Resonant Exciton Scattering Reveals Raman Forbidden Phonon Modes in Layered GeS

Germanium monosulfide with an anisotropic puckered crystalline structure has recently attracted much attention due to its unique optical and electronic properties; however, exciton–phonon interactions were only superficially elucidated. We study the resonant Raman scattering and the photoluminescence of the optically active Γ-exciton in layered GeS flakes and evaluate the exciton and phonon responses on variations in the excitation energy, laser-light and emission polarizations, temperature, and laser power. A double-resonance mechanism allows for observing Raman forbidden (dark) first- and second-order longitudinal-optical phonon modes whose symmetries and energies are moreover calculated by density functional perturbation theory. For (quasi)-resonant exciton excitation, the selection rules become relaxed so that a fourth-order Fröhlich intraband process is mediated by the scattering of the electron with a longitudinal-optical and an acoustic phonon. Our results demonstrate considerable coupling between phonons and photogenerated carriers in GeS flakes and the high efficiency of multiorder scattering in optical processes.