Density, sp3 content and internal layering of DLC films by X-ray reflectivity and electron energy loss spectroscopy

A variety of hydrogenated and non-hydrogenated amorphous carbon thin films have been characterized by means of grazing-incidence X-ray reflectivity (XRR) to give information about their density, thickness, surface roughness and layering. We used XRR to validate the density of ta-C, ta-C:H and a-C:H films derived from the valence plasmon in electron energy loss spectroscopy measurements, up to 3.26 and 2.39 g/cm3 for ta-C and ta-C:H, respectively. By comparing XRR and electron energy loss spectroscopy (EELS) data, we have been able for the first time to fit a common electron effective mass of m*/me = 0.87 for all amorphous carbons and diamond, validating the `quasi-free' electron approach to density from valence plasmon energy. While hydrogenated films are found to be substantially uniform in density across the film, ta-C films grown by the filtered cathodic vacuum arc (FCVA) show a multilayer structure. However, ta-C films grown with an S-bend filter show a high uniformity and only a slight dependence on the substrate bias of both sp3 and layering.

X-ray propagation in carbon nanotubes

The maintenance of the growth of the multibillion-dollar semiconductor industry requires the development of techniques for the fabrication and characterisation of nanoscale devices. Consequently, there is great interest in photolithography techniques such as extreme UV and x-ray. Both of these techniques are extremely expensive and technologically very demanding. In this paper we describe research on the feasibility of exploiting x-ray propagation within carbon nanotubes (CNT's) for the fabrication and characterisation of nanoscale devices. This work discusses the parameters determining the design space available. To demonstrate experimentally the feasibility of x-ray propagation, arrays of carbon nanotubes have been grown on silicon membranes. The latter are required to provide structural support for the CNT's while minimising energy loss. To form a waveguide metal is deposited between the nanotubes to block x-ray transmission in this region at the same time as cladding the CNT's. The major challenge has been to fill the spaces between the CNT's with material of sufficient thickness to block x-ray transmission while maintaining the structural integrity of the CNT's. Various techniques have been employed to fill the gaps between the nanotubes including electroplating, sputtering and evaporation. This work highlights challenges encountered in optimising the process.

Extraction of fibre network architecture by X-ray tomography and prediction of elastic properties using an affine analytical model

This paper proposes a method for extracting reliable architectural characteristics from complex porous structures using micro-computed tomography (μCT) images. The work focuses on a highly porous material composed of a network of fibres bonded together. The segmentation process, allowing separation of the fibres from the remainder of the image, is the most critical step in constructing an accurate representation of the network architecture. Segmentation methods, based on local and global thresholding, were investigated and evaluated by a quantitative comparison of the architectural parameters they yielded, such as the fibre orientation and segment length (sections between joints) distributions and the number of inter-fibre crossings. To improve segmentation accuracy, a deconvolution algorithm was proposed to restore the original images. The efficacy of the proposed method was verified by comparing μCT network architectural characteristics with those obtained using high resolution CT scans (nanoCT). The results indicate that this approach resolves the architecture of these complex networks and produces results approaching the quality of nanoCT scans. The extracted architectural parameters were used in conjunction with an affine analytical model to predict the axial and transverse stiffnesses of the fibre network. Transverse stiffness predictions were compared with experimentally measured values obtained by vibration testing. © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Preparation and characterization of a novel pyrrole-benzophenone copolymerized silica nanocomposite as a reagent in a visual immunologic-agglutination test.

