Polaron Vibronic Progression Shapes the Optical Response of 2D Perovskites

Abstract The optical response of 2D layered perovskites is composed of multiple equally‐spaced spectral features, often interpreted as phonon replicas, separated by an energy Δ ≃ 12 − 40 meV, depending upon the compound. Here the authors show that the characteristic energy spacing, seen in both absorption and emission, is correlated with a substantial scattering response above ≃ 200 cm −1 (≃ 25 meV) observed in resonant Raman. This peculiar high‐frequency signal, which dominates both Stokes and anti‐Stokes regions of the scattering spectra, possesses the characteristic spectral fingerprints of polarons. Notably, its spectral position is shifted away from the Rayleigh line, with a tail on the high energy side. The internal structure of the polaron consists of a series of equidistant signals separated by 25–32 cm −1 (3–4 meV), depending upon the compound, forming a polaron vibronic progression. The observed progression is characterized by a large Huang‐Rhys factor ( S > 6) for all of the 2D layered perovskites investigated here, indicative of a strong charge carrier – lattice coupling. The polaron binding energy spans a range ≃ 20–35 meV, which is corroborated by the temperature‐dependent Raman scattering data. The investigation provides a complete understanding of the optical response of 2D layered perovskites via the direct observation of polaron vibronic progression. The understanding of polaronic effects in perovskites is essential, as it directly influences the suitability of these materials for future opto‐electronic applications.