Analytical electron microscopy analysis of insulating and metallic phases in nanostructured vanadium dioxide.

Vanadium dioxide (VO2) is a strongly correlated material that exhibits the insulator-to-metal transition (IMT) near room temperature, which makes it a promising candidate for applications in nanophotonics or optoelectronics. However, creating VO2 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 VO2 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 the 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 VO2 samples.

MXenes with ordered triatomic-layer borate polyanion terminations.

Surface terminations profoundly influence the intrinsic properties of MXenes, but existing terminations are limited to monoatomic layers or simple groups, showing disordered arrangements and inferior stability. Here we present the synthesis of MXenes with triatomic-layer borate polyanion terminations (OBO terminations) through a flux-assisted eutectic molten etching approach. During the synthesis, Lewis acidic salts act as the etching agent to obtain the MXene backbone, while borax generates BO2- species, which cap the MXene surface with an O-B-O configuration. In contrast to conventional chlorine/oxygen-terminated Nb2C with localized charge transport, OBO-terminated Nb2C features band transport described by the Drude model, exhibiting a 15-fold increase in electrical conductivity and a 10-fold improvement in charge mobility at the d.c. limit. This transition is attributed to surface ordering that effectively mitigates charge carrier backscattering and trapping. Additionally, OBO terminations provide Ti3C2 MXene with substantially enriched Li+-hosting sites and thereby a large charge-storage capacity of 420 mAh g-1. Our findings illustrate the potential of intricate termination configurations in MXenes and their applications for (opto)electronics and energy storage.

2D calculation of parasitic fields in misaligned multipole electron-optical systems.

The effects of geometrical imperfections in electron-optical components are usually evaluated in 3D simulations. These calculations inherently take a long time, require a large amount of memory, and do not directly produce the necessary axial field functions. We present a 2D perturbation method to calculate parasitic fields in misaligned multipole systems. Our method is based on finding an equivalent potential perturbation, similarly to Sturrock's method, but does not rely on the potential being differentiable. The method is directly applicable to both electrostatic and non-saturated magnetic problems. It does not require any 3D data and it is fully compatible with existing finite element method codes such as EOD. The proposed method produces axial field functions with an accuracy of units to a few tens of percents, depending on the number of unperturbed multipole field components used and the geometry. The results can then be used, for instance, to determine the parasitic imaging aberrations of the misaligned optical system using standard methods, in order to evaluate the effect of mechanical design tolerances.

Correlative Imaging of Individual CsPbBr3 Nanocrystals: Role of Isolated Grains in Photoluminescence of Perovskite Polycrystalline Thin Films.

We report on the optical properties of a CsPbBr3 polycrystalline thin film on a single grain level. A sample composed 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 a blue shift up to 9 nm for the smallest analyzed NCs. The magnitude of the blueshift is smaller than the emission line width, thus detectable only by high-resolution PL mapping. By comparing the emission energies obtained from the experiment and a rigorous effective mass model, we can fully attribute the observed variations to the size-dependent quantum confinement effect.

Plasmonic Properties of Individual Gallium Nanoparticles.

Gallium is a plasmonic material offering ultraviolet to near-infrared tunability, facile and scalable preparation, and good stability of nanoparticles. In this work, 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 and 200 nm were grown directly on a silicon nitride membrane using an effusion cell developed in house that was operated under ultra-high-vacuum conditions. We have experimentally proven that they support localized surface plasmon resonances and their dipole mode can be tuned through their size from the ultraviolet to near-infrared spectral region. The measurements are supported by numerical simulations using realistic particle shapes and sizes. Our results pave the way for future applications of gallium nanoparticles such as hyperspectral absorption of sunlight in energy harvesting or plasmon-enhanced luminescence of ultraviolet emitters.

Low temperature 2D GaN growth on Si(111) 7 × 7 assisted by hyperthermal nitrogen ions.

