Template‐Fabricated Gold Nanowires and Nanotubes

Gold nanowires and nanotubes are prepared via electroless deposition of Au onto the pore walls of a porous polymeric membrane. The pores in the support membrane act as a template for the nanostructures. The support is a commercially available nanoporous polycarbonate filter with cylindrical nanoscopic pores. We have shown that by controlling the Au deposition time, Au nanotubes (short deposition times) or nanowires (longer deposition times) can be prepared. The gold nanowires and nanotube membranes can be utilized for nanoelectrode ensembles, molecular filters and as chemical switches.     

Energetics and electronic structures of AlN nanotubes/wires and their potential application as ammonia sensors

Aluminium nitride (AlN) one-dimensional (1D) nanostructures, including crystalline nanowires, faceted nanotubes and conventional single-walled nanotubes, were investigated by means of density functional theory (DFT) using the generalized gradient approximation (GGA). While the larger diameter crystalline nanowires are the most favoured energetically of all these 1D nanostructures, the thick faceted nanotubes have comparable binding energies and can be obtained experimentally. The single-walled nanotubes have the lowest binding energies, and are less feasible experimentally. Due to the surface states at the band edges, the band gaps of all the AlN 1D nanostructures are much smaller than that of bulk AlN. The band structures of AlN nanowires can be modified by NH(3) adsorption. Consequently AlN nanowires have potential applications as gas sensors, since their electronic structures are very sensitive to NH(3) adsorption.     

WS2 nanobuds as a new hybrid nanomaterial

We report on the first inorganic nanobuds: WS2 nanotubes decorated with fullerene-like particles. They were synthesized by sulfurization of W5O14 nanowires. The fullerene-like particles nucleate in surface corrugations of the nanowires and grow by a diffusion process simultaneously with the transformation of nanowires into hollow multiwall nanotubes. Electron microscopy data are correlated with details of the transformation process revealing the possible mechanism of the formation of these new complex nanomaterials.     

Novel vapor phase reactions for the synthesis and modification of carbon nanotubes and inorganic nanowires

Several vapor phase methods have been developed for the preparation and modification of carbon nanotubes and inorganic nanowires. Thus, nebulized spray pyrolysis has been employed for the synthesis of carbon nanotubes and metal nanowires. Multi-walled carbon nanotubes (MWNTs) with fairly uniform diameters and aligned nanotube bundles have been obtained by nebulized spray pyrolysis using solutions of organometallics such as ferrocene in hydrocarbon solvents. Single-crystalline nanowires of zinc, cadmium, cobalt, and lead are obtained by the decomposition of metal acetates. By reacting acid-treated carbon nanotubes with vapors of metal halides, followed by reaction with water and calcination chemically-bonded oxide layers can be obtained on the nanotubes. A similar procedure has been employed to prepare chemically-bonded oxide layers on Al2O3, ZnO, and silicon nanowires by the reaction of the metal halides with the surface hydroxyl groups present on these nanowire surfaces.     

Characterizing the Structure and Properties of Individual Wire‐Like Nanoentities

A new approach to the characterization of the mechanical and electrical properties of individual nanowires and nanotubes is demonstrated by in‐situ transmission electron microscopy (TEM). The technique allows a one‐to‐one correlation between the structure and properties of the nanowires. Recent developments include the determination of the Young's modulii of carbon nanotubes and semiconductor nanowires, femtogram nanobalance of a single fine particle, field emission of carbon nanotubes, and quantum ballistic conductance in carbon nanotubes.     

Synthesis of single crystal metal sulfide nanowires and nanowire arrays by chemical precipitation in templates

Single crystal metal sulfide nanowires and nanowire arrays were synthesized by chemical precipitation reaction in the channels of anodic aluminum oxide templates under ambient conditions with simple inorganic salts as precursors. Aligned metal sulfide arrays were achieved by dissolving the template. This template-directed synthesis yielded well-defined nanowires of varied lengths and diameters for almost all precursors. The crystal quality of metal sulfide nanowires was concentration-dependent, high single crystal nanowires were achieved at low concentrations.     

Synthesis of Inorganic Nanotubes

Nanotubes constitute an exciting class of one‐dimensional nanomaterials of which carbon nanotubes are recognized widely as materials of importance. The possibility of having inorganic nanotubes was recognized early in the 1990s, accompanied by the report of nanotubes of MoS₂ and WS₂. Since then, nanotubes of several inorganic materials have been prepared and characterized. While nanotubes of metal chalcogenides and oxides form a high proportion of the inorganic nanotubes investigated hither to, nanotubes of many other materials have also been prepared and characterized. Several synthetic strategies including both physical and chemical methods have been employed, of which the use of templates, precursors, and hydro‐ or solvothermal methods are prominent. In this article, we shall present a brief account of the present status of the synthesis of nanotubes of elemental materials as well as binary and complex metal oxides, chalcogenides, pnictides and carbides.     

