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We report on the design, realization, and experimental investigation by spatially resolved monochromated electron energy loss spectroscopy (EELS) of high-quality-factor cavities with modal volumes smaller than λ3, with λ being the free-space wavelength of light. The cavities are based on a slot defect in a 2D photonic crystal slab made up of silicon. They are optimized for high coupling of electrons accelerated to 100 kV to quasi-transverse electrical modes polarized along the slot direction. We studied the cavities in two geometries and took advantage of the deep sub-optical wavelength spatial resolution of the electron microscope and high spectral resolution of the monochromator to comprehensively describe the optical excitations of the slab. The first geometry, for which the cavities have been designed, corresponds to an electron beam traveling along the slot direction. The second consists of the electron beam traveling perpendicular to the slab. In both cases, a large series of modes is identified. The dielectric slot mode energies are measured to be in the 0.8–0.85 eV range, as per design, and surrounded by two bands of dielectric and air modes of the photonic structure. The dielectric even slot modes, to which the cavity mode belongs, are highly coupled to the electrons with up to 3.2% probability of creating a slot photon per incident electron. Although the experimental spectral resolution (around 30 meV) alone does not allow to disentangle cavity photons from other slot photons, the excellent agreement between the experiments and finite-difference time-domain simulations allows us to deduce that among the photons created in the slot, around 30% are stored in the cavity mode. A systematic study of the energy and coupling strength as a function of the photonic band gap parameters permits us to foresee an increase of coupling strength by fine-tuning phase-matching. Our work demonstrates free electron coupling to high-quality-factor cavities with low mode densities and sub-λ3modal volumes, making it an excellent candidate for applications such as quantum nano-optics with free electrons.

The optical properties of metallic nanoparticles are dominated by localized surface plasmons (LSPs). Their properties depend on the constituting material, the size, and shape of the nano-object as well as its surrounding medium. In anisotropic structures, such as metallic nanorods, two families of modes generally exist, transverse and longitudinal. Their spectral and spatial overlaps usually impede their separate measurements in electron energy loss spectroscopy (EELS). In this work, we propose three different strategies to overcome this difficulty and selectively probe longitudinal and transverse modes. The first strategy is numeric and relies on morphing of nanostructures, rooted in the geometrical nature of LSPs. The two other strategies exploit the relativistic and wave nature of the electrons in an EELS experiment. The first one is the phase-matching between the electron and the plasmon excitation to enhance their coupling by either tilting the sample or modifying the electron kinetic energy. The second one─polarized EELS (pEELS)─exploits the wave nature of electrons to mimic selection rules analogous to the one existing in light spectroscopies. The abovementioned strategies are exemplified─either experimentally or numerically─on a canonical plasmonic toy model: the nanorod. The goal of the paper is to bring together the state-of-the-art concepts of EELS for plasmonics to tackle a pedestrian problem in this field.

Scanning transmission electron microscopy coupled with electron energy loss spectroscopy (STEM-EELS) provides spatially resolved chemical information down to the atomic scale. However, studying radiation-sensitive specimens such as organic–inorganic composites remains extremely challenging. Here, we analyzed metal–organic framework nanoparticles (nanoMOFs) at low-dose (10 e–/Å2) and liquid nitrogen temperatures, similar to cryo-TEM conditions usually employed for high-resolution imaging of biological specimens. Our results demonstrate that monochromated STEM-EELS enables damage-free analysis of nanoMOFs, providing in a single experiment, signatures of intact functional groups comparable with infrared, ultraviolet, and X-ray data, with an energy resolution down to 7 meV. The signals have been mapped at the nanoscale (<10 nm) for each of these energy spectral ranges, including the chemical features observed for high energy losses (X-ray range). By controlling beam irradiation and monitoring spectral changes, our work provides insights into the possible pathways of chemical reactions occurring under electron exposure. These results demonstrate the possibilities for characterizing at the nanoscale the chemistry of sensitive systems such as organic and biological materials.

