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Vanadium dioxide (VO$_2$) has received significant interest in the context of nanophotonic metamaterials and memories owing to its reversible insulator-metal transition associated with significant changes in its optical and electronic properties. While the VO$_2$ transition has been extensively studied for several decades, the hysteresis dynamics of individual single-crystal VO$_2$ nanoparticles (NPs) remains largely unexplored. Here, employing transmission electron microscopy techniques, we investigate phase transitions of single VO$_2$ NPs in real time. Our analysis reveals the statistical distribution of the transition temperature and steepness and how they differ during forward (heating) and backward (cooling) transitions. We assess the stability of coexisting phases in individual NPs and prove the persistent multilevel memory at near-room temperatures using only a few VO$_2$ NPs. Our findings shed new light on the underlying physical mechanisms governing the hysteresis of VO$_2$ and establish VO$_2$ NPs as a promising component of optoelectronic and memory devices with enhanced functionalities.

We present annular dark field scanning transmission electron microscopy (ADF-STEM) as an efficient, fast, and non-destructive nanoscale tool for monitoring solid-state phase transition. Using metal-insulator transition in vanadium dioxide nanoparticles as an example, we characterize lattice and electronic signatures of the phase transition using analytical transmission electron microscopy including diffraction and electron energy-loss spectroscopy. We demonstrate that ADF-STEM shows a clear contrast across the transition, interpreted with the help of convergent electron beam diffraction as stemming from the crystal-lattice modification accompanying the transition. In addition, ADF-STEM utilizes 3--6 orders of magnitude lower electron dose when compared to electron microscopy techniques able to reveal the phase transition with the same spatial resolution and universality. The benefits of ADF-STEM are emphasized by recording a full hysteresis loop for the metal-insulator transition of a single vanadium dioxide nanoparticle. Our study opens the prospect for fast, non-destructive, large-area and nanoscale characterization of solid-state phase transitions.

The plasmonic lightning-rod effect refers to the formation of a strong electric near field of localized surface plasmons at the sharp features of plasmonic antennas. While this effect is intuitively utilized in the design and optimization of plasmonic antennas, the relation between the magnitude of the electric field and the local curvature of the plasmonic antenna has not been yet rigorously established. Here, we provide such a study. We design sets of plasmonic antennas that allow to isolate the role of the local curvature from other effects influencing the field. The near electric field is inspected by electron energy loss spectroscopy and electrodynamic simulations. We demonstrate the existence of the plasmonic lightning-rod effect and establish its quantitative description, showing that its strength is comparable to the electrostatic lightning-rod effect. We also provide a simple phenomenological formula for the spatial dependence of the field. Finally, we introduce the effective radius of curvature related to the spatial distribution of induced charge in plasmonic antennas, significantly smaller than their geometrical radius.

The behavior of plasmonic antennas is influenced by a variety of factors, including their size, shape, and material. Even minor changes in the deposition parameters during the thin film preparation process may have a significant impact on the dielectric function of the film, and thus on the plasmonic properties of the resulting antenna. In this work, we deposited gold thin films with thicknesses of 20 nm, 30 nm, and 40 nm at various deposition rates using an ion-beam-assisted deposition. We evaluate their morphology and crystallography by atomic force microscopy, X ray diffraction, and transmission electron microscopy. Next, we examined the ease of fabricating plasmonic antennas using focused-ion-beam lithography. Finally, we evaluate their plasmonic properties by electron energy loss spectroscopy measurements of individual antennas. Our results show that the optimal gold thin film for plasmonic antenna fabrication of a thickness of 20 and 30 nm should be deposited at the deposition rate of around 0.1 nm/s. The thicker 40 nm film should be deposited at a higher deposition rate like 0.3 nm/s.

