Molecular Origin of the Asymmetric Photoluminescence Spectra of CsPbBr3 at Low Temperature

CsPbBr3 has received wide attention due to its superior emission yield and better thermal stability compared to other organic-inorganic lead halide perovskites. In this study, through an interplay of theory and experiments, we investigate the molecular origin of the asymmetric low-temperature photoluminescence spectra of CsPbBr3. We conclude that the origin of this phenomenon lies in a local dipole moment (and the induced Stark effect) due to the preferential localization of Cs+ in either of two off-center positions of the empty space between the surrounding PbBr6 octahedra. With increasing temperature, Cs+ ions are gradually occupying positions closer and closer to the center of the cavities. The gradual loss of ordering in the Cs+ position with increasing temperature is the driving force for the formation of tetragonal-like arrangements within the orthorhombic lattice.

Automated summary

This study investigates the molecular origin of the asymmetric low-temperature photoluminescence spectra of CsPbBr3 through a combination of theory and experiments, revealing that the local dipole moment of Cs+ in off-center positions between PbBr6 octahedra contributes to this phenomenon. The gradual loss of ordering in Cs+ position with increasing temperature drives the formation of tetragonal-like arrangements within the orthorhombic lattice.