Les microscopes électroniques en transmission ultrarapides combinent la résolution temporelle des sources laser femtosecondes avec la résolution spatiale des microscopes électroniques. Cette résolution spatio-temporelle inégalée, la richesse des techniques de microscopie électronique et les immenses possibilités de façonnage des impulsions optiques et électroniques ultrabrèves ouvrent des perspectives fascinantes pour l’exploration et le contrôle de la dynamique de la matière condensée.

Récemment, les microscopies électroniques à balayage et/ou en transmission se sont imposées comme des techniques de choix pour étudier les phénomènes optiques avec des résolutions spatiales bien meilleures que la limite de diffraction optique. Les spectroscopies de perte et de gain d’énergie, ainsi que la cathodoluminescence permettent ainsi d’étudier à une échelle pertinente des excitations comme les plasmons de surface dans les nanoparticules métalliques ou les excitons dans des structures confinées quantiquement.

Whispering-gallery mode resonators host multiple trapped narrow-band circulating optical resonances that find applications in quantum electrodynamics, optomechanics, and sensing. However, the spherical symmetry and low field leakage of dielectric microspheres make it difficult to probe their high-quality optical modes using far-field radiation. Even so, local field enhancement from metallic nanoparticles (MNPs) coupled to the resonators can interface the optical far field and the bounded cavity modes. In this work, we study the interaction between whispering-gallery modes and MNP surface plasmons with nanometric spatial resolution by using electron-beam spectroscopy with a scanning transmission electron microscope. We show that gallery modes are induced over a selective spectral range of the nanoparticle plasmons, and additionally, their polarization can be controlled by the induced dipole moment of the MNP. Our study demonstrates a viable mechanism to effectively excite high-quality-factor whispering-gallery modes and holds potential for applications in optical sensing and light manipulation.

Spectromicroscopy techniques with fast electrons can quantitatively measure the optical response of excitations with unrivalled spatial resolution. However, owing to their inherently scalar nature, electron waves cannot access the polarization-related quantities. Despite promising attempts based on the conversion of concepts originating from singular optics (such as vortex beams), the definition of an optical polarization analogue for fast electrons has remained an open question. Here we establish such an analogue using the dipole transition vector of the electron between two well-chosen singular wave states. We show that electron energy loss spectroscopy allows the direct measurement of the polarized electromagnetic local density of states. In particular, in the case of circular polarization, it directly measures the local optical spin density. This work establishes electron energy loss spectroscopy as a quantitative technique to tackle fundamental issues in nano-optics, such as super-chirality, local polarization of dark excitations or polarization singularities at the nanoscale.

Silver, king among plasmonic materials, features low inelastic absorption in the visible-infrared (vis-IR) spectral region compared to other metals. In contrast, copper is commonly regarded as too lossy for actual applications. Here, we demonstrate vis-IR plasmons with quality factors >60 in long copper nanowires (NWs), as determined by electron energy-loss spectroscopy. We explain this result by noticing that most of the electromagnetic energy in these plasmons lies outside the metal, thus becoming less sensitive to inelastic absorption. Measurements for silver and copper NWs of different diameters allow us to elucidate the relative importance of radiative and nonradiative losses in plasmons spanning a wide spectral range down to <20 meV. Thermal population of such low-energy modes becomes significant and generates electron energy gains associated with plasmon absorption, rendering an experimental determination of the NW temperature. Copper is therefore emerging as an attractive, cheap, abundant material platform for high-quality plasmonics in elongated nanostructures.

Atomic vibrations and phonons are an excellent source of information on nanomaterials that we can access through a variety of methods including Raman scattering, infrared spectroscopy, and electron energy-loss spectroscopy (EELS). In the presence of a plasmon local field, vibrations are strongly modified and, in particular, their dipolar strengths are highly enhanced, thus rendering Raman scattering and infrared spectroscopy extremely sensitive techniques. Here, we experimentally demonstrate that the interaction between a relativistic electron and vibrational modes in nanostructures is fundamentally modified in the presence of plasmons. We finely tune the energy of surface plasmons in metallic nanowires in the vicinity of hexagonal boron nitride, making it possible to monitor and disentangle both strong phonon–plasmon coupling and plasmon-driven phonon enhancement at the nanometer scale. Because of the near-field character of the electron beam–phonon interaction, optically inactive phonon modes are also observed. Besides increasing our understanding of phonon physics, our results hold great potential for investigating sensing mechanisms and chemistry in complex nanomaterials down to the molecular level.

