Cation dynamics and structural stabilization in formamidinium lead iodide perovskites

The vibrational dynamics of pure and methylammonium-doped formamidinium lead iodide perovskites (FAPbI3) has been investigated by high-resolution neutron spectroscopy. For the first time, we provide an exhaustive and accurate analysis of the cation vibrations and underlying local structure around the organic moiety in these materials using first-principles electronic-structure calculations validated by the neutron data. Inelastic neutron scattering experiments on FAPbI3 provide direct evidence of the formation of a low-temperature orientational glass, unveiling the physicochemical origin of phase metastability in the tetragonal structure. Further analysis of these data provides a suitable starting point to explore and understand the stabilization of the perovskite framework via doping with small amounts of organic cations. In particular, we find that the hydrogen-bonding interactions around the formamidinium cations are strengthened as a result of cage deformation. This synergistic effect across perovskite cages is accompanied by a concomitant weakening of the methylammonium interactions with the surrounding framework.
K.D. and F.F.A. gratefully acknowledge financial support from the Gipuzkoako Foru Aldundia under grant no. 2020-CIEN-000009-01. This work has been supported by PL-Grid Infrastructure and the PROMETHEUS facility. M.K. is grateful for financial support from the Swedish Research Council (2016-06258).