Electronic structures, spectroscopic properties, and thermodynamic characterization of alkali- and transition-metals incorporated perovskite crystals by first-principles calculation

Influence of alkali metals (Na, K) and transition metals (Co, Cr, Cu, and Y) incorporated into perovskite crystal on the electronic structures, spectroscopic and magnetic properties, and thermodynamic properties was investigated by first-principles calculation using density functional theory. Incorporation of 12.5% Na or K into the perovskite crystal generated 3s, 3p, 4s, and 4p orbitals of Na or K above the conduction band, which promoted the charge transfer from alkali metal to the conduction band, accelerating the electron diffusion related to the photovoltaic properties. For the Cr, Cu and Y-incorporated FAPbI₃ perovskite crystals, the electron density distribution of d-p hybrid orbital on the transition metal and iodine halogen ligand were delocalized at the frontier orbital.