When circularly polarized light interacts with a nanostructure, the optical response depends on the geometry of the structure. If the nanostructure is chiral (i.e., it cannot be superimposed on its mirror image), then its optical response, both in near-field and far-field, depends on the handedness of the incident light. In contrast, achiral structures exhibit identical far-field responses for left- and right-circular polarization. Here, we show that a perfectly achiral nanostructure, a plasmonic metamolecule with trigonal D3hsymmetry, exhibits a near-field response that is sensitive to the handedness of light. This effect stems from the near-field interference between the different plasmonic modes sustained by the plasmonic metamolecule under circularly polarized light excitation. The local chirality in a plasmonic trimer is then experimentally evidenced with nanoscale resolution using a molecular probe. Our experiments demonstrate that the optical near-field chirality can be imprinted into the photosensitive polymer, turning an optical chirality into a geometrical chirality that can be imaged using atomic force microscopy. These results are of interest for the field of polarization-sensitive photochemistry.

Probing optical excitations with nanometer resolution is important for understanding their dynamics and interactions down to the atomic scale. Electron microscopes currently offer the unparalleled ability of rendering spatially resolved electron spectra with combined meV and sub-nm resolution, while the use of ultrafast optical pulses enables fs temporal resolution and exposure of the electrons to ultraintense confined optical fields. Here, we theoretically investigate fundamental aspects of the interaction of fast electrons with localized optical modes that are made possible by these advances. We use a quantum optics description of the optical field to predict that the resulting electron spectra strongly depend on the statistics of the sample excitations (bosonic or fermionic) and their population (Fock, coherent, or thermal), whose autocorrelation functions are directly retrieved from the ratios of electron gain intensities. We further explore feasible experimental scenarios to probe the quantum characteristics of the sampled excitations and their populations. In particular, we present realistic simulations for electron beams interacting with optical cavities infiltrated with optically pumped quantum emitters, which we show to undergo a varied temporal evolution in the cavity mode statistics that causes radical modifications in the transmitted electron spectra depending on pump-electron delay.

We develop here a comprehensive experimental approach to independently determine charge carrier parameters, namely, carrier density and mass, in plasmonic indium tin oxide nanocrystals. Typically, in plasmonic nanocrystals, only the ratio between these two parameters is accessible through optical absorption experiments. The multitechnique methodology proposed here combines single particle and ensemble optical and magneto-optical spectroscopies, also using 119Sn solid-state nuclear magnetic resonance spectroscopy to probe the surface depletion layer. Our methodology overcomes the limitations of standard fitting approaches based on absorption spectroscopy and ultimately gives access to carrier effective mass directly on the NCs, discarding the use of literature value based on bulk or thin film materials. We found that mass values depart appreciably from those measured on thin films; consequently, we found carrier density values that are different from reported literature values for similar systems. The effective mass was found to deviate from the parabolic approximation at a high carrier density. Finally, the dopant activation and defect diagram for ITO NCs for tin doping between 2.5 and 15% are determined. This approach can be generalized to other plasmonic heavily doped semiconductor nanostructures and represents, to the best of our knowledge, the only method to date to characterize the full Drude parameter space of 0-D nanosystems.

Control over the optical properties of atomically thin two-dimensional (2D) layers, including those of transition metal dichalcogenides (TMDs), is needed for future optoelectronic applications. Here, the near-field coupling between TMDs and graphene/graphite is used to engineer the exciton line shape and charge state. Fano-like asymmetric spectral features are produced in WS2, MoSe2, and WSe2van der Waals heterostructures combined with graphene, graphite, or jointly with hexagonal boron nitride (h-BN) as supporting or encapsulating layers. Furthermore, trion emission is suppressed in h-BN encapsulated WSe2/graphene with a neutral exciton red shift (44 meV) and binding energy reduction (30 meV). The response of these systems to electron beam and light probes is well-described in terms of 2D optical conductivities of the involved materials. Beyond fundamental insights into the interaction of TMD excitons with structured environments, this study opens an unexplored avenue toward shaping the spectral profile of narrow optical modes for application in nanophotonic devices.

