Pressure coefficients for direct optical transitions in MoS2, MoSe2, WS2, and WSe2 crystals and semiconductor to metal transitions

The electronic band structure of MoS 2 , MoSe 2 , WS 2 , and WSe 2 , crystals has been studied at various hydrostatic pressures experimentally by photoreflectance (PR) spectroscopy and theoretically within the density functional theory (DFT). In the PR spectra direct optical transitions (A and B) have been clearly observed and pressure coefficients have been determined for these transitions to be: α A = 2.0 ± 0.1 and α B = 3.6 ± 0.1 meV/kbar for MoS 2 , α A = 2.3 ± 0.1 and α B = 4.0 ± 0.1 meV/kbar for MoSe 2 , α A = 2.6 ± 0.1 and α B = 4.1 ± 0.1 meV/kbar for WS 2 , α A = 3.4 ± 0.1 and α B = 5.0 ± 0.5 meV/kbar for WSe 2 . It has been found that these coefficients are in an excellent agreement with theoretical predictions. In addition, a comparative study of different computational DFT approaches has been performed and analyzed. For indirect gap the pressure coefficient have been determined theoretically to be −7.9, −5.51, −6.11, and −3.79, meV/kbar for MoS 2 , MoSe 2 , WS 2 , and WSe 2 , respectively. The negative values of this coefficients imply a narrowing of the fundamental band gap with the increase in hydrostatic pressure and a semiconductor to metal transition for MoS 2 , MoSe 2 , WS 2 , and WSe 2 , crystals at around 140, 180, 190, and 240 kbar, respectively.