Kinetics of low-pressure, low-temperature graphene growth : toward single-layer, single-crystalline structure

Graphene grown on metal catalysts with low carbon solubility is a highly competitive alternative to exfoliated and other forms of graphene, yet a single-layer, single-crystal structure remains a challenge because of the large number of randomly oriented nuclei that form grain boundaries when stitched together. A kinetic model of graphene nucleation and growth is developed to elucidate the effective controls of the graphene island density and surface coverage from the onset of nucleation to the full monolayer formation in low-pressure, low-temperature CVD. The model unprecedentedly involves the complete cycle of the elementary gas-phase and surface processes and shows a precise quantitative agreement with the recent low-energy electron diffraction measurements and also explains numerous parameter trends from a host of experimental reports. These agreements are demonstrated for a broad pressure range as well as different combinations of precursor gases and supporting catalysts. The critical role of hydrogen in controlling the graphene nucleation and monolayer formation is revealed and quantified. The model is generic and can be extended to even broader ranges of catalysts and precursor gases/pressures to enable the as yet elusive effective control of the crystalline structure and number of layers of graphene using the minimum amounts of matter and energy.

Property-performance control of multidimensional, hierarchical, single-crystalline ZnO nanoarchitectures

Diverse morphologies of multidimensional hierarchical single-crystalline ZnO nanoarchitectures including nanoflowers, nanobelts, and nanowires are obtained by use of a simple thermal evaporation and vapour-phase transport deposition technique by placing Au-coated silicon substrates in different positions inside a furnace at process temperatures as low as 550 °C. The nucleation and growth of ZnO nanostructures are governed by the vapour–solid mechanism, as opposed to the commonly reported vapour–liquid–solid mechanism, when gold is used in the process. The morphological, structural, compositional and optical properties of the synthesized ZnO nanostructures can be effectively tailored by means of the experimental parameters, and these properties are closely related to the local growth temperature and gas-phase supersaturation at the sample position. In particular, room-temperature photoluminescence measurements reveal an intense near-band-edge ultraviolet emission at about 386 nm for nanobelts and nanoflowers, which suggests that these nanostructures are of sufficient quality for applications in, for example, optoelectronic devices.

Plasma-enabled growth of single-crystalline SiC/AlSiC Core–Shell nanowires on porous alumina templates

We report the catalyst-free synthesis of the arrays of core–shell, ultrathin, size-uniform SiC/AlSiC nanowires on the top of a periodic anodic aluminum oxide template. The nanowires were grown using an environmentally friendly, silane-free process by exposing the silicon supported porous alumina template to CH4 + H2 plasmas. High-resolution scanning and transmission electron microscopy studies revealed that the nanowires have a single-crystalline core with a diameter of about 10 nm and a thin (1–2 nm) amorphous AlSiC shell. Because of their remarkable length, high aspect ratio, and very high surface area-to-volume ratio, these unique structures are promising for nanoelectronic and nanophotonic applications that require efficient electron emission, light scattering, etc. A mechanism for nanowire growth is proposed based upon the reduction of the alumina template to nanosized metallic aluminum droplets forming between nanopores. The subsequent incorporation of silicon and carbon atoms from the plasma leads to nucleation and growth from the top of the alumina template.

Single-step, catalyst-free plasma-assisted synthesis and growth mechanism of single-crystalline aluminum nitride nanorods

Synthesis of one-dimensional AlN nanostructures commonly requires high process temperatures (>900 °C), metal catalyst, and hazardous gas/powder precursors. We report on a simple, single-step, catalyst-free, plasma-assisted growth of dense patterns of size-uniform single-crystalline AlN nanorods at a low substrate temperature (∼650 °C) without any catalyst or hazardous precursors. This unusual growth mechanism is based on highly effective plasma dissociation of N2 molecules, localized species precipitation on AlN islands, and reduced diffusion on the nitrogen-rich surface. This approach can also be used to produce other high-aspect-ratio oxide and nitride nanostructures for applications in energy conversion, sensing, and optoelectronics. © 2010 American Institute of Physics.

Plasma-assisted self-sharpening of platelet-structured single-crystalline carbon nanocones

A mechanism and model for the vertical growth of platelet-structured vertically aligned single-crystalline carbon nanostructures by the formation of graphene layers on a flat top surface are proposed and verified experimentally. It is demonstrated that plasma-related effects lead to self-sharpening of tapered nanocones to form needlelike nanostructures, in a good agreement with the predicted dependence of the radius of a nanocone's flat top on the incoming ion flux and surface temperature. The growth mechanism is relevant to a broad class of nanostructures including nanotips, nanoneedles, and nanowires and can be used to improve the predictability of nanofabrication processes. © 2007 American Institute of Physics.

