Hydrogen and helium trapping in hcp beryllium.

Even though hydrogen-metal surface interactions play an important role in energy technologies and metal corrosion, a thorough understanding of these interactions at the nanoscale remains elusive due to obstructive detection limits in instrumentation and the volatility of pure hydrogen. In the present paper we use analytical spectroscopy in TEM to show that hydrogen adsorbs directly at the (0001) surfaces of hexagonal helium bubbles within neutron irradiated beryllium. In addition to hydrogen, we also found Al, Si and Mg at the beryllium-bubble interfaces. The strong attraction of these elements to (0001) surfaces is underlined with ab-initio calculations. In situ TEM heating experiments reveal that hydrogen can desorb from the bubble walls at T ≥ 400 °C if the helium content is reduced by opening the bubbles. Based on our results we suggest the formation of a complex hydride consisting of up to five elements with a remarkably high decomposition temperature. These results therefore promise novel insights into metal-hydrogen interaction behavior and are invaluable for the safety of future fusion power plants.

Chemical homogeneity and optical properties of individual sodium tungsten bronze nanocubes.

The sodium tungsten bronzes (NaxWO3) are sub-stoichiometric metal oxides with variable Na content described by x. Methods to determine the overall x of a sample are well-known, but variations of composition within a particle have not yet been explored. In this work, electron microscopy techniques are used to determine the crystallinity and chemical composition of individual Na0.83WO3 nanocubes. The particles are found to be single crystals, with the top and bottom faces of the nanocubes parallel to the {100} planes. Compositional homogeneity is observed within the particles other than an approximately ≈5 nm Na-depletion layer at the edge of the particle. An O-depleted layer, believed to be the result of beam damage, is observed when the beam is scanned slowly over the edge of the particle. Calculations of the plasmon responses using the boundary element method (BEM) show that this depletion layer has a minor impact on the optical properties of the large (190 nm) particle studied of this work, but is expected to have a dramatic impact for small (20 nm) particles.

The Quest for Zero Loss: Unconventional Materials for Plasmonics.

There has been an ongoing quest to optimize the materials used to build plasmonic devices: first the elements were investigated, then alloys and intermetallic compounds, later semiconductors were considered, and, most recently, there has been interest in using more exotic materials such as topological insulators and conducting oxides. The quality of the plasmon resonances in these materials is closely correlated with their structure and properties. In general gold and silver are the most commonly specified materials for these applications but they do have weaknesses. Here, it is shown how, in specific circumstances, the selection of certain other materials might be more useful. Candidate alternatives include Tix N, VO2 , Al, Cu, Al-doped ZnO, and Cu-Al alloys. The relative merits of these choices and the many pitfalls and subtle problems that arise are discussed, and a frank perspective on the field is provided.

Bulk scale fabrication of sodium tungsten bronze nanoparticles for applications in plasmonics.

In order to advance plasmon-based technologies, new materials with low damping losses and high chemical stability are needed. In this letter, we report the bulk scale fabrication of sodium tungsten bronze (Na x WO3) nanoparticles with high Na content (x ≤ 0.83) using a furnace-assisted method. Phase purity and morphology is confirmed with x-ray diffraction and scanning electron microscopy. Plasmon responses are characterized using spectrophotometry and spatially-resolved electron energy-loss spectroscopy (EELS) in a scanning transmission electron microscope. Experimental EELS maps of individual nanoparticles show the excitation of distinct plasmon resonances at visible and near-infrared (NIR) frequencies, and these observations are supported by boundary element method simulations. Na x WO3 is a promising alternative material for plasmonics due to its strong plasmon resonances when compared to Au, its simple nanofabrication, and low cost. In particular, their high NIR extinction makes these materials ideal for applications in solar control window coatings or plasmonic photocatalysis.

Optical properties and oxidation of α-phase Ag-Al thin films.

