Unlocking the Optoelectronic Potential of AGeX$_{3}$ (A = Ca, Sr, Ba; X = S, Se): A Sustainable Alternative in Chalcogenide Perovskites

Abstract

The quest for environmentally benign and stable optoelectronic materials has intensified, and chalcogenide perovskites (CPs) have emerged as promising candidates owing to their non-toxic composition, stability, small bandgaps, large absorption coefficients. However, a detailed theoretical study of excitonic and polaronic properties of these materials remains underexplored due to high computational demands. Herein, we present a comprehensive theoretical investigation of Germanium-based CPs, AGeX$_{3}$ (A = Ca, Sr, Ba; X = S, Se), which adopt distorted perovskite structures (\beta-phase) with an orthorhombic crystal structure (space group : Pnma) by utilizing state-of-the-art density functional theory (DFT), density functional perturbation theory (DFPT), and many-body perturbation theory (GW and Bethe-Salpeter equation). Our calculations reveal that these materials are thermodynamically and mechanically stable, with the bandgaps calculated using G$_{0}$W$_{0}$@PBE ranging from 0.646 to 2.001 eV - suitable for optoelectronic devices. We analyze the ionic and electronic contributions to dielectric screening using DFPT and BSE methods, finding that the electronic component dominates. The exciton binding energies range from 0.03 to 73.63 meV, indicating efficient exciton dissociation under ambient conditions. Additionally, these perovskites exhibit low to high polaronic mobilities (1.67-167.65 cm$^{2}$V$^{-1}$s$^{-1}$), exceeding many lead-free CPs and halide perovskites due to reduced carrier-phonon interactions. The unique combination of wide tunable bandgaps, low exciton binding energies, and enhanced charge-carrier mobility highlights AGeX$_{3}$ as a potential material for next-generation optoelectronic applications. These compounds are stable, high-performing, and eco-friendly, showing great promise for experimental realization and device integration.