Probing strong coupling in core--shell nanoparticles with fast electron beams

Abstract: Collective optical excitations, such as localized surface plasmons in metallic nanoparticles and Mie resonances in high-index dielectrics, play a central role in nanoscale light--matter interactions. When such optical modes interact with electronic transitions in matter under suitable conditions, they can couple strongly, analogous to two coupled harmonic oscillators, forming hybrid light--matter states. In this work, we probe this coupling in core--shell nanoparticles using fast electrons in electron energy-loss (EEL) and cathodoluminescence (CL) spectroscopy. Owing to their highly localized fields, fast electrons can excite modes inaccessible with light-based spectroscopies, including higher-order nonradiative modes, which offer greater field confinement and potentially stronger coupling. Here, we develop an analytical framework to calculate the EEL and CL probabilities for spherical core--shell nanoparticles under aloof and penetrating electron trajectories. This formalism is applied to two representative systems: an excitonic core with a metallic shell, and a silicon core with an excitonic shell. Our main focus is to examine how the electron beam position and velocity affect our ability to probe this coupling. Depending on the electron beam parameters, we find that the spectral signature of strong coupling remains robust in plasmonic nanospheres. In contrast, it can be significantly suppressed or even completely obscured in dielectric nanospheres. Our developed formalism enables a deeper understanding of the coupling mechanisms in electron--light--matter interactions, thereby accelerating progress in single-nanoparticle-based polaritonic studies.