Phonon Interactions in Metal Halide Perovskites elucidated by Raman Scattering

TL;DR

This paper reviews how Raman scattering reveals phonon interactions in metal halide perovskites, emphasizing the effects of lattice dynamics, disorder, and the origin of the central Raman peak.

Contribution

It provides a comprehensive analysis of Raman signatures related to phonon interactions and disorder effects in metal halide perovskites, clarifying the origin of the central peak.

Findings

Disorder-induced second-order acoustic-phonon Raman scattering explains the central peak.

Raman signatures vary depending on hydrogen bonding or steric hindrance.

The unifying picture aids in interpreting perovskite Raman spectra.

Abstract

There is a growing consensus that the exceptional optoelectronic properties of metal halide perovskites (MHPs) are largely due to the peculiar interplay between the inorganic cage lattice, composed of a labile network of corner-sharing metal halide octahedra, and the A-site cationic sublattice. This interaction significantly affects the vibrational spectrum of MHPs (phonon frequencies, linewidths, and lifetimes), resulting from the effects of lattice potential anharmonicity and/or static/dynamic disorder. Raman scattering is a suitable technique to probe phonon interactions in solids, allowing for the in-situ characterization of chemical environments, revealing the nature of lattice vibrations. In this perspective, the available experimental evidence of the aforementioned interplay will be reviewed with special emphasis on understanding Raman signatures depending on whether the coupling is principally mediated by hydrogen bonding or steric hindrance. The controversy about the origin of a strong Raman background, steeply rising towards zero Raman shift and called central peak, will be specifically addressed. This background signal, which is typically observed in the temperature range of stability of cubic and tetragonal phases when the A-site cation dynamics unfold, will be shown to be mostly due to disorder-induced second-order acoustic-phonon Raman scattering. This interpretation receives support from other semiconductor systems with nanoscale structural disorder, where the central Raman peak arises either from the vertical misalignment of Ge quantum dots in multi-stack heterostructures or from the interface roughness exhibited by short-period GaAs/AlAs superlattices. In this way, a unifying picture of phonon interactions in MHPs and how they impact different Raman processes is provided, which is key to interpreting their Raman spectra.