Excited-state charge polarization and electronic structure of mixed-cation halide perovskites: the role of mixed inorganic–organic cations in CsFAPbI(3)

Mixed-cation perovskite materials have shown great potential for sunlight harvesting and have surpassed unmixed perovskite materials in solar cell efficiency and stability. The role of mixed monovalent cations in the enhanced optoelectronic properties and excited state response, however, are still elusive from a theoretical perspective. Herein, through time dependent density functional theory calculations of mixed cation perovskites, we report the electronic structure of Cs formamidinium (FA) mixed cationic lead iodide (Cs(0.17)FA(0.87)PbI(3)) in comparison to the corresponding single monovalent cation hybrid perovskite. The results show that the Cs(0.17)FA(0.87)PbI(3) and FAPbI(3) had negligible differences in the optical band gap, and partial and total density of states in comparison to a single cation perovskite, while the effective mass of carriers, the local atomic density of states, the directional transport, and the structural distortions were significantly different. A lattice-distortion-induced asymmetry in the ground-state charge density is found, and originates from the co-location of caesium atoms in the lattice and signifies the effect on the charge density upon cation mixing and corresponding symmetry breaking. The excited-state charge response and induced polarizabilities are quantified, and discussed in terms of their importance for effective light absorption, charge separation, and final solar cell performance. We also quantify the impact of such polarizabilities on the dynamics of the structure of the perovskites and the implications this has for hot carrier cooling. The results shed light on the mechanism and origin of the enhanced performance in mixed-cation perovskite-based devices and their merits in comparison to single cation perovskites.