Bidirectional Photoinduced Carrier Transfer in Fluorinated Quasi-2D Perovskites Governing Enhanced Photocurrent Generation

Quasi-two-dimensional (quasi-2D) metal halide perovskites exhibit rich phase heterogeneity that profoundly influences light-matter interactions and charge transport. However, the fundamental mechanisms governing carrier transfer across distinct phases remain poorly understood. Here, we demonstrate effective electron-hole separation in fluorinated multilayered quasi-2D perovskite films nominally prepared for three layers, using femtosecond transient absorption spectroscopy. The films are revealed to comprise a heterogeneous phase distribution (with 1, 2, 3 layers and bulk) naturally stacked along the growth direction. Our ultraviolet photoelectron spectroscopy (UPS) measurements, show the type-two band alignment between the small-n (layer number) phases and the bulk. This alignment drives charge separation via both direct and sequential carrier transfer mechanisms, whereby electrons preferentially migrate into the bulk domains while holes accumulate in the small-n layers, extending even to single layer phase-a process only rarely observed in previous studies. The nearly symmetric transfer times of electrons and holes yield an efficient and balanced spatial separation of carriers. Global target analysis employing a carrier transfer model quantitatively reproduces the spectral evolution, providing a rigorous validation of the mechanism. Nonetheless, we found photocurrent enhancement in the diode devices of this quasi-2D perovskite as a consequence of the efficient transfer of photocarriers in the opposite directions. This work delivers a comprehensive picture of interphase charge transfer in fluorinated quasi-2D perovskites and highlights strategies to engineer directional separation pathways for high-performance photovoltaic, optoelectronic, and quantum devices.