The formation and characterization of palladium nanowires in growing carbon nanotubes using microwave plasma-enhanced chemical vapor deposition

Multi-wall carbon nanotubes were synthesized on electroplated palladium nanoclusters using a microwave plasma-enhanced chemical vapor deposition system in a mixture of methane and hydrogen as precursors. During the synthesis, Pd was melted to fill up the growing multi-wall carbon nanotubes. A growth mechanism was proposed to describe the Pd filling phenomenon. The multi-wall carbon nanotubes could be burned in oxygen plasma and the filled Pd nanowires could thus be collected. The surface morphology of electroplated Pd clusters and the nanostructure of multi-wall carbon nanotubes with filled Pd nanowires were examined by scanning electron microscopy and transmission electron microscopy, respectively. Raman spectra were used to study the first- and second-order signals of multi-wall carbon nanotubes. Bamboo-shaped carbon nanotubes free of filled Pd were observed under a pure methane atmosphere.     

Organic nanowire-templated fabrication of alumina nanotubes by atomic layer deposition

Alumina nanotubes were fabricated by a template method. Tris-(8-hydroxyquinoline) gallium (GaQ3) organic nanowires were used as a soft template for coating with alumina using an atomic layer deposition technique. The deposition was conducted at 25 degrees C by using trimethylaluminum and distilled water as the precursors of Al2O3. Amorphous alumina nanotubes were obtained after removing the GaQ3 by dissolving in toluene or by heat treatment at 350 degrees C. The amorphous nanotubes could be crystallized by heating at 900 degrees C for 1 h in vacuum.     

Filling double-walled carbon nanotubes with WO3 and W nanowires via confined chemical reactions

Carbon nanotubes filled with metals and semiconductors have been regarded as one of the most promising materials for nanodevices. Here, we demonstrate a simple and effective method to produce tungsten trioxide (WO3) and tungsten (W) nanowires with diameters of below 4 nm inside double-walled carbon nanotubes (DWCNTs). First, the precursors, i.e., phosphotungstic acid (HPW, H3PW12O40) molecules, are successfully introduced into DWCNTs. Subsequent decomposition and reduction lead to the formation of WO3 and W nanowires inside DWCNTs. The products were carefully characterized by high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. FTIR spectra provide a direct proof that the HPW molecules enter the DWCNTs as an ionic state, i.e., PW12O40(3-) and H+, instead of the molecular state. HRTEM analysis shows that the diameter of the WO3 nanowires inside DWCNTs is 1.1-2.4 nm with the average length of 16-18 nm, and that for W nanowires is 1.2-3.4 nm with the average length of 15-17 nm. Meanwhile, DWCNTs are doped by the encapsulated WO3 and W nanowires. Tangential band shift in Raman spectra revealed the charge transfer between the nanowires and carbon nanotubes.     

Shape selective growth of single crystalline MnOOH multipods and 1D nanowires by a reductive hydrothermal method

Single crystalline MnOOH multipods were synthesized by a reductive hydrothermal method for the first time based on the use of PEG200 to reduce KMnO₄. When the surfactant, i.e. cetyltrimethylammonium bromide (CTAB), was added into the starting reactant, one-dimensional (1D) single crystalline MnOOH nanowires were formed instead of multipods. Powder X-ray diffraction (XRD), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM) were employed to characterize the microstructure of the products. A possible formation mechanism was proposed. The intermediate products with a lamellar morphology rolled into multipods or nanowires when different surfactants were absorbed on their surface during the further reaction process.     

Shaping Colloidal Rutile into Thermally Stable and Porous Mesoscopic Titania Balls

High crystallinity and controlled porosity are advantageous for many applications such as energy conversion and power generation. Despite many efforts in the last decades, the direct synthesis of organic–inorganic composite materials with crystalline transition metal oxides is still a major challenge. In general, molecules serve as inorganic precursors and heat treatment is required to convert as‐synthesized amorphous composites to stable crystalline materials. Herein, an alternative approach to the direct synthesis of crystalline polymer–metal oxide composites by using a spherical polyelectrolyte brush as the template system is presented. Pre‐synthesized electrostatically stabilized rutile nanocrystals that carry a positive surface charge are used as inorganic precursors. In this approach, the strong Coulomb interactions between anionic polyelectrolyte brush chains and cationic crystalline rutile colloids, whose surfaces are not capped and therefore reactive, are the key factors for the organic–inorganic crystalline composite formation. Stepwise calcination first under argon and followed with a second calcination in air lead to the complete removal of the polymer template without collapse and porous rutile balls are obtained. The results suggest that any colloids that carry a surface charge might serve as inorganic precursors when charged templates are used. It is expected that this hierarchical route for structuring oxides at the mesoscale is generally applicable.     