Vanadium dioxide (VO$_2$) is a strongly-correlated material that exhibits insulator-to-metal transition (IMT) near room temperature, which makes it a promising candidate for applications in nanophotonics or optoelectronics. However, creating VO$_2$ nanostructures with the desired functionality can be challenging due to microscopic inhomogeneities that can significantly impact the local optical and electronic properties. Thin lamellas, produced by focused ion beam milling from a homogeneous layer, provide a useful prototype for studying VO$_2$ at the truly microscopic level using a scanning transmission electron microscope (STEM). High-resolution imaging is used to identify structural inhomogeneities while electron energy-loss spectroscopy (EELS) supported by statistical analysis helps to detect V$_x$O$_y$ stoichiometries with a reduced oxidation number of vanadium at the areas of thickness below 70 nm. On the other hand, the thicker areas are dominated by vanadium dioxide, where the signatures of IMT are detected in both core-loss and low-loss EELS experiments with in-situ heating. The experimental results are interpreted with ab-initio and semi-classical calculations. This work shows that structural inhomogeneities such as pores and cracks present no harm to the desired optical properties of VO$_2$ samples.

Developing methods to sense local variations in nearby materials, such as their refractive index and thickness, is important in different fields including chemistry and biomedical applications, among others. Localized surface plasmons (LSPs) excited in plasmonic nanostructures have demonstrated to be useful in this context due to the spectral location of their associated resonances being sensitive to changes near the plasmonic structures. In this manuscript, Babinet's principle is explored by exploiting LSP resonances excited in complementary metal-dielectric cylindrical plasmonic structures (plasmonic particle-dimers and aperture-dimers in our case). Both plasmonic structures are evaluated numerically and experimentally using Electron Energy Loss Spectroscopy (EELS), providing a full physical understanding of the complementary nature of the excited LSP resonances. The studied plasmonic structures are then exploited for dielectric sensing under two configurations: when a thin dielectric film is positioned atop the plasmonic structures and when the analyte surrounds/fills the plasmonic particles/apertures. The complementary sensing performance of both proposed structures is also evaluated, showing the approximate validity of the Babinet principle with sensitivities values of up to 700 nm/RIU for thin dielectric sensing., Comment: 24 pages, 5 figures

We report on the optical properties of CsPbBr3 polycrystalline thin film on a single grain level. A sample comprised of isolated nanocrystals (NCs) mimicking the properties of the polycrystalline thin film grains that can be individually probed by photoluminescence spectroscopy was prepared. These NCs were analyzed using correlative microscopy allowing the examination of structural, chemical, and optical properties from identical sites. Our results show that the stoichiometry of the CsPbBr3 NCs is uniform and independent of the NCs' morphology. The photoluminescence (PL) peak emission wavelength is slightly dependent on the dimensions of NCs, with the blue shift up to 9 nm for the smallest analyzed NCs. The magnitude of the blueshift is smaller than the emission linewidth, thus detectable only by high-resolution PL mapping. By comparing the emission wavelengths obtained from the experiment and a rigorous effective mass model we can fully attribute the observed variations to the size-dependent quantum confinement effect., Comment: 25 pages, 3 figures

Electron energy loss spectroscopy (EELS) is often utilized to characterize localized surface plasmon modes supported by plasmonic antennas. However, the spectral resolution of this technique is only mediocre, and it can be rather difficult to resolve modes close in the energy, such as coupled modes of dimer antennas. Here we address this issue for a case study of the dimer plasmonic antenna composed of two gold discs. We analyze four nearly degenerate coupled plasmon modes of the dimer: longitudinal and transverse bonding and antibonding dipole modes. With a traditional approach, which takes into account the spectral response of the antennas recorded at specific points, the modes cannot be experimentally identified with EELS. Therefore, we employ the spectral and spatial sensitivity of EELS simultaneously. We propose several metrics that can be utilized to resolve the modes. First, we utilize electrodynamic simulations to verify that the metrics indeed represent the spectral positions of the plasmon modes. Next, we apply the metrics to experimental data, demonstrating their ability to resolve three of the above-mentioned modes (with transverse bonding and antibonding modes still unresolved), identify them unequivocally, and determine their energies. In this respect, the spatio-spectral metrics increase the information extracted from electron energy loss spectroscopy applied to plasmonic antennas.

