Rik Brydson

Transformation of nanodiamond into carbon onions: A comparative study by high-resolution transmission electron microscopy, electron energy-loss spectroscopy, x-ray diffraction, small-angle x-ray scattering, and ultraviolet Raman spectroscopy

The structural properties of both nanodiamond particles synthesized by detonation and the products of their transformation into carbon onions via vacuum annealing at 1000 and 1500°C have been studied using high-resolution transmission electron microscopy (HRTEM), electron energy-loss spectroscopy, x-ray diffraction (XRD), small-angle x-ray scattering (SAXS), and Raman spectroscopy. The advantages of UV Raman spectroscopy over visible Raman spectroscopy for the analysis of these carbon nanomaterials are demonstrated. It was found that the synthesized nanodiamond particles have a composite core-shell structure comprising an ordered diamond core covered by a disordered (amorphous) outer shell formed by the mixed sp2∕sp3 bonding of carbon atoms. The observed structure of the nanodiamond particles are comparable with the structure of the bucky diamond clusters comprising a diamond core and a reconstructed surface which stabilizes the cluster at the average diameter of ∼30A, as predicted recently from theoretic...

Plant-driven fungal weathering: Early stages of mineral alteration at the nanometer scale

Plant-driven fungal weathering is a major pathway of soil formation, yet the precise mechanism by which mycorrhiza alter minerals is poorly understood. Here we report the first direct in situ observations of the effects of a soil fungus on the surface of a mineral over which it grew in a controlled experiment. An ectomycorrhizal fungus was grown in symbiosis with a tree seedling so that individual hyphae expanded across the surface of a biotite flake over a period of three months. Ultramicroscopic and spectroscopic analysis of the fungus-biotite interfaces revealed intimate fungal-mineral attachment, biomechanical forcing, altered interlayer spacings, substantial depletion of potassium (~50 nm depth), oxidation of the biotite Fe(II), and the formation of vermiculite and clusters of Fe(III) oxides. Our study demonstrates the biomechanical-chemical alteration interplay at the fungus-biotite interface at the nanometer scale. Specifically, the weathering process is initiated by physical distortion of the lattice structure of biotite within 1 μm of the attached fungal hypha. Only subsequently does the distorted volume become chemically altered through dissolution and oxidation reactions that lead to mineral neoformation.

Electron energy‐loss near‐edge structure – a tool for the investigation of electronic structure on the nanometre scale

Electron energy‐loss near‐edge structure (ELNES) is a technique that can be used to measure the electronic structure (i.e. bonding) in materials with subnanometre spatial resolution. This review covers the theoretical principles behind the technique, the experimental procedures necessary to acquire good ELNES spectra, including potential artefacts, and gives examples relevant to materials science.

3D morphology of the human hepatic ferritin mineral core: New evidence for a subunit structure revealed by single particle analysis of HAADF-STEM images

Ferritin, the major iron storage protein, has dual functions; it sequesters redox activity of intracellular iron and facilitates iron turn-over. Here we present high angle annular dark field (HAADF) images from individual hepatic ferritin cores within tissue sections, these images were obtained using spherical aberration corrected scanning transmission electron microscopy (STEM) under controlled electron fluence. HAADF images of the cores suggest a cubic morphology and a polycrystalline (ferrihydrite) subunit structure that is not evident in equivalent bright field images. By calibrating contrast levels in the HAADF images using quantitative electron energy loss spectroscopy, we have estimated the absolute iron content in any one core, and produced a three dimensional reconstruction of the average core morphology. The core is composed of up to eight subunits, consistent with the eight channels in the protein shell that deliver iron to the central cavity. We find no evidence of a crystallographic orientation relationship between core subunits. Our results confirm that the ferritin protein shell acts as a template for core morphology and within the core, small (∼2 nm), surface-disordered ferrihydrite subunits connect to leave a low density centre and a high surface area that would allow rapid turn-over of iron in biological systems.

Electron-energy-loss spectroscopy studies of Cu-α-Al2O3 interfaces grown by molecular beam epitaxy

Abstract The electron-energy-loss near-edge structure (ELNES) of a Cu-α-Al2O3 interface grown by molecular beam epitaxy has been studied using spatial difference electron-energy-loss spectroscopy in the scanning transmission electron microscope. Interpretation of the interface-specific Cu L2,3, Al L2,3 and O K ELNES components implies the existence of Cu-O bonding at the interface together with the retention of a local octahedral oxygen coordination of aluminium atoms and hence their non-participation in the interface plane. There is significant evidence for interfacial charge transfer from the copper layer to the oxygen layer, resulting in the existence of one monolayer of copper at the interface nominally in the Cu+ oxidation state. Furthermore, the ELNES studies reveal that the interfacial Cu-O bonds are of mixed ionic-covalent character. This becomes apparent when considering the O K ELNES where the presence of hybridized Cu 3d-O 2p states is indicated. The basal plane of α-Al2O3 at the interface is t...