As the characteristic dimensions of modern top-down devices are getting smaller, such devices reach their operational limits imposed by quantum mechanics. Thus, two-dimensional (2D) structures appear to be 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) 7 × 7 surface using post-nitridation of Ga droplets by hyperthermal (E = 50 eV) nitrogen ions at low substrate temperatures (T < 220 °C). The deposition of Ga droplets and their post-nitridation are carried out using an effusion cell and a special atom/ion beam source developed by our group, respectively. This low-temperature droplet epitaxy (LTDE) approach provides well-defined ultra-high vacuum growth conditions during the whole fabrication process resulting in unique 2D GaN nanostructures. A sharp interface between the GaN nanostructures and the silicon substrate together with a suitable elemental composition of nanostructures was confirmed by TEM. In addition, SEM, X-ray photoelectron spectroscopy (XPS), AFM and Auger microanalysis were successful in enabling a detailed characterization of the fabricated GaN nanostructures.

Controlling the Metamagnetic Phase Transition in FeRh/MnRh Superlattices and Thin-Film Fe50-xMnxRh50 Alloys.

Equiatomic and chemically ordered FeRh and MnRh compounds feature a first-order metamagnetic phase transition between antiferromagnetic and ferromagnetic order in the vicinity of room temperature, exhibiting interconnected structural, magnetic, and electronic order parameters. We show that these two alloys can be combined to form hybrid metamagnets in the form of sputter-deposited superlattices and alloys on single-crystalline MgO substrates. Despite being structurally different, the magnetic behavior of the alloys with substantial Mn content resembles that of the FeRh/MnRh superlattices in the ultrathin individual layer limit. For FeRh/MnRh superlattices, dissimilar lattice distortions of the constituent FeRh and MnRh layers at the antiferromagnetic-ferromagnetic transition cause double-step transitions during cooling, while the magnetization during the heating branch shows a smooth, continuous trend. For Fe50-xMnxRh50 alloy films, the substitution of Mn at the Fe sites introduces an effective tensile in-plane strain and magnetic frustration in the highly ordered epitaxial films, largely influencing the phase transition temperature TM (by more than 150 K). In addition, Mn acts as a surfactant, enabling the growth of continuous thin films at higher temperatures. Thus, the introduction of hybrid FeRh-MnRh systems with adjustable parameters provides a pathway for the realization of tunable spintronic devices based on magnetic phase transitions.

Fundamental Limit of Plasmonic Cathodoluminescence.

We use cathodoluminescence (CL) spectroscopy in a transmission electron microscope to probe the radial breathing mode of plasmonic silver nanodisks. A two-mirror detection system sandwiching the sample collects the CL emission in both directions, that is, backward and forward with respect to the electron beam trajectory. We unambiguously identify a spectral shift of about 8 nm in the CL spectra acquired from both sides and show that this asymmetry is induced by the electron beam itself. By numerical simulations, we confirm the observations and identify the underlying physical effect due to the interference of the CL emission patterns of an electron-beam-induced dipole and the breathing mode. This effect can ultimately limit the achievable fidelity in CL measurements on any system involving multiple excitations and should therefore be considered with care in high-precision experiments.

Structural and optical properties of monocrystalline and polycrystalline gold plasmonic nanorods.

The quality of lithographically prepared structures is intimately related to the properties of the metal film from which they are fabricated. Here we compare two kinds of thin gold films on a silicon nitride membrane: a conventional polycrystalline thin film deposited by magnetron sputtering and monocrystalline gold microplates that 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. The structural and optical properties of the nanorods were characterized by analytical transmission electron microscopy including electron energy loss spectroscopy. The dimensions of the nanorods in both substrates reproduced well the designed size of 240×80 nm2 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, monocrystalline nanorods featured inclined boundaries while the boundaries of the polycrystalline nanorods were upright. Q factors and peak loss probabilities of the modes in both structures are within the experimental uncertainty identical. We demonstrate that the optical response of the plasmonic nanorods is not deteriorated when the polycrystalline metal is used instead of the monocrystalline metal.

