Emergent Moiré Phonons Due to Zone Folding in WSe₂–WS₂ Van der Waals Heterostructures

Bilayers of 2D materials offer opportunities for creating devices with tunable electronic, optical, and mechanical properties. In van der Waals heterostructures (vdWHs) where the constituent monolayers have different lattice constants, a moiré superlattice forms with a length scale larger than the lattice constant of either constituent material regardless of twist angle. Here, we report the appearance of moiré Raman modes from nearly aligned WSe2–WS2 vdWHs in the range of 240–260 cm–1, which are absent in both monolayers and homobilayers of WSe2 and WS2 and in largely misaligned WSe2–WS2 vdWHs. Using first-principles calculations and geometric arguments, we show that these moiré Raman modes are a consequence of the large moiré length scale, which results in zone-folded phonon modes that are Raman active. These modes are sensitive to changes in twist angle, but notably, they occur at identical frequencies for a given small twist angle away from either the 0-degree or 60-degree aligned heterostructure. Our measurements also show a strong Raman intensity modulation in the frequency range of interest, with near 0 and near 60-degree vdWHs exhibiting a markedly different dependence on excitation energy. In near 0-degree aligned WSe2–WS2 vdWHs, a nearly complete suppression of both the moiré Raman modes and the WSe2 A1g Raman mode (∼250 cm–1) is observed when exciting with a 532 nm CW laser at room temperature. Temperature-dependent reflectance contrast measurements demonstrate the significant Raman intensity modulation arises from resonant Raman effects.