The phase of iron catalyst nanoparticles during carbon nanotube growth

We study the Fe-catalyzed chemical vapor deposition of carbon nanotubes by complementary in situ grazing-incidence X-ray diffraction, in situ X-ray reflectivity, and environmental transmission electron microscopy. We find that typical oxide supported Fe catalyst films form widely varying mixtures of bcc and fcc phased Fe nanoparticles upon reduction, which we ascribe to variations in minor commonly present carbon contamination levels. Depending on the as-formed phase composition, different growth modes occur upon hydrocarbon exposure: For γ-rich Fe nanoparticle distributions, metallic Fe is the active catalyst phase, implying that carbide formation is not a prerequisite for nanotube growth. For α-rich catalyst mixtures, Fe3C formation more readily occurs and constitutes part of the nanotube growth process. We propose that this behavior can be rationalized in terms of kinetically accessible pathways, which we discuss in the context of the bulk iron-carbon phase diagram with the inclusion of phase equilibrium lines for metastable Fe3C. Our results indicate that kinetic effects dominate the complex catalyst phase evolution during realistic CNT growth recipes. © 2012 American Chemical Society.

A non-intrusive in situ method of optical beam profiling in LCOS-based optical fiber switches

This paper proposed a non-intrusive method of measuring the optical beam profile at the surface of the liquid crystal on silicon (LCOS) device in an optical fiber switch. This method is based on blazed grating and can be employed in situ (on-line) for two-dimensional beam profiling in the LCOS-based optical fiber switches without introducing additional components or rearranging the system. The measured beam radius was in excellent agreement with that measured by the knife-edge technique. © 2013 Elsevier Ltd.

Transducer and base compliance alter the in situ 6 dof force measured from muscle during an isometric contraction in a multi-joint limb.

Although musculoskeletal models are commonly used, validating the muscle actions predicted by such models is often difficult. In situ isometric measurements are a possible solution. The base of the skeleton is immobilized and the endpoint of the limb is rigidly attached to a 6-axis force transducer. Individual muscles are stimulated and the resulting forces and moments recorded. Such analyses generally assume idealized conditions. In this study we have developed an analysis taking into account the compliances due to imperfect fixation of the skeleton, imperfect attachment of the force transducer, and extra degrees of freedom (dof) in the joints that sometimes become necessary in fixed end contractions. We use simulations of the rat hindlimb to illustrate the consequences of such compliances. We show that when the limb is overconstrained, i.e., when there are fewer dof within the limb than are restrained by the skeletal fixation, the compliances of the skeletal fixation and of the transducer attachment can significantly affect measured forces and moments. When the limb dofs and restrained dofs are matched, however, the measured forces and moments are independent of these compliances. We also show that this framework can be used to model limb dofs, so that rather than simply omitting dofs in which a limb does not move (e.g., abduction at the knee), the limited motion of the limb in these dofs can be more realistically modeled as a very low compliance. Finally, we discuss the practical implications of these results to experimental measurements of muscle actions.

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.

Visible diffraction from graphene and its application in holograms

A fundamental study of visible diffraction effects from patterned graphene layers is presented. By patterning graphene into optical gratings, visible diffraction from graphene is experimentally measured as a function of the number of layers and visible wavelengths. A practical application of these effects is also presented, by demonstrating an optical hologram based on graphene. A high resolution (pixel size 400 nm) intensity hologram is fabricated which, in response to incident laser light, generates a visible image. These findings suggest that visible diffraction in graphene can find practical application in holograms and should also be considered during the design and characterisation of graphene-based optical applications. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polarization switchable diffraction based on subwavelength plasmonic nanoantennas.

We prove theoretically and experimentally the concept of polarization holography by producing visible diffraction through radiation emitted by plasmonic nanoantennas. We show a methodology to selectively activate the nanoantenna emission by controlling the orientation of the electric field of a beam. Additionally, we demonstrate that it is possible to superpose two independent transverse nanoantennas in the same plane without producing interference in their radiated field. Hence, we introduce an alternative view to the traditional concept of holography where fringes (or diffractive units) are band-limited to half the wavelength.

Stabilization of a complex perovskite superstructure under ambient conditions: Influence of cation composition and ordering, and evaluation as an SOFC cathode

Ba1.6Ca2.3Y1.1Fe5O13 is an Fe3+ oxide adopting a complex perovskite superstructure, which is an ordered intergrowth between the Ca2Fe2O5 and YBa2Fe3O8 structures featuring octahedral, square pyramidal, and tetrahedral B sites and three distinct A site environments. The distribution of A site cations was evaluated by combined neutron and X-ray powder diffraction. Consistent with the Fe3+ charge state, the material is an antiferromagnetic insulator with a Néel temperature of 480-485 °C and has a relatively low d.c. conductivity of 2.06 S cm-1 at 700 °C. The observed area specific resistance in symmetrical cell cathodes with the samarium-doped ceria electrolyte is 0.87 Ω cm2 at 700 °C, consistent with the square pyramidal Fe3+ layer favoring oxide ion formation and mobility in the oxygen reduction reaction. Density functional theory calculations reveal factors favoring the observed cation ordering and its influence on the electronic structure, in particular the frontier occupied and unoccupied electronic states. © 2010 American Chemical Society.