Influence of experimental conditions on localized surface plasmon resonances measurement by electron energy loss spectroscopy.

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 found that the primary beam energy should be high enough to suppress the scattering in the sample and at the same time should be low enough to avoid the appearance of relativistic effects. Consequently, 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.

Fundamentals of cathodoluminescence in a STEM: The impact of sample geometry and electron beam energy on light emission of semiconductors.

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 Mönch 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.

Comparative study of plasmonic antennas fabricated by electron beam and focused ion beam lithography.

We present a comparative study of plasmonic antennas fabricated by electron beam lithography and direct focused ion beam milling. We have investigated optical and structural properties and chemical composition of gold disc-shaped plasmonic antennas on a silicon nitride membrane fabricated by both methods to identify their advantages and disadvantages. Plasmonic antennas were characterized using transmission electron microscopy including electron energy loss spectroscopy and energy dispersive X-ray spectroscopy, and atomic force microscopy. We have found stronger plasmonic response with better field confinement in the antennas fabricated by electron beam lithography, which is attributed to their better structural quality, homogeneous thickness, and only moderate contamination mostly of organic nature. Plasmonic antennas fabricated by focused ion beam lithography feature weaker plasmonic response, lower structural quality with pronounced thickness fluctuations, and strong contamination, both organic and inorganic, including implanted ions from the focused beam. While both techniques are suitable for the fabrication of plasmonic antennas, electron beam lithography shall be prioritized over focused ion beam lithography due to better quality and performance of its products.

Accurate interpolation of 3D fields in charged particle optics.

Standard 3D interpolation polynomials often suffer from numerical errors of the calculated field and lack of node points in the 3D solution. We introduce a novel method for accurate and smooth interpolation of arbitrary electromagnetic fields in the vicinity of the optical axis valid up to 90% of the bore radius. Our method combines Fourier analysis and Gaussian wavelet interpolation and provides the axial multipole field functions and their derivatives analytically. The results are accurate and noiseless, usually up to the 5th derivative. This is very advantageous for further applications, such as accurate particle tracing, and evaluation of aberration coefficients and other optical properties. The proposed method also enables studying the strength and orientation of all multipole field components. To illustrate the capabilities of the proposed algorithm, we present three examples: a magnetic lens with a hole in the polepiece, a saturated magnetic lens with an elliptic polepiece, and an electrostatic 8-electrode multipole.

The Cerenkov limit of Si, GaAs and GaP in electron energy loss spectrometry.

Since the advent of monochromated electron energy loss spectrometry (EELS) the experimental detection of band gaps in semiconducting materials is of great importance. In the non-relativistic limit of this technique the onset of the inelastic signal represents the band gap. But due to relativistic energy losses, like Cerenkov losses and the corresponding light guiding modes, appearing at high beam energies the band gap is usually hidden. The highest beam energy, which does not excite relativistic losses in a certain material, is called the Cerenkov limit of the material. In this work the low loss EELS signals of Si, GaAs and GaP are measured at various beam energies and the calculated Cerenkov limits are experimentally confirmed.

Strong near-field enhancement of radiative heat transfer between metallic surfaces.

Near-field heat transfer across a gap between plane-parallel tungsten layers in vacuo was studied experimentally with the temperature of the cold sample near 5 K and the temperature of the hot sample in the range 10-40 K as a function of the gap size d. At gaps smaller than one-third of the peak wavelength λ(m) given by Wien's displacement law, the near-field effect was observed. In comparison with blackbody radiation, hundred times higher values of heat flux were achieved at d≈1 µm. Heat flux normalized to the radiative power transferred between black surfaces showed scaling (λ(m)/d)(n), where n≈2.6. This Letter describes the results of experiment and a comparison with present theory over 4 orders of magnitude of heat flux.