Resonant Raman and Exciton Coupling in High-Quality Single Crystals of Atomically Thin Molybdenum Diselenide Grown by Vapor-Phase Chalcogenization

We report a detailed investigation on Raman spectroscopy in vapor-phase chalcogenization grown, high-quality single-crystal atomically thin molybdenum diselenide samples. Measurements were performed in samples with four different incident laser excitation energies ranging from 1.95 eV ⩽ E_ex ⩽ 2.71 eV, revealing rich spectral information in samples ranging from N = 1-4 layers and a thick, bulk sample. In addition to previously observed (and identified) peaks, we specifically investigate the origin of a peak near ω ≈ 250 cm^-1. Our density functional theory and Bethe-Salpeter calculations suggest that this peak arises from a double-resonant Raman process involving the ZA acoustic phonon perpendicular to the layer. This mode appears prominently in freshly prepared samples and disappears in aged samples, thereby offering a method for ascertaining the high optoelectronic quality of freshly prepared 2D-MoSe₂ crystals. We further present an in-depth investigation of the energy-dependent variation of the position of this and other peaks and provide evidence of C-exciton-phonon coupling in monolayer MoSe₂. Finally, we show how the signature peak positions and intensities vary as a function of layer thickness in these samples.