Formation of single-wall carbon nanohorn aggregates hybridized with carbon nanocapsules by laser vaporization

Single-wall carbon nanohorn (SWNH) aggregates hybridized with carbon nanocapsules (CNCs) were fabricated at a high yield (∼70%). The carbon was laser-vaporized for 2 s into an Ar gas atmosphere with one of the following: Fe, Al, Si, Co, Ni, Cu, Ag, La₂O₃, Y₂O₃, and G₂O₃. By optimizing the Ar gas pressure and metal content, we were able to produce hybridized SWNH structures for Fe, Co, Ni, Cu, and Ag. Possible mechanisms for governing hybrid production, which occurs with smaller CNCs (<100 nm) with only certain metals and carbide, are discussed on the basis of thermal and catalytic graphitization. PACS 61.46.Df; 68.37.Lp; 81.16.Mk     

Environmental transmission electron microscopy observations of the growth of carbon nanotubes under nanotube-nanotube and nanotube-substrate interactions

The growth process of carbon nanotubes (CNTs) under CNT-CNT and CNT-substrate interactions has been observed directly by environmental transmission electron microscopy. Even a free standing CNT occasionally swings during the growth until it touches the substrate. In addition, we show that the growth direction of CNTs changes due to the interaction between CNTs.     

Structural and optical characterization of undoped, doped, and clustered ZnO thin films obtained by PLD for gas sensing applications

The synthesis by pulsed laser deposition technique of zinc oxide thin films suitable for gas sensing applications is herein reported. The ZnO targets were irradiated by an UV KrF^* (λ = 248 nm, τ_FWHM ∼7 ns) excimer laser source, operated at 2.8 J/cm² incident fluence value, whilst the substrates consisted of SiO₂(0 0 1) wafers heated at 150 °C during the thin films growth process. The experiments were performed in an oxygen dynamic pressure of 10 Pa. Structural and optical properties of the thin films were investigated. The obtained results have demonstrated that the films are c-axis oriented. Their average transmission in the visible-infrared spectral region was found to be about 85%. The equivalent refractive indexes and extinction coefficients were very close to those of the tabulated reference values. Doping with 0.5% Au and coating with 100 pulses of Au clusters caused but a very slight decrease (with a few percent) of both transmission and refractive index values. The coatings with the most appropriate optical properties as waveguides have been selected and their behavior was tested for butane sensing.     

Hot filament effects on CVD of carbon nanotubes

We grew vertically aligned CNTs via HFCVD using mixtures of methane and hydrogen as feedstock, and investigated the dependence of CNT growth on feedstock composition, filament temperature, and filament types. At the filament temperature of 2050 °C tungsten filaments were more efficient for CNT growth than tantalum ones, and higher CNT growth rates were observed when tungsten filaments were operated at 1900 °C. Regardless of filament temperatures and types, monotonic increase in growth rate of vertically aligned CNTs was observed as we increased the methane concentration in the feedstock. In‐situ investigation of feedstock dissociation revealed the generation of various radical species, and, moreover, a strong correlation between CNT growth rates and relative mole fractions of single‐carbon radicals. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Integration and characterization of aligned carbon nanotubes on metal/silicon substrates and effects of water

We report here a facile way to grow aligned multi-walled carbon nanotubes (MWCNTs) on various metal (e.g. gold, tungsten, vanadium and copper)/silicon electrically conductive substrates by aerosol-assisted chemical vapor deposition (AACVD). Without using any buffer layers, integration of high quality MWCNTs to the conductive substrates has been achieved by introducing appropriate amount of water vapor into the growth system. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) determination indicate tidy morphology and narrow diameter distribution of the nanotubes as well as promising growth rate suitable for industrial applications. Raman spectra analysis illustrates that the structural order and purity of the nanotubes are significantly improved in the presence of water vapor. The growth mechanism of the nanotubes has been discussed. It is believed that water vapor plays a key role in the catalyst-substrate interaction and nucleation of the carbon nanotubes on the conductive substrates. This synthesis approach is expected to be extended to other catalyst-conductive substrate systems and provide some new insight in the direct integration of carbon nanotubes onto conductive substrates, which promises great potential for applications in electrical interconnects, contacts for field emitters, and other electronic nanodevices.     

