Nonlinear Optical Properties of Transition Metal Dichalcogenide MX$_2$ (M = Mo, W; X = S, Se) Monolayers and Trilayers from First-principles Calculations

Abstract: Due to the absence of interlayer coupling and inversion symmetry, transition metal dichalcogenide (MX$_2$) semiconductor monolayers exhibit novel properties that are distinctly different from their bulk crystals such as direct optical band gaps, large band spin splittings, spin-valley coupling, piezoelectric and nonlinear optical responses, and thus have promising applications in, e.g., opto-electronic and spintronic devices. Here we have performed a systematic first-principles study of the second-order nonlinear optical properties of MX$_2$ (M = Mo, W; X = S, Se) monolayers and trilayers within the density functional theory with the generalized gradient approximation plus scissors correction. We find that all the four MX$_2$ monolayers possess large second-order optical susceptibility $\chi^{(2)}$ in the optical frequency range and significant linear electro-optical coefficients in low frequency limit, thus indicating their potential applications in non-linear optical devices and electric optical switches. The $\chi^{(2)}$ spectra of the MX$_2$ trilayers are overall similar to the corresponding MX$_2$ monolayers, {\it albeit} with the magnitude reduced by roughly a factor of 3. The prominent features in the $\chi^{(2)}$ spectra of the MX$_2$ multilayers are analyzed in terms of the underlying band structures and optical dielectric function, and also compared with available experiments.