The interplay of structural and optical properties in individual ZnO nanostructures

Semiconductor nanostructures exhibit unique properties distinct from their bulk counterparts by virtue of nanoscale dimensions; in particular, exceptionally large surface area-to-volume ratios relative to that of the bulk produce variations in surface state populations that have numerous consequences on materials properties. Of the low-dimensional semiconductor nanostructures, nanowires offer a unique prospect in nanoscale optoelectronics due to their one-dimensional architecture. Already, many devices based upon individual nanowires have been demonstrated, but questions about how nano-size and structural variations affect the underlying materials properties still remain unanswered. Here, we focus on understanding the growth mechanism and kinetics of ZnO nanowires and related nanowalls, and their effects on nanoscale structural and optical properties.     

Fundamental electronic properties and applications of single-walled carbon nanotubes

Recent scanning tunneling microscopy studies of the intrinsic electronic properties of single-walled carbon nanotubes (SWNTs) are overviewed in this Account. A brief theoretical treatment of the electronic properties of SWNTs is developed, and then the effects of finite curvature and broken symmetry on electronic properties, the unique one-dimensional energy dispersion in nanotubes, the interaction between local spins and carriers in metallic nanotubes systems, and the atomic structure and electronic properties of intramolecular junctions are described. The implications of these studies for understanding fundamental one-dimensional physics and future nanotube device applications are also discussed.     

Tip-Induced Charging of Free Standing Semiconductor Nanowires and Carbon Nanotubes

We investigate the distribution of charges injected into one-dimensional nanostructures like semiconductor nanowires and carbon nanotubes. The charges are injected by an atomic force microscope tip and monitored by means of electrostatic force microscopy. We demonstrate that the charges distribute rapidly along the axes of both types of nanostructures. The charges deposited on nanowires are shown to migrate to the substrate on a shorter time scale than those deposited on nanotubes, while the holes migrate even slower than the electrons. This behaviour is attributed to the amount and type of available trap states in the respective nanostructure.     

A computational and experimental investigation of the mechanical properties of single ZnTe nanowires

One-dimensional nanostructures such as ZnTe, CdTe, Bi(2)Te(3) and others have attracted much attention in recent years for their potential in thermoelectric devices among other applications. A better understanding of their mechanical properties is important for the design of devices. A combined experimental and computational approach has been used here to investigate the size effects on the Young's modulus of ZnTe nanowires (NWs). The mechanical properties of individual ZnTe nanowires in a wide diameter range (50-230 nm) were experimentally measured inside a high resolution transmission electron microscope using an atomic force microscope probe with the ability to record in situ continuous force-displacement curves. The in situ observations showed that ZnTe NWs are flexible nanostructures with the ability to withstand relatively high buckling forces without becoming fractured. The Young's modulus is found to be independent of nanowire diameter in the investigated range, in contrast to reported results for ZnO NWs and carbon nanotubes where the modulus increases with a decrease in diameter. Molecular dynamics simulations performed for nanowires with diameters less than 20 nm show limited size dependence for diameters smaller than 5 nm. The surface atoms present lower Young's modulus according to the simulations and the limited size dependency of the cylindrical ZnTe NWs is attributed to the short range covalent interactions.     

Constructing high-performance radiation-resistant ternary YSZ-MgO-CNT nanocomposites via tailored nanostructures

Developing long-lifetime bulk-form ceramic-based materials with high irradiation resistance is crucial for advanced nuclear systems. Here, we incorporated carbon nanotubes (CNTs) into yttria-stabilized zirconia (YSZ) and magnesia (MgO) nanocrystals to fabricate bulk YSZ-MgO-CNT nanocomposites with abundant ternary nanostructures by spark plasma sintering. To understand the role of tailored ternary nanostructure on irradiation, we investigated the microstructure and mechanical properties evolutions of the YSZ-MgO-CNT nanocomposites irradiated by multi-energy He⁺ ions at high temperature to different fluences. Compared with the single-phase YSZ and ultrafine-grained YSZ-MgO composites, the YSZ-MgO-CNT nanocomposites possessed higher ability to manage irradiation-induced He bubbles/defects via the defect-interface interactions of proposed “loading-unloading” and “loading-transporting-unloading” mechanisms for controlling the dynamical behaviors of He atoms/defects in the CNT-doped ternary nanostructures, thereby presenting more stable microstructure and better performance in resisting irradiation hardening. This work provides insight into the design of advanced inert matrix nuclear fuel and new nuclear waste management materials.     

