Direct evidence of weakly dispersed and strongly anharmonic optical phonons in hybrid perovskites

Abstract

Hybrid organolead perovskites (HOP) have started to establish themselves in the field of photovoltaics, mainly due to their great optoelectronic properties and steadily improving solar cell efficiency. Study of the lattice dynamics is key in understanding the electron-phonon interactions at play, responsible for such properties. Here, we investigate, via neutron and Raman spectroscopies, the optical phonon spectrum of four different HOP single crystals: MAPbBr₃, FAPbBr₃, MAPbI₃, and α-FAPbI₃. Low temperature spectra reveal weakly dispersive optical phonons, at energies as low as 2-5 meV, which seem to be the origin of the limit of the charge carriers mobilities in these materials. The temperature dependence of our neutron spectra shows as well a significant anharmonic behaviour, resulting in optical phonon overdamping at temperatures as low as 80 K, questionning the validity of the quasi-particle picture for the low energy optical modes at room temperature where the solar cells operate.

Interest in hybrid organolead perovskites is driven by their promising optoelectronic properties and potential application as photovoltaics. In this work, insight into the electron-phonon interactions influencing these properties is gained from neutron and Raman spectroscopic measurements.