Deterministic surface growth of single-crystalline iron oxide nanostructures in nonequilibrium plasma

An innovative approach to precise tailoring of surface density, shapes, and sizes of single-crystalline α-Fe 2O 3 nanowires and nanobelts by controlling interactions of reactive oxygen plasma-generated species with the Fe surface is proposed. This strongly nonequilibrium, rapid, almost incubation-free, high-rate growth directly from the solid-solid interface can also be applied to other oxide materials and is based on deterministic control of the density of oxygen species and the surface conditions, which determine the nanostructure nucleation and growth.

Nanofabrication of single-crystalline flat-panel display microemitters : a plasma-building unit approach

This contribution is focused on plasma-enhanced chemical vapor deposition systems and their unique features that make them particularly attractive for nanofabrication of flat panel display microemitter arrays based on ordered patterns of single-crystalline carbon nanotip structures. The fundamentals of the plasma-based nanofabrication of carbon nanotips and some other important nanofilms and nanostructures are examined. Specific features, challenges, and potential benefits of using the plasma-based systems for relevant nanofabrication processes are analyzed within the framework of the "plasma-building unit" approach that builds up on extensive experimental data on plasma diagnostics and nanofilm/nanostructure characterization, and numerical simulation of the species composition in the ionized gas phase (multicomponent fluid models), ion dynamics and interaction with ordered carbon nanotip patterns, and ab initio computations of chemical structure of single crystalline carbon nanotips. This generic approach is also applicable for nanoscale assembly of various carbon nanostructures, semiconductor quantum dot structures, and nano-crystalline bioceramics. Special attention is paid to most efficient control strategies of the main plasma-generated building units both in the ionized gas phase and on nanostructured deposition surfaces. The issues of tailoring the reactive plasma environments and development of versatile plasma nanofabrication facilities are also discussed.

Nanoparticle manipulation in plasma-assisted nanofabrication of electron field emitters based on single crystalline carbon nanotip patterns

Nanoparticle manipulation by various plasma forces in near-substrate areas of the Integrated Plasma-Aided Nanofabrication Facility (IPANF) is investigated. In the IPANF, high-density plasmas of low-temperature rf glow discharges are sustained. The model near-substrate area includes a variable-length pre-sheath, where a negatively charged nanoparticle is accelerated, and a self-consistent collisionless sheath with a repulsive electrostatic potential. Conditions enabling the nanoparticle to overcome the repulsive barrier and deposit onto the substrate are investigated numerically and experimentally. Under certain conditions the momentum gained by the nanoparticle in the pre-sheath area appears to be sufficient for the driving ion drag force to outbalance the repulsive electrostatic and thermophoretic forces. Numerical results are applied for the explanation of size-selective nanoparticle deposition in the Ar+H2+CH4 plasma-assisted chemical vapor deposition of various carbon nanostructure patterns for electron field emitters and are cross-referenced by the field emission scanning electron microscopy. It is shown that the nanoparticles can be efficiently manipulated by the temperature gradient-controlled thermophoretic force. Experimentally, the temperature gradients in the near-substrate areas are measured in situ by means of the temperature gradient probe and related to the nanofilm fabrication conditions. The results are relevant to plasma-assisted synthesis of numerous nanofilms employing structural incorporation of the plasma-grown nanoparticles, including but not limited to nanofabrication of ordered single-crystalline carbon nanotip arrays for electron field emission applications.

As-deposited near-single crystalline high Tc and Jc superconducting thin films by a pulsed lased deposition process

As-deposited high Tc superconducting Y1Ba2Cu3O7−x films with zero resistance temperatures of similar, equals89 K and critical current densities about 0.7×106 A/cm2 at 77 K have been reproducibly fabricated at a substrate holder temperature at 650°C, using pulsed laser deposition, without post-annealing. One key to these results is the injection of gaseous oxygen into laser produced plume just in front of the target. In this way, the correct amount of oxygen is incorporated into the as-grown film so that post-deposition treatment becomes unnecessary. Axial ion channeling in these as-deposit high Tc superconducting films on (100) SrTiO3 and X-ray photoelectron spectroscopy (XPS) on the film surfaces were performed. Angular yield profile near the film surface for Ba, and the surface peak intensity were measured using 3 MeV He ions. For channeling normal to the substrate a minimum yield of 7%, compared to similar, equals3% for single crystals, was obtained. The results of ion channeling and XPS studies indicate that the as-deposited films have good crystallinity as well as toichiometry to within similar, equals1 nm of the film surface. The in-situ growth of such high Tc and Jc films is an important step in the use of the laser deposition technique to fabricate multilayer structures and the surface perfection is of importance in tunneling devices such as Josephson junctions.