Gallium is a plasmonic material offering ultraviolet to near-infrared tunability, facile and scalable preparation, and good stability of nanoparticles. In our contribution, we experimentally demonstrate the link between the shape and size of individual gallium nanoparticles and their optical properties. To this end, we utilize scanning transmission electron microscopy combined with electron energy loss spectroscopy. Lens-shaped gallium nanoparticles with a diameter between 10 nm and 200 nm were grown directly on a silicon nitride membrane using an in-house developed effusion cell operated at ultra-high vacuum conditions. We have experimentally proved that they support localized surface plasmon resonances and their dipole mode can be tuned through their size from ultraviolet to near-infrared spectral region. The measurements are supported by numerical simulations using realistic particle shapes and sizes. Our results open the way for future applications of gallium nanoparticles such as hyperspectral absorption of sunlight in energy harvesting or plasmon-enhanced luminescence of ultraviolet emitters.

As the characteristic dimensions of modern top-down devices are getting smaller, such devices reach their operational limits given by quantum mechanics. Thus, two-dimensional (2D) structures appear as one of the best solutions to meet the ultimate challenges of modern optoelectronic and spintronic applications. The representative of III-V semiconductors, gallium nitride (GaN), is a great candidate for UV and high-power applications at a nanoscale level. We propose a new way of fabrication of 2D GaN on the Si(111) 7x7 surface using post-nitridation of Ga droplets by hyperthermal (E < 50 eV) nitrogen ions at low substrate temperatures (T < 220{\deg}C). Both deposition of Ga droplets and their post-nitridation is carried out using a special atom-ion beam source developed in our group. This low-temperature droplet epitaxy (LTDE) approach provides well-defined ultra-high vacuum growth conditions during the whole fabrication process resulting in high purity GaN nanostructures. A sharp interface between the GaN nanostructures and the silicon substrate together with a correct elemental composition of nanostructures was confirmed by TEM. In addition, SEM, X-ray photoelectron spectroscopy (XPS), AFM and Auger microanalysis showed unique characteristics of the fabricated GaN nanostructures., Comment: 14 pages, 5 figures

Plasmonic structures are often fabricated by lithographic patterning of a thin metallic film. Properties of the thin film are intimately related to the quality of the resulting structures. Here we compare two kinds of thin gold films on silicon nitride membrane: a conventional polycrystalline thin film deposited by magnetron sputtering, and monocrystalline gold microplates which were chemically synthesised directly on the membrane's surface for the first time. Both pristine metals were used to fabricate plasmonic nanorods using focused ion beam lithography. Structural and optical properties of the nanorods were characterized by analytical transmission electron microscopy. The dimensions of the nanorods in both substrates reproduced well the designed size of $240 \times 80\ \mathrm{nm^2}$ with the deviations up to 20 nm in both length and width. The shape reproducibility was considerably improved among monocrystalline nanorods fabricated from the same microplate. Interestingly, monocrystal nanorods featured inclined boundaries while the boundaries of the polycrystal nanorods were upright. Q factors and peak loss probabilities of the modes in both structures are within the experimental uncertainty identical. We conclude that the optical response of the plasmonic antennas is not deteriorated when the polycrystalline metal is used instead of the monocrystalline metal.

Scanning transmission electron microscopy (STEM) combined with electron energy loss spectroscopy (EELS) has become a standard technique to map localized surface plasmon resonances with a nanometer spatial and a sufficient energy resolution over the last 15 years. However, no experimental work discussing the influence of experimental conditions during the measurement has been published up to now. We present an experimental study of the influence of the primary beam energy and the collection semi-angle on the plasmon resonances measurement by STEM-EELS. To explore the influence of these two experimental parameters we study a series of gold rods and gold bow-tie and diabolo antennas. We discuss the impact on experimental characteristics which are important for successful detection of the plasmon peak in EELS, namely: the intensity of plasmonic signal, the signal to background ratio, and the signal to zero-loss peak ratio. We show that the best results are obtained using a medium primary beam energy, in our case 120 keV, and an arbitrary collection semi-angle, as it is not a critical parameter at this primary beam energy. Our instructive overview will help microscopists in the field of plasmonics to arrange their experiments.

