Nano-size nature of the α-FAPbI_3 by means of large-scale ab initio simulations

Formamidinium-lead-iodide (FAPbI_3) has established itself as the state of the art for high solar-energy conversion efficiency in perovskite-based solar cells. At room temperature, FAPbI_3 has a peculiar crystal structure with tetragonal symmetry where the PbI_6 framework is distorted from the perfect cubic structure, while the FA molecules are randomly rotated. This is well known experimentally, but the theory is still deficient in describing FAPbI_3 with appropriate models in which the system size is adequately taken into account. Using ab initio molecular dynamics at 300 K and first-principle calculations, we prove that, in order to obtain a proper description of the system, three factors must be satisfied simultaneously: the band gap, the minimization of structural distortion, and the zeroing out of the dipole moment. We show that the net dipole moment zeroes out as the system size increases due to PbI6 octahedra distortions rather than FA rotations. We also show that the band gap oscillations in temperature are correlated to octahedra tilting. The optimum between simulations and experimental properties indicates that FAPbI_3 is properly described by a system size approaching the nano-scale.