Synthesis and characterization of single-crystalline alpha-MoO3 nanofibers for enhanced Li-ion intercalation applications

High quality, single-crystalline alpha-MoO3 nanofibers are synthesized by rapid hydrothermal method using a polymeric nitrosyl-complex of molybdenum(II) as molybdenum source without employing catalysts, surfactants, or templates. The possible reaction pathway is decomposition and oxidation of the complex to the polymolybdate and then surface condensation on the energetically favorable 001] direction in the initially formed nuclei of solid alpha-MoO3 under hydrothermal conditions. Highly crystalline alpha-MoO3 nanofibers have grown along 001] with lengths up to several micrometres and widths ranging between 280 and 320 nm. The alpha-MoO3 nanofibers exhibit desirable electrochemical properties such as high capacity reversibility as a cathode material of a Li-ion battery.

Insulating State and Breakdown of Fermi Liquid Description in Molecular-Scale Single-Crystalline Wires of Gold

Electrical transport measurements on ultrathin single-crystalline Au nanowires, synthesized via a wet chemical route, show an unexpected insulating behavior. The linear response electrical resistance exhibits a power-law dependence on temperature. In addition, the variation of current over a wide range of temperature and voltage obeys a universal scaling relation that provides compelling evidence for a non-Fermi liquid behavior. Our results demonstrate that the quantum ground state In ultrathin nanowires of simple metallic systems can be radically different from their bulk counterparts and can be described In terms of a Tomonaga-Luttinger liquid (TLL), in the presence of remarkably strong electron-electron interactions.

Single crystalline ultrathin gold nanowires: Promising nanoscale interconnects

Using first principles based density functional calculation we study the mechanical, electronic and transport properties of single crystalline gold nanowires. While nanowires with the diameter less than 2 nm retain hexagonal cross-section, the larger diameter wires show a structural smoothening leading to circular cross-section. These structural changes significantly affect the mechanical properties of the wires, however, strength remains comparable to the bulk. The transport calculations reveal that the conductivity of these wires are in good agreement with experiments. The combination of good mechanical, electronic and transport properties make these wires promising as interconnects for nano devices. Copyright 2013 Author(s). This article is distributed under a Creative Commons Attribution 3.0 Unported License. http://dx.doi.org/10.1063/1.4796188]

Single crystalline magnetite, maghemite, and hematite nanoparticles with rich coercivity

One-pot synthesis of amorphous iron oxide nanoparticles with two different dimensions (<5 nm and 60 nm) has been achieved using the reverse micelle method, with <5 nm nanoparticles separated from the stable colloid by exploiting their magnetic behaviour. The transformation of the as-prepared amorphous powders into Fe3O4 and Fe2O3 phases (gamma and alpha) is achieved by carrying out controlled annealing at elevated temperatures under different optimized conditions. The as-prepared samples resulting from micellar synthesis and the corresponding annealed ones are thoroughly characterized by powder X-ray diffraction, transmission electron microscopy (TEM), and by Raman and X-ray photoelectron spectroscopies. Expectedly, the magnetic characteristics of Fe3O4 and Fe2O3 phase (gamma and alpha) nanoparticles are found to have strong dependence on their phase, dimension, and morphology. The coercivity of Fe3O4 and Fe2O3 (gamma and alpha) nanoparticles is reasonably high, even though high resolution TEM studies bring out that these nanoparticles are single crystalline. This is in contrast with previous reports wherein poly-crystallinity of iron oxides nanoparticles has been regarded as a prerequisite for high coercivity.

Theory Of Phase Transformation And Reorientation In Single Crystalline Shape Memory Alloys

A constitutive model, based on an (n + 1)-phase mixture of the Mori-Tanaka average theory, has been developed for stress-induced martensitic transformation and reorientation in single crystalline shape memory alloys. Volume fractions of different martensite lattice correspondence variants are chosen as internal variables to describe microstructural evolution. Macroscopic Gibbs free energy for the phase transformation is derived with thermodynamics principles and the ensemble average method of micro-mechanics. The critical condition and the evolution equation are proposed for both the phase transition and reorientation. This model can also simulate interior hysteresis loops during loading/unloading by switching the critical driving forces when an opposite transition takes place.