Near-field characterization of chemical vapor deposition graphene in the microwave regime

Near-field measurements were performed at X-band frequencies for graphene on copper microstrip transmission lines. An improvement in radiation of 0.88 dB at 10.2 GHz is exhibited from the monolayer graphene antenna which has dc sheet resistivity of 985 Ω/sq. Emission characteristics were validated via ab initio simulations and compared to empirical findings of geometrically comparable copper patches. This study contributes to the current knowledge of the electronic properties of graphene. © 2013 AIP Publishing LLC.

Chemical nano-gardens: growth of salt nanowires from supramolecular self-assembly gels.

In this article, we examine the phenomenon of single-crystal halide salt wire growth at the surface of porous materials. We report the use of a single-step casting technique with a supramolecular self-assembly gel matrix that upon drying leads to the growth of single-crystal halide (e.g., NaCl, KCl, and KI) nanowires with diameters ~130-200 nm. We demonstrate their formation using electron microscopy and electron-dispersive X-ray spectroscopy, showing that the supramolecular gel stabilizes the growth of these wires by facilitating a diffusion-driven base growth mechanism. Critically, we show that standard non-supramolecular gels are unable to facilitate nanowire growth. We further show that these nanowires can be grown by seeding, forming nanocrystal gardens. This study helps understand the possible prefunctionalization of membranes to stimulate ion-specific filters or salt efflorescence suppressors, while also providing a novel route to nanomaterial growth.

Structural and optical properties of III-V nanowires and nanowire heterostructures grown by metalorganic chemical vapour deposition

We have investigated the structural and optical properties of III-V nanowires grown by metalorganic chemical vapour deposition. Binary GaAs, InAs and InP nanowires, and ternary InGaAs and AlGaAs nanowires, have been fabricated and characterised. A variety of axial and radial heterostructures have also been fabricated, including GaAs/AlGaAs core-multishell and GaAs/InGaAs superlattice nanowires. GaAs/AlGaAs core-shell nanowires exhibit strong photoluminescence as the AlGaAs shell passivates the GaAs nanowire surface reducing the surface nonradiative recombination. © 2007 IEEE.

Growth of III-V nanowires and nanowire heterostructures by metalorganic chemical vapor deposition

We have investigated the structural and optical properties of III-V nanowires, and axial and radial nanowire heterostructures, fabricated by metalorganic chemical vapor deposition. In addition to binary nanowires, such as GaAs, InAs, and InP, we have demonstrated ternary InGaAs and AlGaAs nanowires. Core-shell nanowires consisting of GaAs cores with AlGaAs shells, and core-multishell nanowires with alternating shells of AlGaAs and GaAs, exhibit strong photoluminescence. Axial segments of InGaAs have been incorporated within GaAs nanowires to form GaAs/InGaAs nanowire superlattices. We have developed a two-temperature growth procedure to optimize nanowire morphology. An initial high temperature step promotes nucleation and epitaxial growth of straight (111)B-oriented nanowires. Lower temperatures are employed subsequently, to minimise radial growth. © 2007 IEEE.

Structural and optical properties of axial and radial heterostructure III-V nanowires grown by metalorganic chemical vapour deposition

We have investigated the structural properties and photoluminescence of novel axial and radial heterostructure III-V nanowires, fabricated by metalorganic chemical vapour deposition. Segments of InGaAs have been incorporated within GaAs nanowires, to create axial heterostructure nanowires which exhibit strong photoluminescence. Photoluminescence is observed from radial heterostructure nanowires (core-shell nanowires), consisting of GaAs cores with AlGaAs shells. Core-multishell nanowires, of GaAs cores clad in several alternating layers of thick AlGaAs barrier shells and thin GaAs quantum well shells, exhibit a blue-shifted photoluminescence peak arising from quantum confinement effects. © 2006 Crown Copyright.

Optimised two-temperature growth of GaAs nanowire s by metalorganic chemical vapour deposition

We report a two-temperature procedure for the growth of GaAs nanowires by metalorganic chemical vapour deposition. An initial high temperature step affords effective nucleation and promotes epitaxial growth of straight (111)B-oriented nanowires. Lower temperatures are employed subsequently, to minimise nanowire tapering during growth. © 2006 IEEE.

