Self-assembled vapor-liquid-solid growth of aligned Cu-SiO2 core-shell nanocable arrays on Cu substrates

The Cu-SiO2 core-shell nanocable arrays on the Cu wafers have been synthesized via a simple thermal evaporation of the SiO powder. The morphology and structure of the as-synthesized Cu-SiO2 core-shell nanocables are characterized by using scanning electron microscopy, high-resolution transmission electron microscopy, and X-ray energy dispersive spectrometer. The growth of amorphous SiO2 shell follows a vapor-liquid-solid mechanism, and then molten metal Cu will be diffused into the SiO2 nanotubes, forming the Cu-SiO2 core-shell nanocable arrays. It is found that the aligned Cu-SiO2 core-shell nanocables prefer to grow along the grooves of the Cu substrate, and the density of the Cu-SiO2 core-shell nanocable arrays can be controlled by adjusting the growth temperature.     

硅纳米线的制备与生长机理

硅纳米线是一种新型的一维半导体光电材料.本文较系统地介绍了硅纳米线在制备技术、生长机理方面的研究现状与最新进展,主要就激光烧蚀法、化学气相沉积法、热气相沉积法及溶液法等制备方法和基于气-液-固机理的生长机理、氧化物辅助生长机理及固-液-固生长机理等作了较为详尽的论述.     

Cobalt silicide nanocables grown on Co films: synthesis and physical properties

Single-crystalline cobalt silicide/SiO(x) nanocables have been grown on Co thin films on an SiO(2) layer by a self-catalysis process via vapor-liquid-solid mechanism. The nanocables consist of a core of CoSi nanowires and a silicon oxide shell with a length of several tens of micrometers. In the confined space in the oxide shell, the CoSi phase is stable and free from agglomeration in samples annealed in air ambient at 900?°C for 1?h. The nanocable structure came to a clear conclusion that the thermal stability of the silicide nanowires can be resolved by the shell encapsulation. Cobalt silicide nanowires were obtained from the nanocable structure. The electrical properties of the CoSi nanowires have been found to be compatible with their thin film counterpart and a high maximum current density of the nanowires has been measured. One way to obtain silicate nanowires has been demonstrated. The silicate compound, which is composed of cobalt, silicon and oxygen, was achieved. The Co silicide/oxide nanocables are potentially useful as a key component of silicate nanowires, interconnects and magnetic units in nanoelectronics.     

Large-scale growth of Cu2ZnSnSe4 and Cu2ZnSnSe4/Cu2ZnSnS4 core/shell nanowires

We present a fast and simple protocol for large-scale preparation of quaternary Cu(2)ZnSnSe(4) (CZTSe), as well as CZTSe/Cu(2)ZnSnS(4) (CZTS) core/shell nanowires using CuSe nanowire bundles as self-sacrificial templates. CuSe nanowire bundles were synthesized by reacting Cu(2 - x)Se nanowire bundles with sodium citrate solution. CZTSe nanowires were prepared by reacting CuSe nanowire bundles with Zn(CH(3)COO)(2) and SnCl(2) in triethylene glycol. X-ray diffraction (XRD) and selected area electron diffraction studies show that stannite CZTSe is formed. The formed CZTSe nanowire bundles have diameters of 200-400 nm and lengths of up to hundreds of micrometers. CZTSe/CZTS nanocable bundles with similar morphologies were grown by the addition of some elemental sulfur to the reaction system for growth of CZTSe bundles. The stannite CZTSe/kesterite CZTS core/shell structure of the grown nanocables was confirmed by XRD and high-resolution transmission electron microscope investigation. The influence of S/Se molar ratio in the reaction system on the crystallographic structures and optical properties of CZTSe/CZTS nanocables was studied. The obtained CZTSe/CZTS core/shell nanocable bundles show broad and enhanced optical absorption over the visible and near-infrared region, which is promising for use in photovoltaic applications.     

Synthesis of polyaniline/multi-walled carbon nanotube nanocomposites in water/oil microemulsion

A water/oil microemulsion system having been successfully used for synthesizing polyaniline(PANi) nanoparticles, was employed for preparing PANi/multi-walled carbon nanotube (MWCNT) nanocomposites via in situ chemical oxidative polymerization. The structures and the electrical property of PANi/MWCNT nanocomposites were also studied. The studies showed that PANi could coat MWCNTs to form nanocables with core-shell structure, and the backbone structure of PANi was not damaged by the introduction of MWCNTs. The conductivities of PANi/MWCNT nanocomposites were higher than that of PANi. Moreover, a model was supposed to be used for describing a PANi/MWCNT nanocable formation by in situ microemulsion polymerization.     