Grain boundary curvatures in polycrystalline SrTiO3: Dependence on grain size,topology, and crystallography

By mapping grain orientations on parallel serial sections of a SrTiO₃ ceramic, it was possible to reconstruct three-dimensional orientation maps containing more than 3000 grains. The grain boundaries were approximated by a continuous mesh of triangles and mean curvatures were determined for each triangle. The integral mean curvatures of grain faces were determined for all grains. Small grains with fewer than 16 neighbors mostly have positive mean curvatures while larger grains with more than 16 neighbors mostly have negative mean curvatures. It is also possible to correlate the mean curvature of individual triangles with the crystallographic characteristics of the grain boundary. The mean curvature is lowest for grain boundaries with (100) orientations and highest for grain boundaries with (111) orientations. This trend is inversely correlated to the relative areas of grain boundaries and directly correlated to the relative grain boundary energy. The direct correlation between the energy and curvature is consistent with the expected behavior of grain boundaries made up of singular orientations. Furthermore, because both the relative energy and curvature of grain boundaries with (100) orientations are minima in the distributions, these boundaries also have the lowest driving force for migration.     

Influence of electrodeposition techniques on Ni nanostructures

Different Ni nanostructure arrays were fabricated by pulsed electrodeposition from a Watts bath inside the pores of anodic alumina membrane (AAM) templates. Under a trapezoidal waveform of potential, consisting of fast linear sweeps between 0 and −3 V (SCE) interleaved by delay times at 0 (10 s) and −3 V (0.1 s), Ni nanowires were grown. The rate of nanowires growth was constant up to 60 min of deposition. For longer times, the growth of nanowires was not uniform, and after about 180 min some nanowires reached the template surface exposed to the electrolyte. Under square potential pulses between the same potentials (pulse length 1 s), nanotubes of Ni are obtained. Morphological analysis of these nanostructures at different lengths revealed that the inner profile of nanotubes evolved from cylindrical to conical with increasing deposition time. The possibility to grow either nanowires or nanotubes in dependence of the potential waveform, as well as the growth rate of nanostructures were discussed taking into account the reaction of hydrogen evolution, occurring simultaneously with Ni electrodeposition.     

One dimensional nanostructure/nanoparticle composites as photoanodes for dye-sensitized solar cells

Dye-sensitized solar cells (DSCs) show potential as a low cost alternative to silicon solar cells. Power conversion efficiencies exceeding 12% have been achieved for DSCs. Typical DSCs are based on TiO(2) nanoparticle photoanodes, which have numerous grain boundaries, surface defects and trap states as electrons transport from one particle to the other. Such defects and trap states increase back charge transfer (charge recombination) from the photoanode to electrolyte. One dimensional (1D) nanostructures such as nanofibers, nanorods, nanowires, and nanotubes can offer direct and fast electron transport to the electron collecting electrode. However, these 1D nanostructures have a major disadvantage of having insufficient surface area and inefficient dye attachment. To solve this challenge, mixtures of TiO(2) nanoparticles and 1D nanostructures (e.g. nanofibers, nanorods, nanowires, and nanotubes) are used to take advantage of the large surface area of nanoparticles and efficient charge transport of 1D nanostructures. In this article, we review the recent developments in using mixtures of 1D nanostructures and nanoparticles as photoanodes for efficient DSCs. Various randomly oriented and vertically aligned 1D nanostructures and their composites with nanoparticles are discussed. Future increase of efficiency in DSCs using 1D nanostructure/nanoparticle composites will rely on the optimization of diameters of 1D nanostructures, control of ratios of 1D nanostructures and nanoparticles, increase of crystallinity, and reduction of surface defects on the 1D nanostructures. This work will provide guidance for designing and growing appropriate 1D nanostructures, and combining them with nanoparticles at an optimal ratio for efficient DSCs.     

