Octahedral Distortions Generate a Thermally Activated Phonon-Assisted Radiative Recombination Pathway in Cubic...

Exciton-phonon interactions elucidate structure-function relationships that aid in the control of color purity and carrier diffusion, which is necessary for the performance-driven design of solid-state optical emitters. Temperature-dependent steady-state photoluminescence (PL) and time-resolved PL (TRPL) reveal that thermally activated exciton-phonon interactions originate from structural distortions related to vibrations in cubic CsPbBr₃ perovskite quantum dots (PQDs) at room temperature. Exciton-phonon interactions cause performance-degrading PL line width broadening and slower electron-hole recombination. Structural distortions in cubic PQDs at room temperature exist as the bending and stretching of the PbBr₆ octahedra subunit. The PbBr₆ octahedral distortions cause symmetry breaking, resulting in thermally activated longitudinal optical (LO) phonon coupling to the photoexcited electron-hole pair that manifests as inhomogeneous PL line width broadening. At cryogenic temperatures, the line width broadening is minimized due to a decrease in phonon-assisted recombination through shallow traps. A fundamental understanding of these intrinsic exciton-phonon interactions gives insight into the polymorphic nature of the cubic phase and the origins of performance degradation in PQD optical emitters.