Mechanism of Hot‐Carrier Photoluminescence in Sn‐Based Perovskites

Abstract Metal halide perovskites have shown exceptionally slow hot‐carrier cooling, which has been attributed to various physical mechanisms without reaching a consensus. Here, experiment and theory are combined to unveil the carrier cooling process in formamidinium (FA) and caesium (Cs) tin triiodide thin films. Through impulsive vibrational spectroscopy and molecular dynamics, much shorter phonon dephasing times of the hybrid perovskite, which accounts for the larger blueshift in the photoluminescence seen at high excitation density for FASnI ₃ compared to CsSnI ₃ is reported. Density functional theory investigations reveal that the largest contribution to the blueshift is accounted by a giant, dynamic band‐filling effect in Sn‐based perovskites, which in turn can explain the cooling disparity with the Pb‐based counterparts. Several years after the first experimental observations, here a deeper understanding of the cooling mechanism of these materials is provided. Design principles for hot‐carrier materials, which may be useful for future implementations of hot‐carrier solar cells are further provided.