The Effect of Ionic Composition on Acoustic Phonon Speeds in Hybrid Perovskites from Brillouin Spectroscopy and Density Functional Theory

Abstract

Hybrid organic-inorganic perovskites (HOIPs) have recently emerged as highly promising solution-processable materials for photovoltaic (PV) and other optoelectronic devices. HOIPs represent a broad family of materials with properties highly tuneable by the ions that make up the perovskite structure as well as their multiple combinations. Interestingly, recent high-efficiency PV devices using HOIPs with substantially improved long-term stability have used combinations of different ionic compositions. The structural dynamics of these systems are unique for semiconducting materials and are currently argued to be central to HOIPs stability and charge-transport properties. Here, we studied the impact of ionic composition on phonon speeds of HOIPs from Brillouin spectroscopy experiments and density functional theory calculations for FAPbBr${}_3$, MAPbBr${}_3$, MAPbCl${}_3$, and the mixed halide MAPbBr${}_{1.25}$Cl${}_{1.75}$. Our results show that the acoustic phonon speeds can be strongly modified by ionic composition, which we explain by analysing the lead-halide sublattice in detail. The vibrational properties of HOIPs are therefore tuneable by using targeted ionic compositions in the perovskite structure. This tuning can be rationalized with non-trivial effects, for example, considering the influence of the shape and dipole moment of organic cations. This has an important implication to further improvements in the stability and charge-transport properties of these systems.

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Cited by in corpus (5)

• Electronic Defects in Metal Oxide Photocatalysts
• Structure and Binding in Halide Perovskites: Analysis of Static and Dynamic Effects from Dispersion-Corrected Density Functional Theory
• A-site Cation Influence on the Conduction Band of Lead Bromide Perovskites
• Static and Dynamic Disorder in Formamidinium Lead Bromide Single Crystals
• A perspective on inelastic light scattering spectroscopy for probing transport of collective acoustic excitations