LAUSR

Fluorinated spacer cations in quasi-2D (Q-2D) perovskites have recently been demonstrated to improve the Q-2D perovskite solar cell (PSC) performance. However, the underlying mechanism of fluorination of organic cations on the improvement is still unclear. Here, using fluorinated benzylammonium (named F-BZA) as a spacer cation in Q-2D Ruddlesden-Popper (RP) perovskites, we deeply investigate the effect of fluorination of organic cations on perovskite crystallization and intermolecular interactions for improving the charge transport and device performance. It is found that fluorination of spacer cations can slow down the crystallization rate of perovskites, resulting in vertically aligned large grains. Moreover, the interaction between the adjacent spacer cations is further enhanced, constructing a new faster charge-transport channel with a lifetime of 77 ps. Accordingly, the carrier mobility is improved by an order of magnitude and a power conversion efficiency (PCE) of 16.82% is achieved in much more stable F-BZA-based Q-2D RP PSCs, 35% higher than that of BZA-based devices (12.39%). Our results elucidate the mechanism and its importance of fluorinating spacer cations for high-performance Q-2D PSC development.