Controlling silicon nanowire growth direction via surface chemistry

We report on the first in situ chemical investigation of vapor-liquid-solid semiconductor nanowire growth and reveal the important, and previously unrecognized, role of transient surface chemistry near the triple-phase line. Real-time infrared spectroscopy measurements coupled with postgrowth electron microscopy demonstrate that covalently bonded hydrogen atoms are responsible for the (left angle bracket 111 right angle bracket) to (left angle bracket 112 right angle bracket) growth orientation transition commonly observed during Si nanowire growth. Our findings provide insight into the root cause of this well-known nanowire growth phenomenon and open a new route to rationally engineer the crystal structure of these nanoscale semi-conductors.     

Zigzag zinc blende ZnS nanowires: Large scale synthesis and their structure evolution induced by electron irradiation

Large scale zigzag zinc blende single crystal ZnS nanowires have been successfully synthesized during a vapor phase growth process together with a small yield of straight wurtzite single crystal ZnS nanowires. AuPd alloy nanoparticles were utilized to catalyze a vapor-solid-solid growth process of both types of ZnS nanowires, instead of the more common vapor-liquid-solid growth process. Surprisingly, the vapor-phase grown zigzag zinc blende ZnS nanowires are metastable under high-energy electron irradiation in a transmission electron microscope, with straight wurtzite nanowires being much more stable. Upon exposure to electron irradiation, a wurtzite ZnO nanoparticle layer formed on the zigzag zinc blende ZnS nanowire surface with concomitant displacement damage. Both electron inelastic scattering and surface oxidation as a result of electron-beam heating occur during this structure evolution process. When prolonged higher-voltage electron irradiation was applied, local zinc blende ZnS nanowire bodies evolved into ZnS-ZnO nanocables, and dispersed ZnS-ZnO nanoparticle networks. Random AuPd nanoparticles were observed distributed on zigzag ZnS nanowire surfaces, which might be responsible for a catalytic oxidation effect and speed up the surface oxidation-induced structure evolution.      

Calculation of the Electronic and Thermal Properties of C/BN Nanotubular Heterostructures

Modeling results are presented on the electronic, structural, and thermal properties of a (5,5)C@(17,0)BN-NT tubular heterostructure (a metal-like carbon nanotube inside a dielectric boron nitride nanotube) regarded as a prototype of nanocables. It is shown that the electronic properties of the nanocable remain unchanged up to about 3500 K. The properties of the nanocable are analyzed in comparison with those of a [C₆₀]_∞@(17,0)BN-NT peapod, a potential precursor to C/BN nanocables.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 6, 2005, pp. 687–695.Original Russian Text Copyright © 2005 by Enyashin, Seifert, Ivanovskii.     

Temperature-dependent growth of germanium oxide and silicon oxide based nanostructures, aligned silicon oxide nanowire assemblies, and silicon oxide microtubes

We demonstrate the temperature-dependent growth of germanium oxide and silicon oxide based composite nanostructures (multiple nanojunctions of Ge nanowires and SiO(x) nanowires, Ge-filled SiO(2) nanotubes, Ge/SiO(2) coaxial nanocables, and a variety of interesting micrometer-sized structures), aligned SiO(x) nanowire assemblies, and SiO(x) microtubes. The structures were characterized by SEM, TEM, energy-dispersive X-ray spectroscopy, and electron diffraction. The combination of laser ablation of a germanium target and thermal evaoporation of silicon monoxide powders resulted in the formation of Ge and SiO(x) species in a carrier gas; the nano/micro-sized structures grow by either a Ge-catalyzed vapor-liquid-solid or a Ge-nanowire-templated vapor-solid process.     

Novel C/Cu sheath/core nanostructures synthesized via low-temperature MOCVD

C/Cu sheath/core nanocable arrays were mass-produced on various substructures, such as Si, SiO(2), Cu or glass, by using a one-step low-temperature metal-organic chemical vapor deposition. The novel nanostructures consist of a faceted Cu nanowire core with six side surfaces and four top surfaces, and a sheath of carbon. The as-synthesized nanocables are demonstrated excellent oxidization resistance and field emission properties, and are expected to be excellent candidates as nano-interconnectors, or nanocables, in electronic devices and nano-emitters for field emissions.     