Controllable melting and flow of β-Sn in flexible amorphous carbon nanotubes

A high-yield of carbon nanotubes filled with β-Sn nanowires has been produced by the thermal pyrolysis of acetylene over SnO₂ catalysts. Electron beam irradiation (EBI) induced melting and flow of Sn in the nanotubes and this could be controlled by changing the electron beam current density. The mass flow rate of the Sn ranged from 0.9 to 8.2 fg/s. The melting of the nanowires is a result of the temperature rise caused by the EBI. Many factors, including temperature variation, charging, and EBI induced deformation of the carbon shells, contribute to the flow of Sn.     

Thermal stabilization of thin gold nanowires by surfactant-coating: a molecular dynamics study

The thermal stabilization of thin gold nanowires with a diameter of about 2 nm by surfactants is investigated by means of classical molecular dynamics simulations. While the well-known melting point depression leads to a much lower melting of gold nanowires compared to bulk gold, coating the nanowires with surfactants can reverse this, given that the attractive interaction between surfactant molecules and gold atoms lies beyond a certain threshold. It is found that the melting process of coated nanowires is dominated by surface instability patterns, whereas the melting behaviour of gold nanowires in a vacuum is dominated by the greater mobility of atoms with lower coordination numbers that are located at edges and corners. The suppression of the melting by surfactants is explained by the isotropic pressure acting on the gold surface (due to the attractive interaction) which successfully suppresses large-amplitude thermal motions of the gold atoms.     

Ordered arrays of copper nanowires enveloped in polyaniline nanotubes

Copper nanowires enveloped in polyaniline (PANI) nanotubes were obtained by ‘second order’ electrodeposition into the pores of anodic porous alumina. The templated synthesis of copper nanowires was performed by both potentiostatic and galvanostatic methods. The morphology of the polyaniline nanotubes, copper nanowires as well as the copper-filled polyaniline nanotubes was investigated by means of scanning electron microscopy. The copper nanowires were protected from corrosion and oxidation by the PANI nanotubes. Energy-dispersive X-ray spectroscopy was performed for the microanalysis of the copper deposition into the polyaniline nanotubes. Cyclic voltammetry was employed to assess the electrochemical properties of the obtained nanostructures as well as the influence of the copper nanowires synthesis method on the properties of filled polyaniline nanotubes.     

Recent advances in synthesis, physical properties and applications of conducting polymer nanotubes and nanofibers

This article summarizes and reviews the various preparation methods, physical properties, and potential applications of one-dimensional nanostructures of conjugated polyaniline (PANI), polypyrrole (PPY) and poly(3,4-ethylenedioxythiophene) (PEDOT). The synthesis approaches include hard physical template method, soft chemical template method, electrospinning, and lithography techniques. Particularly, the electronic transport (e.g., electrical conductivity, current-voltage (I-V) characteristics, magnetoresistance, and nanocontact resistance) and mechanical properties of individual nanowires/tubes, and specific heat capacity, magnetic susceptibility, and optical properties of the polymer nanostructures are presented with emphasis on size-dependent behaviors. Several potential applications and corresponding challenges of these nanofibers and nanotubes in chemical, optical and bio-sensors, nano-diodes, field effect transistors, field emission and electrochromic displays, super-capacitors and energy storage, actuators, drug delivery, neural interfaces, and protein purification are also discussed.     

Synthesis of different magnetic carbon nanostructures by the pyrolysis of ferrocene at different sublimation temperatures

Various magnetic nanostructures such as Fe nanoparticles (Fe-NPs) adhering to single-walled carbon nanotubes, carbon-encapsulated Fe-NPs, Fe-NP decorated multi-walled carbon nanotubes (MWCNTs), and Fe-filled MWCNTs have been synthesized by the pyrolysis of pure ferrocene. It is found that the formation of the nanostructures can be selectively controlled by simply adjusting the sublimation temperature of ferrocene, while keeping all other experimental parameters unchanged. Magnetic characterization reveals that these nanostructures have an enhanced coercivity, higher than that of bulk Fe at room temperature. Based on the experimental results, the formation mechanism of the nanostructures is discussed in detail.     