We revisit plasmonic modes in nanoparticle dimers with conductive or insulating junction resulting in conductive or capacitive coupling. In our study which combines electron energy loss spectroscopy, optical spectroscopy, and numerical simulations, we show coexistence of strongly and weakly hybridized modes. While the properties of the former ones strongly depend on the nature of the junction, the properties of the latter ones are nearly unaffected. This opens up a prospect for independent engineering of different plasmonic modes in a single plasmonic antenna. In addition, we show that Babinet's principle allows to engineer the near field of plasmonic modes independent of their energy. Finally, we demonstrate that combined electron energy loss imaging of a plasmonic antenna and its Babinet-complementary counterpart allows to reconstruct the distribution of both electric and magnetic near fields of localised plasmonic resonances supported by the antenna as well as charge and current antinodes of related charge oscillations.

Plasmonic nanoparticles from unconventional materials can improve or even bring some novel functionalities into the disciplines inherently related to plasmonics such as photochemistry or (spectro)electrochemistry. They can, for example, catalyze various chemical reactions or act as nanoelectrodes and optical transducers in various applications. Silver amalgam is the perfect example of such an unconventional plasmonic material, albeit it is well-known in the field of electrochemistry for its wide cathodic potential window and strong adsorption affinity of biomolecules to its surface. In this study, we investigate in detail the optical properties of nanoparticles and microparticles made from silver amalgam and correlate their plasmonic resonances with their morphology. We use optical spectroscopy techniques on the ensemble level and electron energy loss spectroscopy on the single-particle level to demonstrate the extremely wide spectral range covered by the silver amalgam localized plasmonic resonances, ranging from ultraviolet all the way to the mid-infrared wavelengths. Our results establish silver amalgam as a suitable material for introduction of plasmonic functionalities into photochemical and spectroelectrochemical systems, where the plasmonic enhancement of electromagnetic fields and light emission processes could synergistically meet with the superior electrochemical characteristics of mercury.

Cathodoluminescence has attracted interest in scanning transmission electron microscopy since the advent of commercial available detection systems with high efficiency, like the Gatan Vulcan or the Attolight M\"onch system. In this work we discuss light emission caused by high-energy electron beams when traversing a semiconducting specimen. We find that it is impossible to directly interpret the spectrum of the emitted light to the inter-band transitions excited by the electron beam, because the Cerenkov effect and the related light guiding modes as well as transition radiation is altering the spectra. Total inner reflection and subsequent interference effects are changing the spectral shape dependent on the sample shape and geometry, sample thickness, and beam energy, respectively. A detailed study on these parameters is given using silicon and GaAs as test materials., Comment: 21 pages, 16 figures

We theoretically study plasmonic antennas featuring areas of extremely concentrated electric or magnetic field, known as hot spots. We combine two types of electric-magnetic complementarity to increase the degree of freedom for the design of the antennas: bow-tie and diabolo duality and Babinet's principle. We evaluate the figures of merit for different plasmon-enhanced optical spectroscopy methods: field enhancement, decay rate enhancement, and quality factor of the plasmon resonances. The role of Babinet's principle in interchanging electric and magnetic field hot spots and its consequences for practical antenna design are discussed. In particular, diabolo antennas exhibit slightly better performance than bow-ties in terms of larger field enhancement and larger Q factor. For specific resonance frequency, diabolo antennas are considerably smaller than bow-ties which makes them favourable for the integration into more complex devices but also makes their fabrication more demanding in terms of spatial resolution. Finally, we propose Babinet-type dimer antenna featuring electromagnetic hot spot with both the electric and magnetic field components treated on equal footing.