Raman spectra of IVB and VIB transition metal disulfides using laser energies near the absorption edges

In this paper, we present Raman spectra of ZrS₂, HfS₂, MoS₂ and WS₂ using laser energies near the energies of the absorption edges. The Raman spectra probe the properties of the first-excited electronic state and the nature of the electron-phonon coupling. The spectra of the IVB disulfides are independent of the laser excitation energy, suggesting weak electron-phonon interaction. In contrast, additional Raman bands appear in the spectra of the VIB disulfides as the laser energy approaches the band gap energy. The new modes in the spectra of MoS₂ and WS₂ cannot be assigned as first-order processes nor as combination bands of the phonons with zero momentum. The resonance Raman scattering of MoS₂ is analyzed in terms of second-order scattering due to the coupling of phonon modes of nonzero momentum with an electronic transition associated with excitonic states.