Polaritons are compositional light-matter quasiparticles that have enabled remarkable breakthroughs in quantum and nonlinear optics, as well as in material science. Recently, plasmon–exciton polaritons (plexcitons) have been realized in hybrid material systems composed of transition metal dichalcogenide (TMDC) materials and metal nanoparticles, expanding polaritonic concepts to room temperature and nanoscale systems that also benefit from the exotic properties of TMDC materials. Despite the enormous progress in understanding TMDC-based plexcitons using optical-based methods, experimental evidence of plexcitons formation has remained indirect and mapping their nanometer-scale characteristics has remained an open challenge. Here, we demonstrate that plexcitons generated by a hybrid system composed of an individual silver nanoparticle and a few-layer WS2flake can be spectroscopically mapped with nanometer spatial resolution using electron energy loss spectroscopy in a scanning transmission electron microscope. Experimental anticrossing measurements using the absorption-dominated extinction signal provide the ultimate evidence for plexciton hybridization in the strong coupling regime. Spatially resolved EELS maps reveal the existence of unexpected nanoscale variations in the deep-subwavelength nature of plexcitons generated by this system. These findings pioneer new possibilities for in-depth studies of the local atomic structure dependence of polariton-related phenomena in TMDC hybrid material systems with nanometer spatial resolution.

Progress in electron-beam spectroscopies has recently enabled the study of optical excitations with combined space, energy and time resolution in the nanometre, millielectronvolt and femtosecond domain, thus providing unique access into nanophotonic structures and their detailed optical responses. These techniques rely on ~1–300 keV electron beams focused at the sample down to sub-nanometre spots, temporally compressed in wavepackets a few femtoseconds long, and in some cases controlled by ultrafast light pulses. The electrons undergo energy losses and gains (also giving rise to cathodoluminescence light emission), which are recorded to reveal the optical landscape along the beam path. This Review portraits these advances, with a focus on coherent excitations, emphasizing the increasing level of control over the electron wavefunctions and ensuing applications in the study and technological use of optically resonant modes and polaritons in nanoparticles, 2D materials and engineered nanostructures.

The physical properties of metals change when their dimensions are reduced to the nano-scale and new phenomena such as the localized surface-plasmon resonance (LSPR) appear. This collective electronic excitation can be tuned over a large spectral range by adapting the material, size and shape. The existing literature is as rich as it is controversial—for example, size-dependent spectral shifts of the LSPR in small metal nanoparticles, induced by quantum effects, are reported to the red, to the blue or entirely absent. Here we report how complementary experiments on size-selected small silver nanoparticles embedded in silica can yield inconsistent results on the same system: whereas optical absorption shows no size effect in the range between only a few atoms and ~10 nm, a clear spectral shift is observed in single-particle electron spectroscopy. Our quantitative interpretation, based on a mixed classical/quantum model, resolves the apparent contradictions, not only within our experimental data, but also in the literature. Our comprehensive model describes how the local environment is the crucial parameter controlling the manifestation or absence of quantum size effects.

The orthogonal eigenmodes are well-defined solutions of Hermitian equations describing many physical situations from quantum mechanics to acoustics. However, a large variety of non-Hermitian problems, including gravitational waves close to black holes or leaky electromagnetic cavities, require the use of a bi-orthogonal eigenbasis with consequences challenging our physical understanding1–4 . The need to compensate for energy losses made the few successful attempts5–8 to experimentally probe non-Hermiticity extremely complicated. We overcome this problem by considering localized plasmonic systems. As the non-Hermiticity in these systems does not stem from temporal invariance breaking but from spatial symmetry breaking, its consequences can be observed more easily. We report on the theoretical and experimental evidence for non-Hermiticity-induced strong coupling between surface plasmon modes of different orders within silver nanodaggers. The symmetry conditions for triggering this counter-intuitive self-hybridization phenomenon are provided. Similar observable effects are expected to exist in any system exhibiting bi-orthogonal eigenmodes. A combined theoretical and experimental study of plasmonic nanostructures reveals a self-hybridization effect that arises from the non-Hermitian eigenmodes of localized surface plasmons.

