Control of Charge Carrier Relaxation at the Au/WSe2 Interface by Ti and TiO₂ Adhesion Layers: Ab Initio Quantum Dynamics

Phonon-mediated charge relaxation plays a vital role in controlling thermal transport across an interface for efficient functioning of two-dimensional (2D) nanostructured devices. Using a combination of nonadiabatic molecular dynamics with real-time time-dependent density functional theory, we demonstrate a strong influence of adhesion layers at the Au/WSe2 interface on nonequilibrium charge relaxation, rationalizing recent ultrafast time-resolved experiments. Ti oxide layers (TiOx) create a barrier to the interaction between Au and WSe2 and extend hot carrier lifetimes, creating benefits for photovoltaic and photocatalytic applications. In contrast, a metallic Ti layer accelerates the energy flow, as needed for efficient heat dissipation in electronic devices. The interaction of metallic Ti with WSe2 causes W-Se bond scissoring and pins the Fermi level. The Ti adhesion layer enhances the electron-phonon coupling due to an increased density of states and the light mass of the Ti atom. The conclusions are robust to presence of typical point defects. The atomic-scale ab initio analysis of carrier relaxation at the interfaces advances our knowledge in fabricating nanodevices with optimized electronic and thermal properties.