Structural, Electronic, Mechanical, Thermodynamic, and Linear and Nonlinear Optical Properties of MoS2, MoSe2, and their MoS2xSe2(1−x) Alloys: Ab Initio Calculations

Abstract

The Born effective charge tensors, high-frequency dielectric constants, phonon frequencies at Г symmetry point, and phonon dispersion curves of MoS2xSe2(1−x) (x = 0, 0.25, 0.5, 0.75, and 1) alloys are calculated based on density functional perturbation theory using optimized lattice parameters. The structural stability, stiffness, ductility, and plasticity of these alloys are explored in detail by calculating the polycrystalline structural properties. The calculated Born effective charges and Poisson’s ratio indicate the existence of a combination of ionic and covalent bonding between the transition metal and chalcogens in each layer. Based on the calculated phonon frequencies, the temperature dependence of the specific heat at constant volume, entropy, and Helmholtz free energy of MoS2xSe2(1−x) (x = 0, 0.25, 0.5, 0.75, and 1) alloys are calculated in the harmonic approximation. Structurally, the spatial inversion symmetry in the MoS2xSe2(1−x) (x = 0.25, 0.5, and 0.75) alloys is broken. This leads MoS2xSe2(1−x) (x = 0.25, 0.5, and 0.75) alloys to exhibit novel nonlinear optical properties that do not exist in the 2H-MoX2 (X = S, Se) compounds. So, the nonlinear optical properties are calculated by applying the 2n + 1 theorem to an electric-field-dependent energy functional. It is found that MoS2xSe2(1−x) (x = 0.25, 0.5, and 0.75) alloys exhibit remarkable large nonlinear optical susceptibility and electro-optic coefficients and would be promising candidates for use in nonlinear optical applications. Van der Waals interactions are included in all the first-principles calculations, to correctly describe the interaction between adjacent layers. The calculated lattice parameters, electronic energy bandgaps, phonon frequencies, and high-frequency dielectric constants of 2H-MoX2 (X = S, Se) compounds are in good agreement with available theoretical and experimental results.