Electron Energy-Loss Spectroscopy of Coupled Plasmonic Systems: Beyond the Standard Electron Perspective

Electron energy-loss spectroscopy (EELS) has become an experimental method of choice for the investigation of localized surface plasmon resonances, allowing the simultaneous mapping of the associated field distributions and their resonant energies with a nanoscale spatial resolution. The experimental observations have been well-supported by numerical models based on the computation of the Lorentz force acting on the impinging electrons by the scattered field. However, in this framework, the influence of the intrinsic properties of the plasmonic nanostructures studied with the electron energy-loss (EEL) measurements is somehow hidden in the global response. To overcome this limitation, we propose to go beyond this standard, and well-established, electron perspective and instead to interpret the EELS data using directly the intrinsic properties of the nanostructures, without regard to the force acting on the electron. The proposed method is particularly well-suited for the description of coupled plasmonic systems, because the role played by each individual nanoparticle in the observed EEL spectrum can be clearly disentangled, enabling a more subtle understanding of the underlying physical processes. As examples, we consider different plasmonic geometries in order to emphasize the benefits of this new conceptual approach for interpreting experimental EELS data. In particular, we use it to describe results from samples made by traditional thin film patterning and by arranging colloidal nanostructures.