Unraveling the Ordered Phase of the Quintessential Hybrid Perovskite MAPbI3─Thermophysics to the Rescue

J Phys Chem Lett. 2022 Sep 15;13(36):8422-8428. doi: 10.1021/acs.jpclett.2c02208. Epub 2022 Sep 7.

Abstract

Hybrid perovskites continue to attract an enormous amount of attention, yet a robust microscopic picture of their different phases as well as the extent and nature of the disorder present remains elusive. Using specific-heat data along with high-resolution inelastic neutron scattering and ab initio modeling, we address this ongoing challenge for the case of the ordered phase of the quintessential hybrid-perovskite MAPbI3. At low temperatures, the specific heat of MAPbI3 reveals strong deviations from the Debye limit, a common feature of pure hybrid perovskites and their mixtures. Our thermophysical analysis demonstrates that the (otherwise ordered) structure around the organic moiety is characterized by a substantial lowering of the local symmetry relative to what can be inferred from crystallographic studies. The physical origin of the observed thermophysical anomalies is unequivocally linked to excitations of sub-terahertz optical phonons responsible for translational-librational distortions of the octahedral units.