Template assisted formation of micro- and nanotubular carbon nitride materials

Micro- and nanotubes of an amorphous carbon nitride material were synthesized by metathesis reactions between cyanuric chloride (C₃N₃Cl₃) and different nitrogen sources, such as Li₂(CN₂) or Li₃(BN₂). The intermediate formation of needle-shaped crystals of N(C₃N₃Cl₂)₃ was always observed in our reactions, and investigated with respect to their role as a template in the formation of tubes. Chemical analyses of the micro- and nanotubes reveal carbon to nitrogen ratios near 3:4, consistent with the suspected material C₃N₄. Synthesized carbon nitride materials were thermally stable up to 600 ^°C in inert atmosphere. They were inspected by a number of physical measurements, mainly using TEM, EDX and IR investigations.     

Highly selective growth of vertically aligned double‐walled carbon nanotubes by a controlled heating method and their electric double‐layer capacitor properties

Vertically aligned double‐walled carbon nanotubes (DWCNTs) with the highest selectivity of 90% were synthesized by a controlled heating method and their electric double‐layer capacitor characteristics were evaluated. DWCNT arrays had a specific capacitance of 83 F/g, which is one of the highest values among CNT arrays in a nonaqueous solution and is almost equivalent to that for single‐walled CNT (SWCNT) arrays reported previously. At the same specific capacitance, DWCNTs with superior structural properties are more promising for practical capacitors than SWCNTs. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Large-scale purification of single-wall carbon nanotubes: process, product, and characterization

Received: 13 February 1998     

Structural characterization of nc-Si films grown by low-energy PECVD on different substrates

The knowledge and control of the structural details (texture, crystallite environment and size) of nanocrystalline silicon films is a prerequisite for their proper application in various technological fields. To this purpose, nanocrystalline silicon films grown by low energy plasma enhanced chemical vapour deposition (LEPECVD) on different kinds of substrates were submitted to a systematic characterization using Raman spectroscopy, X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). The results showed how the difference in substrate morphology is responsible for a deep difference in the film structural properties, particularly in the case of high silane dilutions.     

Boron doped carbon nanotubes via ceramic catalysts

A facile metal catalyst free route to synthesize boron doped (0.6%–1.0%) carbon nanotubes via ceramic nanowires in which the formation of the nanowires (probably serving as templates), the carbon nanotubes and their doping all occur unanimously in the reaction, is presented.

     

Effect of nickel,iron and cobalt on growth of aligned carbon nanotubes

The effect of pure nickel, iron and cobalt on growth of aligned carbon nanotubes was systematically studied by plasma-enhanced hot-filament chemical vapor deposition. It is found that the catalyst has a strong effect on the nanotube diameter, growth rate, wall thickness, morphology and microstructure. Ni yields the highest growth rate, largest diameter and thickest wall, whereas Co results in the lowest growth rate, smallest diameter and thinnest wall. The carbon nanotubes catalyzed by Ni have the best alignment and the smoothest and cleanest wall surface, whereas those from Co are covered with amorphous carbon and nanoparticles on the outer surface. The carbon nanotubes produced from Ni catalyst also exhibit a reasonably good graphitization. Therefore, Ni is considered as the most suitable catalyst for growth of aligned carbon nanotubes. Received: 30 November 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

A comparative study of field-emission from different one dimensional carbon nanostructures synthesized via thermal CVD system

Different one dimensional (1D) carbon nanostructures, such as carbon nanonoodles (CNNs), carbon nanospikes (CNSs) and carbon nanotubes (CNTs) have been synthesized via thermal chemical vapour deposition (TCVD) technique. The different 1D morphologies were synthesized by varying the substrate material and the deposition conditions. The as-prepared samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM). FESEM and TEM images showed that the diameters of the CNNs and CNTs were ∼40 nm while the diameters of the CNSs were around 100 nm. Field emission studies of the as-prepared samples showed that CNSs to be a better field emitter than CNNs, whereas CNTs are the best among the three producing large emission current. The variation of field emission properties with inter-electrode distance has been studied in detail. Also the time dependent field emission studies of all the nanostructures have been carried out.     