Thermal Stability of Single Walled SiGe Nanotube with Vacancy Defects: a Molecular Dynamics Simulation Study

The aim of this investigation was to study thermal properties of perfect and imperfect single-walled Si-x%Ge (atomic percentages) armchair nanotubes. We have performed molecular dynamics simulation computations based on Tersoff many body potential in the constant temperature and pressure ensemble. The temperature and pressure of the nanotube were controlled by a Nose-Hoover thermostat and barostat, respectively. The phase diagram of the Si-x%Ge nanotube was built by changing atomic percentages of Ge and then melting the nanotube. Our results show that cohesive energy increases, isobaric heat capacity, and thermal stability of Si-x%Ge nanotube decrease with increasing Ge composition in the nanotube. Moreover, we created 0.5, 1, 1.5, …, 4 at% vacancy defects in the nanotubes to study thermal properties of imperfect Si-Ge nanotubes. Finally, the average of formation energy per defect was calculated as 0.39 eV by MD simulation.     

Enhancing Solar Cell Efficiencies through 1-D Nanostructures

The current global energy problem can be attributed to insufficient fossil fuel supplies and excessive greenhouse gas emissions resulting from increasing fossil fuel consumption. The huge demand for clean energy potentially can be met by solar-to-electricity conversions. The large-scale use of solar energy is not occurring due to the high cost and inadequate efficiencies of existing solar cells. Nanostructured materials have offered new opportunities to design more efficient solar cells, particularly one-dimensional (1-D) nanomaterials for enhancing solar cell efficiencies. These 1-D nanostructures, including nanotubes, nanowires, and nanorods, offer significant opportunities to improve efficiencies of solar cells by facilitating photon absorption, electron transport, and electron collection; however, tremendous challenges must be conquered before the large-scale commercialization of such cells. This review specifically focuses on the use of 1-D nanostructures for enhancing solar cell efficiencies. Other nanostructured solar cells or solar cells based on bulk materials are not covered in this review. Major topics addressed include dye-sensitized solar cells, quantum-dot-sensitized solar cells, and p-n junction solar cells.     

The effects of confinement inside carbon nanotubes on catalysis

The unique tubular morphology of carbon nanotubes (CNTs) has triggered wide research interest. These structures can be used as nanoreactors and to create novel composites through the encapsulation of guest materials in their well-defined channels. The rigid nanotubes restrict the size of the encapsulated materials down to the nanometer and even the sub-nanometer scale. In addition, interactions may develop between the encapsulated molecules and nanomaterials and the CNT surfaces. The curvature of CNT walls causes the π electron density of the graphene layers to shift from the concave inner to the convex outer surface, which results in an electric potential difference. As a result, the molecules and nanomaterials on the exterior walls of CNTs likely display different properties and chemical reactivities from those confined within CNTs. Catalysis that utilizes the interior surface of CNTs was only explored recently. An increasing number of studies have demonstrated that confining metal or metal oxide nanoparticles inside CNTs often leads to a different catalytic activity with respect to the same metals deposited on the CNT exterior surface. Furthermore, this inside and outside activity difference varies based on the metals used and the reactions catalyzed. In this Account, we describe the efforts toward understanding the fundamental effects of confining metal nanoparticles inside the CNT channels. This research may provide a novel approach to modulate their catalytic performance and promote rational design of catalysts. To achieve this, we have developed strategies for homogeneous dispersion of nanoparticles inside nanotubes. Because researchers have previously demonstrated the insertion of nanoparticles within larger nanotubes, we focused specifically on multiwalled carbon nanotubes (MWCNTs) with an inner diameter (i.d.) smaller than 10 nm and double-walled carbon nanotubes (DWCNTs) with 1.0-1.5 nm i.d. The results show that CNTs with well-defined morphology and unique electronic structure of CNTs provide an intriguing confinement environment for catalysis.     

