Control of Charge Carrier Dynamics in Plasmonic Au Films by TiO Substrate Stoichiometry.

Plasmonic excitations in noble metals have many fascinating properties and give rise to a broad range of applications. We demonstrate, using nonadiabatic molecular dynamics combined with time-domain density functional theory, that the chemical composition and stoichiometry of substrates can have a strong influence on charge dynamics. By changing oxygen content in TiO, including stoichiometric, oxygen rich, and oxygen poor phases, and Ti metal, one can alter lifetimes of charge carriers in Au by a factor of 5 and control the ratio of electron-to-hole relaxation rates by a factor of 10. Remarkably, a thin TiO substrate greatly alters charge carrier properties in much thicker Au films. Such large variations stem from the fact that the Ti and O atoms are much lighter than Au, and their vibrations are much faster at dissipating the energy. The control over a particular charge carrier and an energy range depends on the Au and TiO level alignment, and the interfacial interaction strength. These factors are easily influenced by the TiO stoichiometry. In particular, oxygen rich and poor TiO can be used to control holes and electrons, respectively, while metallic Ti affects both charge carriers. The detailed atomistic analysis of the interfacial and electron-vibrational interactions generates the fundamental understanding of the properties of plasmonic materials needed to design photovoltaic, photocatalytic, optoelectronic, sensing, nanomedical, and other devices.