Reversible CO2 absorption by the 6H perovskite Ba 4Sb2O9

A novel compound for carbon capture and storage (CCS) applications, the 6H perovskite Ba4Sb2O9, was found to be able to absorb CO2 through a chemical reaction at 873 K to form barium carbonate and BaSb2O6. This absorption was shown to be reversible through the regeneration of the original Ba4Sb 2O9 material upon heating above 1223 K accompanied by the release of CO2. A combined synchrotron X-ray diffraction, thermogravimetric, and microscopy study was carried out to characterize first the physical absorption properties and then to analyze the structural evolution and formation of phases in situ. Importantly, through subsequent carbonation and regeneration of the material over 100 times, it was shown that the combined absorption and regeneration reactions proceed without any significant reduction in the CO2 absorption capacity of the material. After 100 cycles the capacity of Ba4Sb2O9 was ∼0.1 g (CO 2)/g (sorbent), representing 73% of the total molar capacity. This is the first report of a perovskite-type material showing such good properties, opening the way for studies of new classes of inorganic oxide materials with stable and flexible chemical compositions and structures for applications in carbon capture. © 2013 American Chemical Society.

Revealing lithium-silicide phase transformations in nano-structured silicon-based lithium ion batteries via in situ NMR spectroscopy.

Nano-structured silicon anodes are attractive alternatives to graphitic carbons in rechargeable Li-ion batteries, owing to their extremely high capacities. Despite their advantages, numerous issues remain to be addressed, the most basic being to understand the complex kinetics and thermodynamics that control the reactions and structural rearrangements. Elucidating this necessitates real-time in situ metrologies, which are highly challenging, if the whole electrode structure is studied at an atomistic level for multiple cycles under realistic cycling conditions. Here we report that Si nanowires grown on a conducting carbon-fibre support provide a robust model battery system that can be studied by (7)Li in situ NMR spectroscopy. The method allows the (de)alloying reactions of the amorphous silicides to be followed in the 2nd cycle and beyond. In combination with density-functional theory calculations, the results provide insight into the amorphous and amorphous-to-crystalline lithium-silicide transformations, particularly those at low voltages, which are highly relevant to practical cycling strategies.

Measurement of residual stresses in ferroelectric Pb(Zr 0.3Ti0.7)O3 thin films by X-ray diffraction

The residual stresses in Pb(Zr0.3Ti0.7)O3 thin films were measured by the sin2 Ψ method using the normal X-ray incidence. The spacing of different planes (hkl) parallel to the film surface were converted to the spacing of a set of inclined planes (100). The angles between (100) and (hkl) were equivalent to the tilting angles of (100) from the normal of film surface. The residual stresses were extracted from the linear slope of the strain difference between the equivalent inclined direction and normal direction with respect to the sin2 Ψ. The results were in consistency with that derived from the conventional sin2 Ψ method. © 2013 The Japan Society of Applied Physics.

Progress in the understanding of Ni silicide formation for advanced MOS structures

Metallic silicides have been used as contact materials on source/drain and gate in metal-oxide semiconductor (MOS) structure for 40 years. Since the 65 nm technology node, NiSi is the preferred material for contact in microelectronic due to low resistivity, low thermal budget, and low Si consumption. Ni(Pt)Si with 10 at.% Pt is currently employed in recent technologies since Pt allows to stabilize NiSi at high temperature. The presence of Pt and the very low thickness (<10 nm) needed for the device contacts bring new concerns for actual devices. In this work, in situ techniques [X-ray diffraction (XRD), X-ray reflectivity (XRR), sheet resistance, differential scanning calorimetry (DSC)] were combined with atom probe tomography (APT) to study the formation mechanisms as well as the redistribution of dopants and alloy elements (Pt, Pd.) during the silicide formation. Phenomena like nucleation, lateral growth, interfacial reaction, diffusion, precipitation, and transient phase formation are investigated. The effect of alloy elements (Pt, Pd.) and dopants (As, B.) as well as stress and defects induced by the confinement in devices on the silicide formation mechanism and alloying element redistribution is examined. In particular APT has been performed for the three-dimensional (3D) analysis of MOSFET at the atomic scale. The advances in the understanding of the mechanisms of formation and redistribution are discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.