Exciton-Selective Phonon Coupling in a Lead Halide Perovskite

TL;DR

This study uncovers distinct exciton-phonon coupling channels in lead halide perovskites, demonstrating how different excitons interact with specific phonons and how these interactions evolve with temperature, impacting optoelectronic properties.

Contribution

It provides the first direct spectroscopic evidence of simultaneous, exciton-specific phonon coupling in a single lead halide perovskite material, using advanced spectroscopy and machine learning.

Findings

Distinct phonon replica spacings for high-energy and Rashba excitons (~9 meV and ~6 meV)

Replica features broaden and merge with increasing temperature

Room temperature coupling dominated by longitudinal optical phonons

Abstract

Exciton-phonon interactions govern the optical response of semiconductors, yet disentangling multiple coupling channels in lead halide perovskites remains challenging. We investigate CsPbBr3 microcrystals using photoluminescence, Raman and reflectance spectroscopy at low temperature, revealing the simultaneous presence of high-energy and Rashba excitons, each accompanied by distinct phonon replica series. High-energy exciton replicas are uniquely spaced by approximately 9 meV, whereas Rashba exciton replicas exhibit a characteristic approximately 6 meV spacing, indicating the specificity of the exciton-phonon coupling. Unsupervised machine learning applied to a large low-temperature photoluminescence dataset reveals these replica features are prevalent. With increasing temperature, replica features broaden and merge, evolving into a dominant longitudinal optical phonon coupling regime at room temperature. This work establishes direct spectroscopic evidence for concurrent, exciton-specific phonon coupling within a single material, offering new pathways to engineer light-matter interactions for optoelectronic and phonon-photon-based quantum device applications.