Prediction of novel ground-state structures and analysis of phonon transport in two-dimensional GexSy compounds

We conducted this study to explore the ground-state structures of two-dimensional (2D) variable-composition GexSy compounds, driven by the polymorphic characteristics of bulk germanium sulfides and the promising thermoelectric performance of 2D GeS (Pmn21). To accomplish this, we utilized the highly successful evolutionary-algorithm-based code USPEX in conjunction with VASP for total energy calculations, leading to the discovery of three previously unexplored structures of Ge2S (P2/c), GeS (Pm1), and GeS2 (P21/c). These 2D materials exhibit significantly lower formation energies compared to their reported counterparts. We thoroughly scrutinized the structural stability and subsequently analyzed their electronic structures. Our analysis reveals a nearly direct band gap of 0.12/0.84 eV with the PBE/HSE06 functional for 2D Ge2S and an indirect band gap for 2D GeS and GeS2. Their semiconducting nature highlights the crucial importance of lattice thermal conductivity (κl), which we determined by solving the Boltzmann transport equation for phonons. Importantly, we predict a room temperature κl value of 6.82 W m−1 K−1 for GeS, lower than its 2D orthorhombic counterpart. In the case of GeS2, we observed an anisotropic κl value of 16.95/10.68 W m−1 K−1 along the zigzag/armchair directions at 300 K, with an in-plane anisotropy ratio of 1.59, surpassing that of 2D IV–VI compounds. We delve into detailed discussions regarding the role of lattice anharmonicity, group velocities, phonon lifetimes, and three-phonon weighted phase space in the overall thermal conductivity analysis.