Atomic Structure and Dynamics of Organic–Inorganic Hybrid Perovskite Formamidinium Lead Iodide

The atomic dynamic behaviors of formamidinium lead iodide [HC(NH₂)₂PbI₃] are critical for understanding and improving photovoltaic performances. However, they remain unclear. Here, we investigate the structural phase transitions and the reorientation dynamics of the formamidinium cation [HC(NH₂)₂⁺, FA⁺] of FAPbI₃ using neutron scattering techniques. Two structural phase transitions occur with decreasing temperature, from cubic to tetragonal phase at 285 K and then to another tetragonal at 140 K, accompanied by gradually frozen reorientation of FA cations. The nearly isotropic reorientation in the cubic phase is suppressed to reorientation motions involving a two-fold (C₂) rotation along the N···N axis and a four-fold (C₄) rotation along the C-H axis in the tetragonal phase, and eventually to local disordered motion as a partial C₄ along the C-H axis in another tetragonal phase, thereby indicating an intimate interplay between lattice and orientation degrees of freedom in the hybrid perovskite materials. The present complete atomic structure and dynamics provide a solid standing point to understand and then improve photovoltaic properties of organic-inorganic hybrid perovskites in the future.