Tip-enhanced Raman scattering and near-field optical imaging of semiconducting monolayer and few-layer MoTe2

Transition metal dichalcogenides (TMDs) offer exceptional platforms to study unique phenomena in two-dimensional (2D) materials. The understanding of phonon interactions in atomically thin TMDs is crucial for the development of novel applications. However, advancing our knowledge on phonon dynamics in TMDs under optical, thermal, electric, and strain perturbations requires comprehensive and minimally invasive chemical imaging techniques with nanoscale spatial resolution. Tip-enhanced Raman scattering (TERS) provides new promising avenues towards this goal while also enabling a detailed analysis of structural heterogeneity. Here, we demonstrate gap-mode TERS imaging of mechanically exfoliated monolayer and few-layer 2H–MoTe2. At 633 nm, 671 nm, and 785 nm laser excitations, we report an overwhelmingly selective TERS enhancement of the out-of-plane A1g phonon mode relative to in-plane E12g phonon mode for mono-to few-layer MoTe2. The pure near-field spectral line shapes are clearly distinct from the well-characterized far-field counterparts. We demonstrate that near-field interactions of selective phonon modes are extremely sensitive to the excitation wavelength, sample thickness, and structural defects. Our results therefore provide fundamental information for the nanoscale characterization of semiconducting MoTe2-based devices.