Visualization of Surface Charge Carrier Diffusion Lengths in Different Perovskite Crystal Orientations Using 4D Electron Imaging

Abstract Understanding charge carrier dynamics on the surface of materials at the nanometer and femtosecond scales is one of the key elements to optimizing the performance of light‐conversion devices, including solar cells. Unfortunately, most of the pump‐probe characterization techniques are surface‐insensitive and obtain information from the bulk due to the large penetration depth of the pulses. However, ultrafast scanning electron microscopy (USEM) is superior in visualizing carrier dynamics at the surface with high spatial‐temporal resolution. Here, the authors successfully used USEM to uncover the tremendous effect of surface orientations and termination on the charge carrier of MAPbI₃ perovskite single crystals. Time‐resolved secondary electrons snapshots and density functional theory calculations clearly demonstrate that charge carrier diffusion, surface trap density, surface work function, and carrier concentration are strongly facet‐dependent. The results display a diffusion length of 22 micrometers within 6.0 nanoseconds along (001) orientation. While (100) facet forms defect states that prevent carrier diffusion and shows an increase in the surface work function leading to dark contrast and fast charge carrier recombination. These findings provide a new key component to optimizing the surface of perovskites, thus paving the way for even more efficient and stable solar‐cell devices based on perovskite single crystals.