Ultra long SiC/SiO2 core-shell nanocables from organic precursor

Ultra long SiC core and SiO2 shell nanocables have been prepared by pyrolysis of poly(dimethyl siloxane) at 1050 degrees C in flowing Argon. The longest nanocable can be up to at least 6 mm. Transmission electron microscopy observations indicate that the diameter of the cores varies from about 3 to 18 nm, and the thickness of the outer sheaths varies from about 6 to 45 nm and that the cores are crystalline and the sheaths are amorphous. The growth of the nanocables may be governed by a chemical vapor solid process. The nanocables exhibit good photoluminescence property.     

Synthesis and characterization of highly ordered cobalt-magnetite nanocable arrays

Magnetically tunable, high-density arrays of coaxial nanocables within anodic aluminum oxide (AAO) membranes have been synthesized. The nanocables consist of magnetite nanowires surrounded by cobalt nanotube sheaths and cobalt nanowires surrounded by magnetite nanotube sheaths. These materials are a combination of separate hard (Co) and soft (Fe3O4) magnetic materials in a single nanocable structure. The combination of two or more magnetic materials in such a radial structure is seen as a very powerful tool for the future fabrication of magnetoresistive, spin-valve and ultrafast spin-injection devices with nonplanar geometries. The nanocable arrays were prepared using a supercritical-fluid inclusion process, whereby the nanotube was first deposited onto the pore walls of the nanoporous membranes and subsequently filled with core material to form coaxial nanocables. In essence, this paper describes a technique for placing novel magnetic technologies into well-defined building blocks that may ultimately lead to new multifunctional devices, such as spin valves and high-density magnetic storage devices.     

Titanium-assisted growth of silica nanowires: from surface-matched to free-standing morphologies

We report on an oxide-assisted growth technique for silica nanowires which allows tuning the growth from surface-matched nanowires to free-standing morphologies based on growth control by Ti in the role of a catalyst and surfactant. Using an adjustable Ti concentration, we grew silica nanowires with lengths ranging from 100 nm up to several millimetres whose defect chemistry was analysed by electron microscopy tools, monochromatic cathodoluminescence imaging and time resolved photoluminescence spectroscopy. The knowledge of the luminescence properties and the related defect occurrence along with their spatial distribution is pivotal for advancing silica nanowire growth in order to realize successful device designs based on self-assembled Si/SiO(x) nanostructures. We demonstrate a core-shell structure of the grown nanowires with a highly luminescent 150 nm thick shell and outstandingly fast decaying dynamics (≈1 ns) for glass-like materials. The conjunction of the observed efficient and stable luminescences with their attributed decaying behaviours suggests applications for silica nanowires such as active and passive optical interconnectors and white light phosphors. The identification of a time domain difference for the spectral regime from 2.3 to 3.3 eV, within the confined spatial dimensions of a single nanowire, is very promising for future, e.g. data transmission applications, employing silica nanowires which exhibit achievable compatibility with commonly applied silicon-based electronics. A qualitative growth model based on silica particle diffusion and Ti-assisted seed formation is developed for the various types of segregated silica nanowires which extends commonly assumed oxide-assisted growth mechanisms.     

One-dimensional ZnO nanostructures

The wide-gap semiconductor ZnO with nanostructures such as nanoparticle, nanorod, nanowire, nanobelt, nanotube has high potential for a variety of applications. This article reviews the fundamentals of one-dimensional ZnO nanostructures, including processing, structure, property, application and their processing-microstructure-property correlation. Various fabrication methods of the ZnO nanostructures including vapor-liquid-solid process, vapor-solid growth, solution growth, solvothermal growth, template-assisted growth and self-assembly are introduced. The characterization and properties of the ZnO nanostructures are described. The possible applications of these nanostructures are also discussed.     

The key role of hydrogen in the growth of SiC/SiO(2) nanocables

SiC/SiO(2) nanocables, consisting of a crystalline SiC core surrounded by an amorphous silica shell, have been grown by thermal chemical vapour deposition (CVD) at 950?°C on Ni-covered silicon substrates. The addition of methane to a 375?Torr hydrogen atmosphere, after heating the substrate in argon, leads to the growth of the SiC/SiO(2) nanocables, by the carbothermal reduction of silicon oxide as the initial stage. The growth mechanism follows the model previously proposed by us for a reducing medium. From the results obtained, several effects of hydrogen on the deposition process have been established: (a)?reduction of the nickel nucleation sites, thus favouring the formation of SiC from the initial stage; (b)?oxygen removal in the medium hindering the oxidative effect over the SiO and C species, thus promoting the nanocable growth, and (c)?increase of the SiO concentration in the neighbourhood of the active nucleation sites. In addition, it is important to mention that SiC/SiO(2) nanocables, following the already proposed model, are obtained uniquely in a narrow hydrogen pressure range. At?high hydrogen pressure, the unexpected formation of silica nanowires together with the SiC/SiO(2) nanocables has been detected.     

