Structure–Property Relationships in Transition Metal Dichalcogenide Bilayers Under Biaxial Strains

This paper reports a Density Functional Theory (DFT) investigation of the electron density and optoelectronic properties of two-dimensional (2D) MX2 (M = Mo, W and X = S, Se, Te) subjected to biaxial strains. Upon strains ranging from −4% (compressive strain) to +4% (tensile strain), MX2 bilayers keep the same bandgap type but undergo a non-symmetrical evolution of bandgap energies and corresponding effective masses of charge carriers (m*). Despite a consistency regarding the electronic properties of Mo- and WX2 for a given X, the strain-induced bandgap shrinkage and m* lowering are strong enough to alter the strain-free sequence MTe2, MSe2, MS2, thus tailoring the photovoltaic properties, which are found to be direction dependent. Based on the quantum theory of atoms in molecules, the bond degree (BD) at the bond critical points was determined. Under strain, the X-X BD decreases linearly as X atomic number increases. However, the kinetic energy per electron G/ρ at the bond critical point is independent of strains with the lowest values for X = Te, which can be related to the highest polarizability evidenced from the dielectric properties. A cubic relationship between the absolute BD summation of M-X and X-X bonds and the static relative permittivity was observed. The dominant position of X-X bond participating in this cubic relationship in the absence of strain was substantially reinforced in the presence of strain, yielding the leading role of the X-X bond instead of the M-X one in the photovoltaic response of 2D MX2 material.