Free Electron–Plasmon Coupling Strength and Near-Field Retrieval through Electron Energy-Dependent Cathodoluminescence Spectroscopy

Tightly confined optical near fields in plasmonic nanostructures play a pivotal role in important applications ranging from optical sensing to light harvesting. Energetic electrons are ideally suited to probing optical near fields by collecting the resulting cathodoluminescence (CL) light emission. Intriguingly, the CL intensity is determined by the near-field profile along the electron propagation direction, but the retrieval of such field from measurements has remained elusive. Furthermore, the conditions for optimum electron near-field coupling in plasmonic systems are critically dependent on such field and remain experimentally unexplored. In this work, we use electron energy-dependent CL spectroscopy to study the tightly confined dipolar mode in plasmonic gold nanoparticles. By systematically studying gold nanoparticles with diameters in the range of 20-100 nm and electron energies from 4 to 30 keV, we determine how the coupling between swift electrons and the optical near fields depends on the energy of the incoming electron. The strongest coupling is achieved when the electron speed equals the mode phase velocity, meeting the so-called phase-matching condition. In aloof experiments, the measured data are well reproduced by electromagnetic simulations, which explain that larger particles and faster electrons favor a stronger electron near-field coupling. For penetrating electron trajectories, scattering at the particle produces severe corrections of the trajectory that defy existing theories based on the assumption of nonrecoil condition. Therefore, we develop a first-order recoil correction model that allows us to account for inelastic electron scattering, rendering better agreement with measured data. Finally, we consider the albedo of the particles and find that, to approach unity coupling, a highly confined electric field and very slow electrons are needed, both representing experimental challenges. Our findings explain how to reach unity-order coupling between free electrons and confined excitations, helping us understand fundamental aspects of light-matter interaction at the nanoscale.