Understanding Plasmonic Properties in Metallic Nanostructures by Correlating Photonic and Electronic Excitations

A large number of optical phenomena rely on the excitation of localized surface plasmon resonances (LSPR) in metallic nanostructures. Electron-energy loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM) has emerged as a technique capable of mapping plasmonic properties on length scales 100 times smaller than optical wavelengths. While this technique is promising, the connection between electron-driven plasmons, encountered in EELS, and photon-driven plasmons, encountered in plasmonic devices, is not well understood. This Perspective highlights some of the contributions that have been made in correlating optical scattering and STEM/EELS from the exact same nanostructures. The experimental observations are further elucidated by comparison with theoretical calculations obtained from the electron-driven discrete dipole approximation, which provides a method to calculate EEL spectra for nanoparticles of arbitrary shape. Applications of plasmon mapping to the electromagnetic hot-spots encountered in single-molecule surface-enhanced Raman scattering and electron beam induced damage in silver nanocubes are discussed. It is anticipated that the complementarity of both techniques will address issues in fundamental and applied plasmonics going forward.