Optical Excitations with Electron Beams: Challenges and Opportunities

[Image: see text] Free electron beams such as those employed in electron microscopes have evolved into powerful tools to investigate photonic nanostructures with an unrivaled combination of spatial and spectral precision through the analysis of electron energy losses and cathodoluminescence light emission. In combination with ultrafast optics, the emerging field of ultrafast electron microscopy utilizes synchronized femtosecond electron and light pulses that are aimed at the sampled structures, holding the promise to bring simultaneous sub-Å–sub-fs–sub-meV space–time–energy resolution to the study of material and optical-field dynamics. In addition, these advances enable the manipulation of the wave function of individual free electrons in unprecedented ways, opening sound prospects to probe and control quantum excitations at the nanoscale. Here, we provide an overview of photonics research based on free electrons, supplemented by original theoretical insights and discussion of several stimulating challenges and opportunities. In particular, we show that the excitation probability by a single electron is independent of its wave function, apart from a classical average over the transverse beam density profile, whereas the probability for two or more modulated electrons depends on their relative spatial arrangement, thus reflecting the quantum nature of their interactions. We derive first-principles analytical expressions that embody these results and have general validity for arbitrarily shaped electrons and any type of electron–sample interaction. We conclude with some perspectives on various exciting directions that include disruptive approaches to noninvasive spectroscopy and microscopy, the possibility of sampling the nonlinear optical response at the nanoscale, the manipulation of the density matrices associated with free electrons and optical sample modes, and appealing applications in optical modulation of electron beams, all of which could potentially revolutionize the use of free electrons in photonics.