The role of mid-gap phonon modes in thermal transport of transition metal dichalcogenides

We present a comprehensive theoretical study on thermal transport in monolayer transition metal dichalcogenides MX₂ (M: Mo, W; X: S, Se) with various sample sizes. An unusually high anharmonic scattering strength is found in MoSe₂ compared to the other three family members, which arises from its unique phonon band dispersion, specifically the mid-frequency phonon branches associated with the vibrations of Se atoms of MoSe₂. The mid-frequency modes almost completely span the gap that exists between the high-frequency phonon branches and the acoustic ones, allowing the former to readily decay into the latter. The resultant high anharmonic scattering gives rise to a short mean free path which makes the room temperature in-plane thermal conductivity in MoSe₂ even lower than WSe₂ when the sample length is larger than 51.5 nm. With varying sample sizes, the ordering of thermal conductivity among the four materials changes as phonon transport transits from the ballistic to diffusive regime, driven by the competition between the phonon frequency spectrum range and the scattering strength. Our work provides a microscopic picture of phonon transport in TMDs and guidance to tailor their thermal conductivities for electronic and thermoelectric applications.