Nano-size nature of the $\alpha$-FAPbI$_3$ by means of large-scale ab initio simulations

TL;DR

This study uses large-scale ab initio simulations to reveal that the nano-scale structure of $ ext{FAPbI}_3$ is crucial for accurately capturing its electronic and structural properties relevant to solar cell efficiency.

Contribution

The paper demonstrates that a nano-scale system size is essential for correctly modeling $ ext{FAPbI}_3$, highlighting the importance of system size in ab initio simulations of perovskites.

Findings

Net dipole moment cancels out with increasing system size due to octahedral distortions.

Band gap oscillations are linked to octahedral tilting.

Nano-scale models best match experimental properties.

Abstract

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.