Biological sensing is explored through novel stable colloidal dispersions of pyrrole-benzophenone and pyrrole copolymerized silica (PPy-SiO(2)-PPyBPh) nanocomposites, which allow covalent linking of biological molecules through light mediation. The mechanism of nanocomposite attachment to a model protein is studied by gold labeled cholera toxin B (CTB) to enhance the contrast in electron microscopy imaging. The biological test itself is carried out without gold labeling, i.e., using CTB only. The protein is shown to be covalently bound through the benzophenone groups. When the reactive PPy-SiO(2)-PPyBPh-CTB nanocomposite is exposed to specific recognition anti-CTB immunoglobulins, a qualitative visual agglutination assay occurs spontaneously, producing as a positive test, PPy-SiO(2)-PPyBPh-CTB-anti-CTB, in less than 1 h, while the control solution of the PPy-SiO(2)-PPyBPh-CTB alone remained well-dispersed during the same period. These dispersions were characterized by cryogenic transmission microscopy (cryo-TEM), scanning electron microscopy (SEM), FTIR and X-ray photoelectron spectroscopy (XPS).

X-ray observation of micro-failures in granular piles approaching an avalanche

An X-ray imaging technique is used to probe the stability of 3-dimensional granular packs in a slowly rotating drum. Well before the surface reaches the avalanche angle, we observe intermittent plastic events associated with collective rearrangements of the grains located in the vicinity of the free surface. The energy released by these discrete events grows as the system approaches the avalanche threshold. By testing various preparation methods, we show that the pre-avalanche dynamics is not solely controlled by the difference between the free surface inclination and the avalanche angle. As a consequence, the measure of the pre-avalanche dynamics is unlikely to serve as a tool for predicting macroscopic avalanches.

The geometry and the number of contacts of monodisperse sphere packs using X-ray tomography

The three-dimensional structure of very large samples of monodisperse bead packs is studied by means of X-Ray Computed Tomography. We retrieve the coordinatesofeach bead inthe pack and wecalculate the average coordination number by using the tomographic images to single out the neighbors in contact. The results are compared with the average coordination number obtained in Aste et al. (2005) by using a deconvolution technique. We show that the coordination number increases with the packing fraction, varying between 6.9 and 8.2 for packing fractions between 0.59 and 0.64. © 2005 Taylor & Francis Group.

Local structure of Mn in (La1-xHox) 2/3Ca1/3MnO3 studied by X-ray absorption fine structure

Results of X-ray absorption fine structure measurements in manganites (La1-xHox)2/3Ca1/3MnO3 with 0.15 < x < 0.50 are presented. When LaMnO3 is doped with a, divalent element such as Ca2+, substituting for La3+, holes are induced in the filled Mn d orbitais. This leads to a, strong ferromagnetic coupling between Mn sites. Ca ions in La1-xCa xMnO3 introduce a distortion of the crystal lattice and mixed valence Mn ions (Mn3+ and Mn4+). On the other hand, in manganites (La1-xHox)2/3Ca 1/3MnO3 the substitution of La for Ho causes a lattice distortion and induces a disorder, which reduces a magnetic interaction. The ferromagnetic transition temperature and conductivity decrease very quickly with increasing x. The magnetic and transport properties of compounds depend on the local atomic structure around Mn ions. The information on the bond lengths and Debye-Waller factor are obtained from the extended X-ray absorption fine structure (EXAFS) data analysis. The charge state of Mn is determined from the position of the absorption edge in X-ray absorption near edge structure (XANES) data. XAFS results are in good agreement with magnetic characteristics of the studied materials.

Cortical thickness estimation of the proximal femur from multi-view Dual-Energy X-ray Absorptiometry (DXA)

Hip fracture is the leading cause of acute orthopaedic hospital admission amongst the elderly, with around a third of patients not surviving one year post-fracture. Although various preventative therapies are available, patient selection is difficult. The current state-of-the-art risk assessment tool (FRAX) ignores focal structural defects, such as cortical bone thinning, a critical component in characterizing hip fragility. Cortical thickness can be measured using CT, but this is expensive and involves a significant radiation dose. Instead, Dual-Energy X-ray Absorptiometry (DXA) is currently the preferred imaging modality for assessing hip fracture risk and is used routinely in clinical practice. Our ambition is to develop a tool to measure cortical thickness using multi-view DXA instead of CT. In this initial study, we work with digitally reconstructed radiographs (DRRs) derived from CT data as a surrogate for DXA scans: this enables us to compare directly the thickness estimates with the gold standard CT results. Our approach involves a model-based femoral shape reconstruction followed by a data-driven algorithm to extract numerous cortical thickness point estimates. In a series of experiments on the shaft and trochanteric regions of 48 proximal femurs, we validated our algorithm and established its performance limits using 20 views in the range 0°-171°: estimation errors were 0:19 ± 0:53mm (mean +/- one standard deviation). In a more clinically viable protocol using four views in the range 0°-51°, where no other bony structures obstruct the projection of the femur, measurement errors were -0:07 ± 0:79 mm. © 2013 SPIE.

