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.