Probing Excitons, Trions, and Dark Excitons in Monolayer WS₂ Using Resonance Raman Spectroscopy

We present temperature-dependent resonance Raman measurements on monolayer WS₂ for the temperature range 4–295 K using excitation photon energies from 1.9 to 2.15 eV in ∼7 meV steps. These are analyzed to determine the resonance profiles of five previously assigned phonon based Raman peaks (A₁′, E′, 2ZA, LA, 2LA) and a previously unassigned peak at 485 cm^–1 whose possible attributions are discussed. The resonance profiles obtained are fitted to a perturbation theory derived model and it is shown that both excitons and trions are required to explain the profiles. The model is used to separate the contribution of exciton–exciton, trion–trion, and exciton–trion scattering to each of the Raman peaks at 4 K. This separation allows the ratios of the rates of scattering involving the A₁′ and E′ phonons for each of the three types of scattering to be determined. The explanation of the multiphonon Raman peaks requires the coupling of bright excitons and trions to large wavevector dark states. The fitting of the resonance Raman profiles for these Raman peaks demonstrates scattering of bright excitons to bright trions via these large wavevector dark states