. Here, a class of multiple-ring aromatic ammoniums, 1-naphthalenemethylammonium (NpMA) and 9-anthracenemethylammonium (AnMA), was developed as spacers for 2D Ruddlesden–Popper (RP) perovskite solar cells (PSCs). In addition to significantly enhanced stability, the device based on (NpMA)2(MA)n−1PbnI3n+1 (average n = 4) exhibits a champion efficiency of 17.25% and a high open-circuit voltage of 1.24 V. The outstanding photovoltaic performance could be ascribed to the ultrafast exciton migration (within 7 ps) from 2D phases to 3D-like phases, which were confirmed by charge carrier dynamics results, leading to efficient exciton separation, charge transportation, and collection. This work facilitates understanding the working mechanism of 2D PSCs in-depth and offers an efficient way to further boost their efficiency and stability by developing multiple-ring aromatic spacers.