Growth of GaAs/InAs vertical nanowires on GaAs (111)B by metalorganic chemical vapor deposition

The growth mechanism and properties of GaAs/InAs nanowires prepared by metalorganic chemical vapor deposition are investigated. Vertical InAs nanowires on GaAs (111)B substrates are successfully grown despite the large lattice mismatch (-7.2%). The crystallographic perfection of InAs nanowires is confirmed by hexagonal or triangular cross section. An interesting L-shaping of GaAs/InAs heterostructure nanowire which could be useful for novel device application is observed. © 2005 IEEE.

Sorting nanoparticles by centrifugal fields in clean media

The on-demand availability of nanomaterials with selected size and well-defined chemical/physical properties is of fundamental importance for their widespread application. We report two clean, rapid, and non-destructive approaches for nanoparticle (NP) size selection in centrifugal fields. The first exploits rate zonal separation in a high viscosity gradient. The second exploits selective sedimentation of NPs with different sizes. These methods are here applied to metallic nanoparticles (MNPs) with different compositions and surface chemistry, dispersed either in water or organic solvents. The approach is general and can also be exploited for the separation of NPs of any material. We selectively sort both Au and AgNPs with sizes in the 10-30 nm range, achieving chemical-free MNPs with low polydispersivity. We do not use solutes, thus avoiding contamination, and only require low centrifugal fields, easily achievable in benchtop systems. © 2013 American Chemical Society.

Tests of an adaptive QM/MM calculation on free energy profiles of chemical reactions in solution.

We present reaction free energy calculations using the adaptive buffered force mixing quantum mechanics/molecular mechanics (bf-QM/MM) method. The bf-QM/MM method combines nonadaptive electrostatic embedding QM/MM calculations with extended and reduced QM regions to calculate accurate forces on all atoms, which can be used in free energy calculation methods that require only the forces and not the energy. We calculate the free energy profiles of two reactions in aqueous solution: the nucleophilic substitution reaction of methyl chloride with a chloride anion and the deprotonation reaction of the tyrosine side chain. We validate the bf-QM/MM method against a full QM simulation, and show that it correctly reproduces both geometrical properties and free energy profiles of the QM model, while the electrostatic embedding QM/MM method using a static QM region comprising only the solute is unable to do so. The bf-QM/MM method is not explicitly dependent on the details of the QM and MM methods, so long as it is possible to compute QM forces in a small region and MM forces in the rest of the system, as in a conventional QM/MM calculation. It is simple, with only a few parameters needed to control the QM calculation sizes, and allows (but does not require) a varying and adapting QM region which is necessary for simulating solutions.

Intrinsic terahertz plasmon signatures in chemical vapour deposited graphene

Plasmonic resonance at terahertz (THz) frequencies can be achieved by gating graphene grown via chemical vapour deposition (CVD) to a high carrier concentration. THz time domain spectroscopy of such gated monolayer graphene shows resonance features around 1.6 THz, which appear as absorption peaks when the graphene is electrostatically p-doped and change to enhanced transmission when the graphene is n-doped. Superimposed on the Drude-like frequency response of graphene, these resonance features are related to the inherent poly-crystallinity of CVD graphene. An understanding of these features is necessary for the development of future THz optical elements based on CVD graphene. © 2013 AIP Publishing LLC.

Oxygen carrier dispersion in inert packed beds to improve performance in chemical looping combustion

Various packed beds of copper-based oxygen carriers (CuO on Al2O3) were tested over 100 cycles of low temperature (673K) Chemical Looping Combustion (CLC) with H2 as the fuel gas. The oxygen carriers were uniformly mixed with alumina (Al2O3) in order to investigate the level of separation necessary to prevent agglomeration. It was found that a mass ratio of 1:6 oxygen carrier to alumina gave the best performance in terms of stable, repeating hydrogen breakthrough curves over 100 cycles. In order to quantify the average separation achieved in the mixed packed beds, two sphere-packing models were developed. The hexagonal close-packing model assumed a uniform spherical packing structure, and based the separation calculations on a hypergeometric probability distribution. The more computationally intensive full-scale model used discrete element modelling to simulate random packing arrangements governed by gravity and contact dynamics. Both models predicted that average 'nearest neighbour' particle separation drops to near zero for oxygen carrier mass fractions of x≥0.25. For the packed bed systems studied, agglomeration was observed when the mass fraction of oxygen carrier was above this threshold. © 2013 Elsevier B.V.