No abstract

Low-temperature photoluminescence (PL) of hBN-encapsulated monolayer tungsten diselenide (WSe2) shows a multitude of sharp emission peaks below the bright exciton. Some of them have been recently identified as phonon sidebands of momentum-dark states. However, the exciton dynamics behind the emergence of these sidebands has not been revealed yet. In this joint theory–experiment study, we theoretically predict and experimentally observe time-resolved PL, providing microscopic insights into the thermalization of hot excitons formed after optical excitation. In very good agreement between theory and experiment, we demonstrate a spectral red-shift of phonon sidebands on a time scale of tens of picoseconds, reflecting the phonon-driven thermalization of hot excitons in momentum-dark states. Furthermore, we predict the emergence of a transient phonon sideband that vanishes in the stationary PL. The obtained microscopic insights are applicable to a broad class of 2D materials with multiple exciton valleys.

We experimentally demonstrate time-resolved exciton propagation in a monolayer semiconductor at cryogenic temperatures. Monitoring phonon-assisted recombination of dark states, we find a highly unusual case of exciton diffusion. While at 5 K the diffusivity is intrinsically limited by acoustic phonon scattering, we observe a pronounced decrease of the diffusion coefficient with increasing temperature, far below the activation threshold of higher-energy phonon modes. This behavior corresponds neither to wellknown regimes of semiclassical free-particle transport nor to the thermally activated hopping in systems with strong localization. Its origin is discussed in the framework of both microscopic numerical and semiphenomenological analytical models illustrating the observed characteristics of nonclassical propagation. Challenging the established description of mobile excitons in monolayer semiconductors, these results open up avenues to study quantum transport phenomena for excitonic quasiparticles in atomically thin van der Waals materials and their heterostructures.

No abstract