First-principles many-body study for electronic, optical, and excitonic properties of RbTlCl3 perovskite for solar cells

We present a detailed many-body ab initio study of the valence-skipper RbTlCl$_{3}$ perovskite compound for photovoltaic (PV) applications. The electronic and optical properties, both with and without spin-orbit coupling, have been calculated using density functional theory (DFT) and many-body excited-state calculations. The band gap, which is indirect in nature, is found to be 0.95 eV and 0.89 eV from PBE and PBEsol, respectively. The optical properties have been computed using four different approximations: independent particle approximation (IPA), IPA with scissor correction (IQPA), random phase approximation for local-field effects (LFEs), and the Bethe-Salpeter equation (BSE). The estimated highest value of the imaginary part of the dielectric function using IQPA is 7 at 2 eV, which slightly decreases to 5.7 due to LFEs. Within BSE, the peak value is obtained to be maximum at 1.6 eV with a magnitude of 10.8, which indicates the strong excitonic effect below the optical gap. Large number of bright and dark bound excitons are found, where the binding energies of four main bound bright excitons are found in the range of 299-350 meV. The exciton amplitude in both reciprocal and real space is analyzed. The main bound bright exciton is localized in the reciprocal space, while this exhibits a delocalized nature in real space. The BSE predicts a highest absorption coefficient of 3.6 $\times$ $10^{6}$ cm$^{-1}$ at 1.7 eV, while a minimum reflectivity in the active region of the solar energy spectrum is obtained to be around 2.7\%. Finally, the solar efficiency has been estimated using the spectroscopic limited maximum efficiency approach and obtained highest value is 15.5% at a thickness of 0.5 $μ$m. These findings reveal a significant excitonic effect in the absorption spectra of RbTlCl$_{3}$ and highlight its potential as a promising material for single-junction thin-film solar cells.