Quasi-2D layered halide perovskites (quasi-2DLPs) have emerged as promising materials for photovoltaic (PV) applications owing to their advantageous bandgap for absorbing visible light and the improved stability they enable. Their charge transport mechanism is heavily influenced by the grain orientation of their crystals as well as their nanostructures, such as grain boundaries (GBs) and edge states─the formation of which is inevitable in polycrystalline quasi-2DLP thin films. Despite their importance, the impact of these features on charge transport remains unexplored. In this study, we conduct a detailed investigation on polycrystalline quasi-2DLP thin films and devices, carefully analyzing how grain orientation and nanostructures influence charge transport. Employing nondestructive atomic force microscopy (AFM) topography, along with transient absorption spectroscopy (TAS) and grazing-incidence wide-angle X-ray scattering (GIWAXS), we obtained significant insights regarding the phase purity, crystallographic information, and morphologies of these films. Moreover, our systematic investigation using AFM-based techniques, including Kelvin probe force microscopy (KPFM) and conductive AFM (c-AFM), elucidates the roles played by GBs and edge states in shaping charge transport behavior. In particular, the local band structure along the GBs and edge states within both vertical and parallel grains was found to selectively repel electrons and holes, thus facilitating charge carrier separation. These findings provide perspectives for the development of high-performance quasi-2DLP PV devices and highlight potential approaches that can leverage the intrinsic properties of quasi-2DLPs to advance the performance of perovskite solar cells.
Keywords: Charge Transport; Crystal Orientation; Nanoscale Imaging; Quasi-2D Perovskites; Solar Cells.