In situ observations of the atomistic mechanisms of Ni catalyzed low temperature graphene growth.

The key atomistic mechanisms of graphene formation on Ni for technologically relevant hydrocarbon exposures below 600 °C are directly revealed via complementary in situ scanning tunneling microscopy and X-ray photoelectron spectroscopy. For clean Ni(111) below 500 °C, two different surface carbide (Ni2C) conversion mechanisms are dominant which both yield epitaxial graphene, whereas above 500 °C, graphene predominantly grows directly on Ni(111) via replacement mechanisms leading to embedded epitaxial and/or rotated graphene domains. Upon cooling, additional carbon structures form exclusively underneath rotated graphene domains. The dominant graphene growth mechanism also critically depends on the near-surface carbon concentration and hence is intimately linked to the full history of the catalyst and all possible sources of contamination. The detailed XPS fingerprinting of these processes allows a direct link to high pressure XPS measurements of a wide range of growth conditions, including polycrystalline Ni catalysts and recipes commonly used in industrial reactors for graphene and carbon nanotube CVD. This enables an unambiguous and consistent interpretation of prior literature and an assessment of how the quality/structure of as-grown carbon nanostructures relates to the growth modes.

Observing graphene grow: catalyst-graphene interactions during scalable graphene growth on polycrystalline copper.

Complementary in situ X-ray photoelectron spectroscopy (XPS), X-ray diffractometry, and environmental scanning electron microscopy are used to fingerprint the entire graphene chemical vapor deposition process on technologically important polycrystalline Cu catalysts to address the current lack of understanding of the underlying fundamental growth mechanisms and catalyst interactions. Graphene forms directly on metallic Cu during the high-temperature hydrocarbon exposure, whereby an upshift in the binding energies of the corresponding C1s XPS core level signatures is indicative of coupling between the Cu catalyst and the growing graphene. Minor carbon uptake into Cu can under certain conditions manifest itself as carbon precipitation upon cooling. Postgrowth, ambient air exposure even at room temperature decouples the graphene from Cu by (reversible) oxygen intercalation. The importance of these dynamic interactions is discussed for graphene growth, processing, and device integration.

Controlled amine functionality in self-assembled monolayers via the hidden amine route: chemical and electronic tunability.

A synthetic strategy for fabricating a dense amine functionalized self-assembled monolayer (SAM) on hydroxylated surfaces is presented. The assembly steps are monitored by X-ray photoelectron spectroscopy, Fourier transform infrared- attenuated total reflection, atomic force microscopy, variable angle spectroscopic ellipsometry, UV-vis surface spectroscopy, contact angle wettability, and contact potential difference measurements. The method applies alkylbromide-trichlorosilane for the fabrication of the SAM followed by surface transformation of the bromine moiety to amine by a two-step procedure: S(N)2 reaction that introduces the hidden amine, phthalimide, followed by the removal of the protecting group and exposing the free amine. The use of phthalimide moiety in the process enabled monitoring the substitution reaction rate on the surface (by absorption spectroscopy) and showed first-order kinetics. The simplicity of the process, nonharsh reagents, and short reaction time allow the use of such SAMs in molecular nanoelectronics applications, where complete control of the used SAM is needed. The different molecular dipole of each step of the process, which is verified by DFT calculations, supports the use of these SAMs as means to tune the electronic properties of semiconductors and for better synergism between SAMs and standard microelectronics processes and devices.