Multiwall carbon nanotubes continuously filled with micrometre-length ferromagnetic α-Fe nanowires

Carbon nanotubes filled with continuous crystalline nanowires of nanometre-scale diameter and micrometre-scale length of the ferromagnetic phase α-Fe were produced with a new chemical vapour deposition method. We report a new two-stage approach, a perturbed-vapour method of synthesis followed by a post-synthesis heat treatment that produces multiwall carbon nanotubes filled with at least 19 micrometre-length nanowires of α-Fe. Previously reported synthesis routes use steady-state conditions to guarantee nanowire continuity but result only in small (less than one-micrometre length) nanowires comprising isolated or mixed phases of either α-Fe, Fe₃C, or γ-Fe. Here flower-like clusters of carbon nanotubes continuously filled with α-Fe were produced by perturbation of a laminar ferrocene (Fe(C₅H₅)₂) vapour flow in a conventional horizontal chemical vapour deposition reactor. Single-phase filling was achieved by a post-synthesis annealing at 500 °C for 15 h in Ar flow. Electron microscopy studies revealed the high quality of the structural integrity of both nanotubes and encapsulated nanowires. These nanostructures possess a high coercivity of 580 Oe and a very high saturation magnetization of 189.5 emu/g comparable with bulk α-Fe.     

Preparation of carbon-coated TiO2 nanostructures for lithium-ion batteries

Carbon-coated TiO₂ one-dimensional nanostructures are synthesized by hydrothermal reaction followed by post-calcination at various temperatures. Post-calcination induces crystallization of TiO₂ and the complete crystallization of anatase phase is observed at 600 °C of the calcination temperature. Carbon-coated TiO₂ nanostructures show relatively poor crystallinity as compared with the pristine counterparts, but their lithiation capacity and high rate capability are improved throughout all calcination temperatures. The coated carbon suppresses severe agglomeration of TiO₂ nanotubes which allows easy access of Li-ions and electrons to the whole surface of primary nanotubes, leading to the better lithiation performance. Higher calcination temperatures cause excessive growth of nanotube walls, leading to the collapse of tubular morphology and deterioration of lithiation performance. At 700 °C of the calcination temperature, the enhanced electronic conductivity from the graphitization of the coated carbon seems to be the main reason for the improved capacity of TiO₂ nanowires.     

Nanoscale semiconductor-insulator-metal core/shell heterostructures: facile synthesis and light emission

Controllably constructing hierarchical nanostructures with distinct components and designed architectures is an important theme of research in nanoscience, entailing novel but reliable approaches of bottom-up synthesis. Here, we report a facile method to reproducibly create semiconductor-insulator-metal core/shell nanostructures, which involves first coating uniform MgO shells onto metal oxide nanostructures in solution and then decorating them with Au nanoparticles. The semiconductor nanowire core can be almost any material and, herein, ZnO, SnO(2) and In(2)O(3) are used as examples. We also show that linear chains of short ZnO nanorods embedded in MgO nanotubes and porous MgO nanotubes can be obtained by taking advantage of the reduced thermal stability of the ZnO core. Furthermore, after MgO shell-coating and the appropriate annealing treatment, the intensity of the ZnO near-band-edge UV emission becomes much stronger, showing a 25-fold enhancement. The intensity ratio of the UV/visible emission can be increased further by decorating the surface of the ZnO/MgO nanowires with high-density plasmonic Au nanoparticles. These heterostructured semiconductor-insulator-metal nanowires with tailored morphologies and enhanced functionalities have great potential for use as nanoscale building blocks in photonic and electronic applications.     

Electrochemical characterisation of patterned carbon nanotube electrodes on silane modified silicon

Previously we have used atomic force anodisation lithography, with a self-assembled monolayer of hexadecyltrichlorosilane as a resist, to pattern silicon oxide nanostructures onto a p-type silicon (1 0 0) substrate. A condensation reaction was used to immobilise carbon nanotubes with high carboxylic acid functionality directly to the silicon oxide. A further condensation reaction using this surface attached the molecule ferrocenemethanol to the bound nanotubes. These new nanostructures were used as electrodes to observe the oxidation and reduction of ferrocene. However, because the small currents measured are near the detection limits of the electrochemical system used, important electrode kinetics could not to be obtained. A scribing approach made larger regions of oxidised silicon leading to the creation of larger scale patterned arrangements of carbon nanotubes allowing measurement of important electrochemical parameters such as electrode kinetics, electron transfer rates and surface concentration of redox molecules. Knowledge of these characteristics has provided insights into the behaviour of the microelectrodes created using atomic force microscopy.