Nanoscale Energy Transport Dynamics across Nonbonded Solid-Molecule Interfaces and in Molecular Thin Films.

Thermal conductance across a solid-solid interface requires an atomic- or molecular-level understanding, especially when a system is in a non-equilibrium state and/or consists of nanosized materials with prominent differences in structures, properties, and vibrational behaviors. Here, we report the lattice dynamics of graphite-supported molecular thin films of ethanol, whose layers exhibit in-plane hydrogen-bonded chains and out-of-plane van der Waals stacking with clear structural anisotropy. The direct structure-probing method of ultrafast electron diffraction reveals a surprising temperature difference of more than 400 K at pico- to sub-nanosecond times across the graphite-ethanol interface, yet the temporal behavior signifies a reasonably large thermal boundary conductance. This apparent conflict in a non-equilibrium condition can be resolved by considering the coupling of out-of-plane motions, instead of the commonly used temperature-based model, at transient times for energy transport across the interface separated by van der Waals interactions with mismatched unit sizes and no strong bonds. The importance of spatiotemporally resolved structural dynamics at the atomic or molecular level is emphasized.