In this Letter, the ultrafast structural, interfacial, and carrier dynamics of monolayer MoS2 supported on sapphire are cross-examined by the combination of ultrafast electron diffraction (UED) and transient reflectivity techniques. The out-of-plane motions directly probed by reflection UED suggest a limited anisotropy in the atomic motions of monolayer MoS2, which is distinct from that of related materials such as graphene and WSe2. Besides thermal diffusion, the MoS2–sapphire interface exhibits structural dynamics trailing those of the overlaying MoS2 and are in stark contrast with the sapphire bulk, which is consistent with the limited thermal boundary conductance. These structural dynamics provide justification for the determination of carriers being trapped by defects in ∼600 fs and releasing energy within a few picoseconds. The rich findings attest to the strength of combining techniques with real-time optical and direct structure probes for a detailed understanding of dynamical processes in functional materials.

Black phosphorus (bP) exhibits highly anisotropic properties and dynamical behavior that are unique even among two-dimensional and van der Waals (vdW) layered materials. Here, we show that an interlayer lattice contraction and concerted, symmetric intralayer vibrations occur concurrently within few picoseconds following the photoinjection and relaxation of carriers, using ultrafast electron diffraction in the reflection geometry to probe the out-of-plane motions. A strong coupling between the photocarriers and bP’s puckered structure, with the alignment of the electronic band structure, is at work for such directional atomic motions without a photoinduced phase transition. Three temporal regimes can be identified for the phonon thermalization dynamics where a quasi-equilibrium without anisotropy is reached in about 50 ps, followed by propagation of coherent acoustic phonons and heat diffusion into the bulk. The early time out-of-plane dynamics reported here have important implications for single- and few-layer bP and other vdW materials with strong electronic–lattice correlations.