Four-probe electrical transport measurements on individual metallic nanowires

This work presents nanoscale four-probe measurements on metallic nanowires using independently controlled scanning tunnelling microscope tips. This technique has allowed us to follow the change in resistance with probe separation. Gold, zinc and nickel nanowires were grown by electrodeposition within porous polycarbonate membranes. Their structure and composition were studied by transmission electron microscopy. Four-probe electrical transport measurements were taken using four independently controlled scanning tunnelling microscope tips positioned using a high resolution scanning electron microscope. Multiple I–V measurements were taken at varying tip separations, on each nanowire, and the change in resistance with separation was observed to be in good agreement with predictions based on the nanowire geometry. The resistivity values of the nanowires were found to be close to bulk values.

Highly Luminescent and Nontoxic Amine-Capped Nanoparticles from Porous Silicon: Synthesis and Their Use in Biomedical Imaging

Stable and brightly luminescent amine-terminated Si nanoparticles (SiNPs) have been synthesized from electrochemically etched porous silicon (PSi). The surface amine termination was confirmed by FTIR, NMR, and XPS studies. The mean diameter of the crystal core of 4.6 nm was measured by transmission electron microscopy (TEM), which is in a good agreement with the size obtained by dynamic light scattering (DLS). The dry, amine-terminated product can be obtained from bulk silicon wafers in less than 4 h. This represents a significant improvement over similar routines using PSi where times of >10 h are common. The emission quantum yield was found to be about 22% and the nanoparticles exhibited an exceptional stability over a wide pH range (4-14). They are resistant to aging over several weeks. The amine-terminated SiNPs showed no significant cytotoxic effects toward HepG2 cells, as assessed with MTT assays.

Investigating carbonization and graphitization using electron energy loss spectroscopy (EELS) in the transmission electron microscope (TEM)

Electron energy loss spectroscopy (EELS) in the transmission electron microscope (TEM) is explored as a useful characterization technique in the study of carbonization and graphitization of organic precursors. A model series of carbon materials was prepared from highly graphitizable petroleum pitch heat treated in the range 200–2730°C. Initial characterization was performed using the established techniques of X-ray diffraction (XRD), He pycnometry, TEM, electron diffraction and high-resolution lattice imaging (HREM). EELS in the TEM was then examined. Two routes are presented to quantify the change in the proportion of sp 2 type hybridization accompanying the heat treatment as the material transforms to the graphitic state. Both routes suggest an initial relative sp 2 content of ∼70%, rapidly increasing to ∼90% during mesophase development and carbonization, and then slowly increasing to 100% during graphitization. The peak position of the bulk valence plasmon (π + σ) is shown to be an excellent measure of the degree of graphitic character, and its fundamental dependence upon sample density (ρ) is confirmed. The appearance and definition of features within the core loss region representing the density of unoccupied σ* states are demonstrated to be an excellent measure of the extent of order. Finally, a method is established by which to extract the C–C bond length from core loss EELS spectra with an accuracy of ±0.1 pm. This method suggests an average bond length of 1.44 Å in samples with low heat treatment temperatures, decreasing to the theoretical length of 1.42 Å as both the heteroatom content and proportion of non-sp 2-type hybridized carbon atoms decrease.

Quantitative valence plasmon mapping in the TEM: viewing physical properties at the nanoscale

Using a series of graphitising carbons heat treated at different temperatures, the peak position of the bulk (pi+sigma) plasmon was measured using electron energy loss spectroscopy and observed to shift between 22 and 27eV. Experimental data is presented and discussed showing the effects of the collection conditions and sample orientation upon the observed spectra. We present an empirical technique by which quantitative energy filtered transmission electron microscopy (EFTEM) maps with two energy windows selected in the plasmon region can be readily acquired and processed, the results of which may be interpreted as graphitisation maps and subsequently physical property maps. An experimentally established resolution of approximately 1.6nm makes this technique a very useful tool with which to examine nanoscale properties in microstructural regions of interest in TEM specimens such as fibre/matrix interfaces within carbon-carbon composites, multi-walled carbon nanotubes and graphitic inclusions in carbon steels. Also presented is data demonstrating the unsuitability of pi(*)-related chemical EFTEM maps in both the low-loss region and at the carbon K ionisation edge for mapping bonding in such highly anisotropic media due to the strong orientation dependence of the intensity of the transitions involved. This is followed by suggestions for wider application of the plasmon mapping technique within systems other than those based upon carbon.

Enhanced photocatalytic hydrogen generation using polymorphic macroporous TaON.

Macroporous TaON (mac-TaON) is prepared using polymer sphere templating and controlled ammonolysis. In contrast to typical powder synthesis, which gives the β polymorph, mac-TaON is a mixture of β and γ polymorphs. mac-TaON shows twice the activity for photocatalytic hydrogen generation in comparison to mac-TaON when normalised for surface area.