Controlling heterojunction abruptness in VLS-grown semiconductor nanowires via in situ catalyst alloying

For advanced device applications, increasing the compositional abruptness of axial heterostructured and modulation doped nanowires is critical for optimizing performance. For nanowires grown from metal catalysts, the transition region width is dictated by the solute solubility within the catalyst. For example, as a result of the relatively high solubility of Si and Ge in liquid Au for vapor-liquid-solid (VLS) grown nanowires, the transition region width between an axial Si-Ge heterojunction is typically on the order of the nanowire diameter. When the solute solubility in the catalyst is lowered, the heterojunction width can be made sharper. Here we show for the first time the systematic increase in interface sharpness between axial Ge-Si heterojunction nanowires grown by the VLS growth method using a Au-Ga alloy catalyst. Through in situ tailoring of the catalyst composition using trimethylgallium, the Ge-Si heterojunction width is systematically controlled by tuning the semiconductor solubility within a metal Au-Ga alloy catalyst. The present approach of alloying to control solute solubilities in the liquid catalyst may be extended to increasing the sharpness of axial dopant profiles, for example, in Si-Ge pn-heterojunction nanowires which is important for such applications as nanowire tunnel field effect transistors or in Si pn-junction nanowires.     

Suitability of Au- and self-assisted GaAs nanowires for optoelectronic applications

The incorporation of Au during vapor-liquid-solid nanowire growth might inherently limit the performance of nanowire-based devices. Here, we assess the material quality of Au-assisted and Au-free grown GaAs/(Al,Ga)As core-shell nanowires using photoluminescence spectroscopy. We show that at room temperature, the internal quantum efficiency is systematically much lower for the Au-assisted nanowires than for the Au-free ones. In contrast, the optoelectronic material quality of the latter is comparable to that of state-of-the-art planar double heterostructures.     

Vertically Aligned GaAs Nanowires on Graphite and Few-Layer Graphene: Generic Model and Epitaxial Growth

By utilizing the reduced contact area of nanowires, we show that epitaxial growth of a broad range of semiconductors on graphene can in principle be achieved. A generic atomic model is presented which describes the epitaxial growth configurations applicable to all conventional semiconductor materials. The model is experimentally verified by demonstrating the growth of vertically aligned GaAs nanowires on graphite and few-layer graphene by the self-catalyzed vapor-liquid-solid technique using molecular beam epitaxy. A two-temperature growth strategy was used to increase the nanowire density. Due to the self-catalyzed growth technique used, the nanowires were found to have a regular hexagonal cross-sectional shape, and are uniform in length and diameter. Electron microscopy studies reveal an epitaxial relationship of the grown nanowires with the underlying graphitic substrates. Two relative orientations of the nanowire side-facets were observed, which is well explained by the proposed atomic model. A prototype of a single GaAs nanowire photodetector demonstrates a high-quality material. With GaAs being a model system, as well as a very useful material for various optoelectronic applications, we anticipate this particular GaAs nanowire/graphene hybrid to be promising for flexible and low-cost solar cells.     

Dramatic reduction of surface recombination by in situ surface passivation of silicon nanowires

Nanowires have unique optical properties and are considered as important building blocks for energy harvesting applications such as solar cells. However, due to their large surface-to-volume ratios, the recombination of charge carriers through surface states reduces the carrier diffusion lengths in nanowires a few orders of magnitude, often resulting in the low efficiency (a few percent or less) of nanowire-based solar cells. Reducing the recombination by surface passivation is crucial for the realization of high-performance nanosized optoelectronic devices but remains largely unexplored. Here we show that a thin layer of amorphous silicon (a-Si) coated on a single-crystalline silicon nanowire, forming a core-shell structure in situ in the vapor-liquid-solid process, reduces the surface recombination nearly 2 orders of magnitude. Under illumination of modulated light, we measure a greater than 90-fold improvement in the photosensitivity of individual core-shell nanowires, compared to regular nanowires without shell. Simulations of the optical absorption of the nanowires indicate that the strong absorption of the a-Si shell contributes to this effect, but we conclude that the effect is mainly due to the enhanced carrier lifetime by surface passivation.