Role of Inorganic Cations in the Excitonic Properties of Lead Halide Perovskites

Abstract: We theoretically investigate lead iodide perovskites of general formula APbI$_3$ for a series of metallic cations (namely Cs$^+$, Rb$^+$, K$^+$, Na$^+$ and Li$^+$) by means of the density functional theory, GW method and Bethe-Salpeter equation including spin-orbit coupling. We demonstrate that the low-energy edges (up to 1.3 eV) of the absorption spectra are dominated by weakly bound excitons, with binding energies $E_b$ $\sim$ 30-80~meV, and the corresponding intensities grow as metallic %A$^+$ cations become lighter. The middle parts of the spectra (1.8-2.4 eV), on the other hand, contain optical dipole transitions comprising more strongly bound excitons ($E_b$ $\sim$ 150-200~meV) located at PbI$_3$. These parts of the spectra correspond to the optical-gain wavelengths which are experimentally achieved in optically-pumped perovskite lasers. Finally, the higher energy parts, from about 2.8~eV (LiPbI$_3$) to 4.3 eV (CsPbI$_3$), contain optical transitions with very strongly bound excitons ($E_b$ $\sim$ 220-290~meV) located at the halide atoms and the empty states of the metallic cations.