Energy-Resolved Femtosecond Hot Electron Dynamics in Single Plasmonic Nanoparticles

Abstract: Efficient excitation and harvesting of hot carriers from nanoscale metals is central to many emerging photochemical, photovoltaic, and ultrafast optoelectronic applications. Yet direct experimental evidence of the relevant femtosecond dynamics in ubiquitous tens-of-nanometer gold structures remains lacking, despite the rich interplay between interfacial and internal plasmonic fields, excitation distributions, and scattering processes. To explore the effects of nanoscale structure on these dynamics, we employ a new technique for simultaneous time-, angle-, and energy-resolved photoemission spectroscopy of single plasmonic nanoparticles. Photoelectron velocity distributions reveal bulk-like ballistic hot electron transport in nanorod and nanoshell geometries, with no evidence of surface effects. Energy-resolved dynamics observed in the ~1-2 eV range and extrapolated to lower energies via kinetic Boltzmann theory provide the first direct measurements of hot carrier lifetimes within nanoscale gold. Remarkably, we find that particles with dimensions as small as 10 nm serve as exemplary platforms for studying intrinsic metal dynamics.