Conversion of potassium titanate nanowires into titanium oxynitride nanotubes

Tunnel-structured potassium titanate with a K(3)Ti(8)O(17) phase was synthesized by direct oxidation of titanium powder mixed with KF(aq) in water vapor at 923 K. The reaction conditions were adjusted so that uniform single crystalline potassium titanate nanowires with [010] growth direction (length: 5-30 μm, diameter: 80-100 nm) were obtained. Nitridation of the nanowires by NH(3)(g) at 973-1073 K converted the titanate nanowires into rock-salt structured cubic phase single crystalline titanium oxynitride TiN(x)O(y) nanotubes (x = 0.88, y = 0.12, length = 1-10 μm, diameter = 150-250 nm, wall thickness = 30 - 50 nm) and nanorods (x = 0.5, y = 0.5, length = 1-5 μm, diameter = 100-200 nm) with rough surfaces and [200] growth direction. The overall conversion of the titanate nanowires into the nanotubes and the nanorods can be rationalized by Ostwald ripening mechanism. We fabricated an electrode by adhering TiN(x)O(y) nanotubes (0.2 mg) on a screen-printed carbon electrode (geometric area: 0.2 cm(2)). Electrochemical impedance spectroscopy demonstrated its charge transfer resistance to be 20Ω. The electrochemical surface area of the nanotubes on the electrode was characterized by cyclic voltammetry to be 0.32 cm(2). This property suggests that the TiN(x)O(y) nanostructures can be employed as potential electrode materials for electrochemical applications.     

Synthesis of noble metal/carbon nanotube composites in supercritical methanol

A simple and efficient route has been employed to deposit noble metal nanoparticles (Pt, Ru, Pt-Ru, Rh, Ru-Sn) onto carbon nanotubes (CNTs) in supercritical methanol solution. In this method, the inorganic metallic salts acted as metal precursors, and methanol as solvent as well as reductant for the precursors. The as-prepared nanocomposites were structurally and morphologically characterized by X-ray diffraction spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy, and X-ray photoelectron spectroscopy analyses. It was demonstrated that the CNTs were decorated by crystalline metal nanoparticles with uniform sizes and a narrow particle size distribution. The size and loading content of the nanoparticles on CNTs could be tuned by manipulating reaction parameters. Furthermore, the formation mechanism of the composites was also discussed.     

Formation of chiral branched nanowires by the Eshelby Twist

Manipulating the morphology of inorganic nanostructures, such as their chirality and branching structure, has been actively pursued as a means of controlling their electrical, optical and mechanical properties. Notable examples of chiral inorganic nanostructures include carbon nanotubes, gold multishell nanowires, mesoporous nanowires and helical nanowires. Branched nanostructures have also been studied and been shown to have interesting properties for energy harvesting and nanoelectronics. Combining both chiral and branching motifs into nanostructures might provide new materials properties. Here we show a chiral branched PbSe nanowire structure, which is formed by a vapour-liquid-solid branching from a central nanowire with an axial screw dislocation. The chirality is caused by the elastic strain of the axial screw dislocation, which produces a corresponding Eshelby Twist in the nanowires. In addition to opening up new opportunities for tailoring the properties of nanomaterials, these chiral branched nanowires also provide a direct visualization of the Eshelby Twist.     

Growth of Ga-doped ZnS nanowires constructed by self-assembled hexagonal platelets with excellent photocatalytic properties

A new process for making single crystalline undoped and Ga-doped ZnS nanowires with simple evaporation and condensation procedures on Si and GaN is introduced. The process does not need additional catalysts or precursors. The growth mechanism is studied using transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. TEM images show that the undoped ZnS nanowires exhibit an ordinary straight morphology, whereas the Ga-doped nanowires are composed of aligned hexagonal platelets, connected in the center into nanowires to maximize surface area. The Ga 2p3 and S 2p peaks in the XPS results confirm the presence of Ga doping in the form of Ga-S bonding. Raman spectra show that the ZnS LO peak is red-shifted from 349 to 347 cm(-1), indicative of a tensile stress caused by the Ga dopants. The growth mechanism and photocatalytic activity of the Ga-doped ZnS nanowires are discussed. We also demonstrate the excellent photocatalytic activity of Ga-doped ZnS nanowires as compared to those of undoped ZnS nanowires and Ga-doped ZnS nanosheets.     