Le même formalisme est utilisé pour expliquer la diffraction par l’ADN et par les nanotubes de carbone ou leurs analogues d’oxydes métalliques, les nanotubes d’imogolite.

With the help of electron energy loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM) and boundary element method (BEM) simulations, we have shown that silver nanocross can be used to tune the plasmon modes and especially the higher order modes in a very controlled manner. Morphing a nanorod to a nanocross by growing another arm along the perpendicular bisector of a nanorod can lead to a spectacular evolution of various order modes in the EEL spectra. One can keep a mode fixed in energy while bringing the next higher order mode close to it, or even make it cross. This allows one to control the relative separation of energy of the plasmon modes. Hybridization of individual nanocross plasmon modes have also been studied by bringing two nanocrosses close together along one of their arms. An analytical approach based on first order perturbation theory and symmetry arguments based on group theory aptly fits the experimental observations.

Abstract

In bester Ordnung: Ce2Zr2O8‐Nanokristalle wurden durch aberrationskorrigierte Elektronenmikroskopie und Rumpfelektronen‐Energieverlustspektroskopie charakterisiert und in Simulationen untersucht. Dabei gelang der direkte chemische Nachweis für ein geordnetes Kationengitter in Nanokristalliten von 20–30 nm Größe. Lokale Abweichungen der chemischen Zusammensetzung folgen aus der Besetzung von Ce‐Plätzen durch Zr (siehe Schema).

New order: Ce2Zr2O8nanocrystals are characterized by aberration‐corrected electron microscopy, core‐loss electron energy‐loss spectroscopy, and simulations. Direct chemical evidence of an ordered cation sublattice in nanosized (20–30 nm) crystallites is found for the first time. Local deviations in the chemical composition are also detected, with Zr occupying Ce sites (see scheme).

Silver nanorods (AgNRs) with a controllable aspect ratio can be formed by templated growth from pentatwinned seeds. However, it is challenging to control the volume of the AgNRs and their aspect ratio independently because of the selective protection against growth of the lateral facets by halides. Here we demonstrate the preparation of AgNRs with tunable width via the addition of dimethyl sulfoxide (DMSO). AgNRs with custom dimensions were produced by separating the longitudinal and transverse growth in a two-step procedure. In the first step, the length is tuned by directing the overgrowth on the {111} tips of the AgNRs. In the second step, the width is adjusted by directing the overgrowth on the {100} lateral facets in the presence of DMSO. AgNRs of varying dimensions were obtained and characterized by a combination of techniques including scanning transmission electron microscopy, electron energy loss spectroscopy, and cathodoluminescence, which are, respectively, sensitive to the extinction and scattering component of the AgNRs’ response. This method allows tuning the plasmon energies, but also the ratio of the scattering and absorption contributions.

Structural, electronic, and chemical nanoscale modifications of transition metal dichalcogenide monolayers alter their optical properties. A key missing element for complete control is a direct spatial correlation of optical response to nanoscale modifications due to the large gap in spatial resolution between optical spectroscopy and nanometer-resolved techniques. Here, we bridge this gap by obtaining nanometer-resolved optical properties using electron spectroscopy at cryogenic temperatures, specifically electron energy loss spectroscopy for absorption and cathodoluminescence for emission, which are then directly correlated to chemical and structural information. In an h-BN/WS2/h-BN heterostructure, we observe local modulation of the trion (X–) emission due to tens of nanometer wide dielectric patches. Trion emission also increases in regions where charge accumulation occurs, close to the carbon film supporting the heterostructures. The localized exciton emission (L) detected here is not correlated to strain above 1%, suggesting point defects might be involved in their formation.

Single-wire light-emitting diodes based on radial p-i-n multi quantum well (QW) junctions have been realized from GaN wires grown by catalyst-free metal organic vapor phase epitaxy. The InxGa1-xN/GaN undoped QW system is coated over both the nonpolar lateral sidewalls and on the polar upper surface. Cathodo- and electroluminescence (EL) experiments provide evidence that the polar QWs emit in the visible spectral range at systematically lower energy than the nonpolar QWs. The EL of the polar or nonpolar QWs can be selectively activated by varying the sample temperature and current injection level.