Fabrication of completely filled carbon nanotubes with copper nanowires in a confined space

Carbon nanotubes (CNTs) filled completely with polycrystalline Cu nanowires were synthesized by laser vaporization of Cu and graphite under high-pressure Ar gas atmosphere. Depending on the Ar gas pressure (0.1–0.9 MPa) and the Cu content (1–40 at.%) in graphite targets for laser vaporization, various products with different morphologies were observed by scanning and transmission electron microscopy. The ratios of the Cu-filled CNTs and carbon nanocapsules particularly increased as Ar gas pressure was increased. The maximum ∼60% fraction of Cu-filled CNTs with outer diameter of 10–50 nm and length of 0.3–3 μm was achieved at 0.9 MPa from graphite containing 20 at.% Cu. Most of the encapsulated Cu-nanowires were surrounded by single, double, or triple graphitic layers. Although the yield of the Cu-filled CNTs was also dependent on the Cu content in the graphite targets, no unfilled CNTs were produced even for low Cu content. The growth of Cu-filled CNTs is explained by the formation of molten Cu–C composite particles with an unusually C-rich composition in a space confined by high-pressure Ar gas, followed by precipitating Cu and C from the particles and subjecting them to phase separation.     

Role of growth temperature on nanostructure and field emission properties of PLD thin carbon films

Thin carbon films have been deposited in vacuum (∼10⁻⁴ Pa) on Si substrates by pulsed laser ablation of a graphite target using a Nd:YAG laser operating in the near infrared region (λ=1064 nm). The samples have been deposited at different substrate temperatures (T _sub) ranging from room temperature (RT) to 800°C. X-ray diffraction analysis established the progressive formation of nanosized graphene structures as T _sub increased. In fact, film structure evolves from almost amorphous to nanostructured phase characterized by graphene layers oriented perpendicularly to the film plane. The film density, evaluated by X-ray reflectivity measurements, is strongly affected by T _sub. At RT the film density is similar to the graphite one, while it decreases at higher T _sub. The electrical properties of the samples have been characterized by field emission measurements. The parameters describing the emitter properties (threshold field E _th and field enhancement factor β) have been evaluated using variable anode-to-cathode distance method. Samples deposited at low T _sub have shown the best emission properties, presenting lower E _th and larger β values than those deposited at higher T _sub. This is mainly attributed to the sensible density variation, which is in competition with the slighter augment of mean nanoparticle size.     

Pulsed laser CVD investigations of single-wall carbon nanotube growth dynamics

The nucleation and rapid growth of single-wall carbon nanotubes (SWNTs) were explored by pulsed-laser assisted chemical vapor deposition (PLA-CVD). A special high-power, Nd:YAG laser system with tunable pulse width (>0.5 ms) was implemented to rapidly heat (>3×10⁴°C/s) metal catalyst-covered substrates to different growth temperatures for very brief (sub-second) and controlled time periods as measured by in situ optical pyrometry. Utilizing growth directly on transmission electron microscopy grids, exclusively SWNTs were found to grow under rapid heating conditions, with a minimum nucleation time of >0.1 s. By measuring the length of nanotubes grown by single laser pulses, extremely fast growth rates (up to 100 microns/s) were found to result from the rapid heating and cooling induced by the laser treatment. Subsequent laser pulses were found not to incrementally continue the growth of these nanotubes, but instead activate previously inactive catalyst nanoparticles to grow new nanotubes. Localized growth of nanotubes with variable density was demonstrated through this process and was applied for the reliable direct-write synthesis of SWNTs onto pre-patterned, catalyst-covered metal electrodes for the synthesis of SWNT field-effect transistors.     