We investigate a series of Ag-Al thin films containing up to 12 at% Al with the purpose of discovering whether these alloys would be a better choice for nanophotonic applications than pure Ag. Variable angle spectroscopic ellipsometry, AFM, x-ray diffraction and density functional theory are applied to explore and characterize the materials. Electromagnetic simulations of optical properties are used to place the results into a theoretical framework. We find that the increase in electron-to-atom ratio associated with the Al additions changes the optical properties: additions of the order of 1-2 at% Al are beneficial as they are associated with favorable changes in the dielectric function, but for greater additions of Al there is a flattening of the absorption edge and an increase in optical loss. In addition, contents of more than about 2 at% Al are associated with the onset of time-dependent intergranular oxidation, which causes a pronounced dip in the reflectance spectrum at about 2.3-2.4 eV (∼500-540 nm).

Multipolar and dark-mode plasmon resonances on drilled silver nano-triangles.

Dark-mode plasmon resonances can be excited by positioning a suitable nano-antenna above a nanostructure to couple a planar incident wave-front into a virtual point source. We explore this phenomenon using a prototypical nanostructure consisting of a silver nanotriangle into which a hole has been drilled and a rod-like nano-antenna of variable aspect ratio. Using numerical simulations, we establish the behavior of the basic drilled nanotriangle under plane wave illumination and electron beam irradiation to provide a baseline, and then add the nano-antenna to investigate the stimulation of additional dark-mode plasmon resonances. The introduction of a suitably tuned nano-antenna provides a new and general means of exciting dark-mode resonances using plane wave light. The resulting system exhibits a very rich variety of radiant and sub-radiant resonance modes.

Light splitting in nanoporous gold and silver.

Nanoporous gold and silver exhibit strong, omnidirectional broad-band absorption in the far-field. Even though they consist entirely of gold or silver atoms, these materials appear black and dull, in great contrast with the familiar luster of continuous gold and silver. The nature of these anomalous optical characteristics is revealed here by combining nanoscale electron energy loss spectroscopy with discrete dipole and boundary element simulations. It is established that the strong broad-band absorption finds its origin in nanoscale splitting of light, with great local variations in the absorbed color. This nanoscale polychromaticity results from the excitation of localized surface plasmon resonances, which are imaged and analyzed here with deep sub-wavelength, nanometer spatial resolution. We demonstrate that, with this insight, it is possible to customize the absorbance and reflectance wavelength bands of thin nanoporous films by only tuning their morphology.

Optimizing EELS acquisition.

A method for spectral acquisition, called binned gain averaging, will be described and tested. Systematic or correlated noise is efficiently suppressed with this method by averaging the gain over a series of CCD pixels. As a result, improved signal-to-noise ratios are obtained that allow the detection of very weak signals. At the same time, the spectral energy resolution is not degraded--even for long acquisition periods. It will be demonstrated that with this method, it is possible to significantly enhance the acquisition speed and quality of electron energy-loss (EEL) spectra and EELS maps. Examples will be given of double ionic scattering (i.e. the detection of the second boron K-edge) and the mapping of gold surface plasmons in the near-infrared and visible energy range.

Quantitative TEM-based phase retrieval of MgO nano-cubes using the transport of intensity equation.

Through focus series of images are collected from MgO nano-cube crystals in the transmission electron microscope (TEM). The experimental data is used to solve the transport of intensity equation (TIE) to retrieve phase maps, which portray the morphology of the cubes and are quantified by the mean inner potential V(0). Particular attention is given to the practical difficulties associated with TIE phase retrieval of non-conducting polyhedron particles.

Astigmatic intensity equation for electron microscopy based phase retrieval.

Phase retrieval, in principle, can be performed in a transmission electron microscope (TEM) using arbitrary aberrations of electron waves; provided that the aberrations are well-characterised and known. For example, the transport of intensity equation (TIE) can be used to infer the phase from a through-focus series of images. In this work an "astigmatic intensity equation" (AIE) is considered, which relates phase gradients to intensity variations caused by TEM objective lens focus and astigmatism variations. Within the paraxial approximation, it is shown that an exact solution of the AIE for the phase can be obtained using efficient Fourier transform methods. Experimental requirements for using the AIE are the measurement of a through-focus derivative and another intensity derivative, which is taken with respect to objective lens astigmatism variation. Two quasi-experimental investigations are conducted to test the validity of the solution.