过渡族金属硫化物纳米管结构研发现状

随着碳富勒烯和碳纳米管的发现,具有类似层状结构的纳米颗粒MoS2,由于片层状平面结构的不稳定,易形成封闭多面体笼状结构和管状结构.综述了过渡族金属硫化物MS2(M=W,Mo,Nb,Ta,Zr,Ti,Re,Hf)纳米管的合成方法、微观结构、生长机制及其潜在的性能和应用.     

Planar Growth,Integration, and Applications of Semiconducting Nanowires

Silicon and other inorganic semiconductor nanowires (NWs) have been extensively investigated in the last two decades for constructing high-performance nanoelectronics, sensors, and optoelectronics. For many of these applications, these tiny building blocks have to be integrated into the existing planar electronic platform, where precise location, orientation, and layout controls are indispensable. In the advent of More-than-Moore's era, there are also emerging demands for a programmable growth engineering of the geometry, composition, and line-shape of NWs on planar or out-of-plane 3D sidewall surfaces. Here, the critical technologies established for synthesis, transferring, and assembly of NWs upon planar surface are examined; then, the recent progress of in-plane growth of horizontal NWs directly upon crystalline or patterned substrates, constrained by using nanochannels, an epitaxial interface, or amorphous thin film precursors is discussed. Finally, the unique capabilities of planar growth of NWs in achieving precise guided growth control, programmable geometry, composition, and line-shape engineering are reviewed, followed by their latest device applications in building high-performance field-effect transistors, photodetectors, stretchable electronics, and 3D stacked-channel integration.     

Water-soluble organo-silica hybrid nanowires

There has been growing interest in the past decade in one-dimensional (1D) nanostructures, such as nanowires, nanotubes or nanorods, owing to their size-dependent optical and electronic properties and their potential application as building blocks, interconnects and functional components for assembling nanodevices. Significant progress has been made; however, the strict control of the distinctive geometry at extremely small size for 1D structures remains a great challenge in this field. The anisotropic nature of cylindrical polymer brushes has been applied to template 1D nanostructured materials, such as metal, semiconductor or magnetic nanowires. Here, by constructing the cylindrical polymer brushes themselves with a precursor-containing monomer, we successfully synthesized hybrid nanowires with a silsesquioxane core and a shell made up from oligo(ethylene glycol) methacrylate units, which are soluble in water and many organic solvents. The length and diameter of these rigid wires are tunable by the degrees of polymerization of both the backbone and the side chain. They show lyotropic liquid-crystalline behaviour and can be pyrolysed to silica nanowires. This approach provides a route to the controlled fabrication of inorganic or hybrid silica nanostructures by living polymerization techniques.     

Nanowires sheathed inside nanotubes: Manipulation,properties and applications

Since the discovery of metals encapsulated into multi-walled carbon nanotubes (CNTs), such sheathed structures attracted extensive interest with respect to the development of various synthetic strategies for producing the unique structure of nanowires sheathed inside nanotubes. The nanowire materials varied from metals to alloys, from semiconductors to insulators, and even metal–semiconductor heterojunctions were tried. In recent years, the studies on these nanostructures have been mainly focused on in-situ manipulation, property analysis and applications. Exploration of on-demand nano-engineering of the regarded structures toward practical device design and fabrication was mainly guided by high-resolution transmission electron microscopy (TEM) technique combining new capabilities of implementation of atomic force (AFM) or scanning tunneling microscopy (STM) holders, and heating/cooling holders. Such novel in-situ TEM techniques have rapidly developed to a stage where they truly become a very powerful tool for the studies of core/shell nanowire heterostructures. In this review, we summarize the significant developments and achievements in regards of manipulation, property measurements and device applications of inorganic nanowires sheathed inside nanotubes according to different categories of the filling materials, i.e., metals, alloys, compounds and semiconductor–metal heterojunction nanowires. We also highlight the irreplaceable value of in-situ TEM technology in this field, compare different fillings for so-called nanothermometers, discuss mass transportation mechanism in nanotubes, and conclude with an outlook of future developments and challenging issues that are still in the premature stage.