High yield incorporation and washing properties of halides incorporated into single walled carbon nanotubes

We describe here the high yield filling (i.e. >50%) of single walled nanotubes (SWNTs) with a variety of halides, achieved according to various modified filling procedures. Both bundles and discrete SWNTs can be filled continuously up to lengths of several hundred nm, often with filling yields approaching 60–70% or better. In addition some high yield filled SWNTs were subjected to long-term washing in either boiling or room temperature. aqueous media, which does not remove the filling from the tubules, but enables effective removal of water-soluble extraneous materials . Received: 10 May 2002 / Accepted: 25 October 2002 / Published online: 10 March 2003 RID="*" ID="*"Corresponding author. Fax: +44-1865/272-690, E-mail: jeremy.sloan@chem.ox.ac.uk     

Synthesis and application of iron-filled carbon nanotubes coated with FeCo alloy nanoparticles

FeCo alloy nanoparticles were coated onto the iron-filled carbon nanotubes by an electroless plating method. As-prepared samples were then annealed at different temperatures. The morphologies and structures of the samples were characterized, and the relationship between the soft magnetic properties and the Fe/Co ratios of the samples was established. The microwave absorbing characteristics of the samples were also evaluated. The results show that the soft magnetic characteristics of iron-filled carbon nanotubes can be improved after being coated with FeCo alloy nanoparticles and then heat treated, which results in more effective microwave absorption.     

Detailed profiling of CNTs arrays along the growth window in a floating catalyst reactor

We report a detailed longitudinal and depth profiles of multi-wall carbon nanotubes (CNTs) arrays synthesized using xylene and ferrocene in a floating catalyst reactor. Point to point analyses of the CNTs grown in a “growth window” with CNTs arrays longer than 0.5 mm were performed using optical microscopy, Raman spectroscopy, FESEM, high-resolution TGA/DTA, and TEM techniques. The heights of the CNTs arrays show a maximum at a mid point of the growth window, while a reverse trend of minimum is observed for iron-to-CNTs atomic ratios. The ratio of amorphous carbon to CNTs sharply increases along the growth window and from the bottom to top of CNTs arrays. The CNTs diameter also increases along the growth window, due to deposition of the amorphous carbon, which can be almost removed by temperature programmed oxidation up to around 500 °C. A base growth mechanism, the variations of catalyst content, residence time and temperature profile along the growth window, the adsorption and decomposition of polycyclic aromatic hydrocarbons to amorphous carbon, and a limited diffusion of hydrocarbon species through the arrays covered by excessive amorphous carbon may explain the results.     

Epitaxy of m ‐plane ZnO on (112) LaAlO3 substrate

Heteroepitaxial growth of non‐polar m ‐plane (10 0) ZnO has been demonstrated on (112) LaAlO₃ single crystal substrates using the pulsed laser deposition method. X‐ray diffraction, reflection high energy electron diffraction, and cross‐sectional transmission electron microscopy with selected‐area diffraction, have been used to characterize the structural properties of deposited ZnO films. The epitaxial relationship between ZnO and LAO is shown to be (10 0)_ZnO ∥ (112)_LAO, (11 0)_ZnO ∥ ( 1)_LAO and [0001]_ZnO ∥ [ 10]_LAO. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Pulsed laser deposition of multiwalled carbon nanotubes thin films

The physical/chemical properties of multiwalled carbon nanotubes have attracted much interest for applications in different fields, from micro-electronic to coating technology due, in particular, to their peculiar conductivity properties, to their hardness and high resistance to thermal stress. The technology to produce carbon nanotubes thin films with the desired properties, however, is still under development. In this work, we report on multiwalled carbon nanotubes thin films deposited by pulsed laser deposition techniques ablating commercially polystyrene-nanotubes pellets on alumina substrates. MicroRaman spectroscopy and high resolution Transmission Electron Microscopy provide the experimental confirmation that carbon nanotubes-like structures are present on the alumina surface with both minimal morphological damage of the tubes and structural changes induced by laser beam.