Abstract
Polycrystalline perovskite solar cells show high power conversion efficiencies despite the presence of grain boundaries (GBs). The benign nature of GBs on the electronic properties and structural stability in metal-halide perovskites contradicts their propensity for point defect formation, a controversy that is far from being understood. In this work, we combine ab initio molecular dynamics and density functional theory calculations on the sigma 5[130] GB of cesium lead iodide, CsPbI3, to shed light on the structural and electronic properties of such GBs. Our results present the first evidence of structural healing of GBs driven by the facile migration of iodine ions, resulting in stabilized GB structures with reduced hole trap states and shallow electron trap states by strain-induced Pb-Pb dimers. Drift-diffusion simulations reveal that shallow electron trap states in GB mainly lower open-circuit voltage by enhanced non-radiative recombination. Finally, we observe the spontaneous formation of iodine Frenkel defects with reduced formation energies compared to the perovskite bulk. Overall, our study reveals a controversy of GBs showing a moderate impact on the electronic properties by structural healing but a detrimental impact on the point defect densities, both being connected to the facile migration of iodine ions in GBs.