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)     

Electrical properties of transparent carbon nanotube networks prepared through different techniques

Ultra‐thin, optically transparent and electrically conducting films of pure carbon nanotubes (CNTs) are widely studied thanks to their promise for broad applications. In the present work, we study and compare different deposition techniques for the production of these networks: dip‐coating, spray‐coating, vacuum filtration and electrophoretic deposition on a quartz glass using single‐walled carbon nanotubes (SWCNTs) produced by the HiPCo method. In order to optimize the networks, besides the various deposition techniques we also investigate how the optical and electrical properties vary if the networks are fabricated from different CNTs, all synthesized by the CVD method: SWCNTs, DWCNTs and MWCNTs. As the main criteria for evaluating the quality of these CNT networks we measure the electrical surface resistance at a certain optical transmittance and correlate it to the morphology (homogeneity and roughness) of the networks. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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)     

The origin of polarized blackbody radiation from resistively heated multiwalled carbon nanotubes

We observed very pronounced polarization of light emitted by highly aligned free-standing multiwall carbon nanotube (MWNT) sheet in axial direction which is turned to the perpendicular polarization when a number of layers are increased. The radiation spectrum of resistively heated MWNT sheet closely follows to the Plank's blackbody radiation distribution. The obtained polarization features can be described by a classical dielectric cylindrical shell model, taking into consideration the contribution of delocalized π-electrons (π surface plasmons). In absorption (emission) the optical transverse polarizability, which is much smaller than longitudinal one, is substantially suppressed by depolarization effect due to screening by induced charges. This phenomenon suggests very simple and precise method to estimate the alignment of nanotubes in bundles or large assemblies.     

Formation of Y-junction carbon nanotubes by catalytic CVD of methane

Y-junction carbon nanotubes were grown by catalytic CVD of methane at 700 ^°C on NiO-CuO-MoO(7:2:1) (w/w/w)/SiO₂ catalyst. For comparison, NiO-CuO(8:2) (w/w)/SiO₂ and NiO-MoO(8:2) (w/w)/SiO₂ catalysts were tested for carbon nanotube formation. TEM analysis indicates that no Y-junction structures were formed with the latter two catalysts. This finding elucidates why the addition of a small amount of MoO to NiO-CuO/SiO₂ catalyst is crucial for enhancing the formation of Y-junction carbon nanotubes.     

Growth of multiwalled carbon nanotube arrays by chemical vapour deposition over iron catalyst and the effect of growth parameters

Multiwalled carbon nanotube (CNT) arrays were grown by catalytic thermal decomposition of acetylene, over Fe-catalyst deposited on Si-wafer in the temperature range 700-750 °C. The growth parameters were optimized to obtain dense arrays of multiwalled CNTs of uniform diameter. The vertical cross-section of the grown nanotube arrays reveals a quasi-vertical alignment of the nanotubes. The effect of varying the thickness of the catalyst layer and the effect of increasing the growth duration on the morphology and distribution of the grown nanotubes were studied. A scotch-tape test to check the strength of adhesion of the grown CNTs to the Si-substrate surface reveals a strong adhesion between the grown nanotubes and the substrate surface. Transmission electron microscopy analysis of the grown CNTs shows that the grown CNTs are multiwalled nanotubes with a bamboo structure, and follow the base-growth mechanism.     

A simple approach for synthesis of TiO2 nanotubes with through‐hole morphology

The present work reports a simple approach for fabrication of self‐standing titania (TiO₂) nanotube membranes with through‐hole morphology. The method is hydrofluoric acid free and the pore opening of TiO₂ nanotubes is performed by electrochemical thinning of the oxide barrier layer. A reduction of anodization voltage was applied at the end of the anodization process to cause a successful removal of the remaining barrier layer from the TiO₂ nanotubes during their detachment from the underlying titanium substrate. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and Raman scattering study of double-walled carbon nanotube peapods

Double-walled carbon nanotubes (DWNTs) encapsulating C₆₀ fullerenes were successfully synthesized by gas phase diffusion method. The obtained peapods were examined using high-resolution transmission electron microscopy (HRTEM). The HRTEM images indicate that the ordered packing phases of fullerene molecules inside are sensitively related to the inner-tube radius of DWNTs. Also, Raman measurements were carried out for the first time to characterize DWNTs peapods. There are obvious differences between the Raman spectrum of DWNTs peapods and that of SWNTs peapods. The intensities of resonances from C₆₀ in the former are much stronger than those in the latter. In addition, changes of tangential mode (TM) and radial breathing mode (RBM) of DWNTs after C₆₀ doping were observed. The possible reasons are discussed in the text.     

Thermal conductivity of CoSb3 nano‐composites grown via a novel solvothermal nano‐plating technique

We have utilized a solvothermal nano‐plating technique to grow nano‐structured CoSb₃ directly onto the surface of micron‐sized CoSb₃ particles that were subsequently hot pressed and densified into a homogeneous skutterudite nano‐composite. We herein present results for three samples: a bulk sample to serve as a reference, and two samples with solvothermally grown nano‐structures of 5 wt% and 20 wt%, respectively. All three samples used the same bulk starting materials. The thermal conductivity was measured via two independent techniques (steady state and laser flash) and both show a systematic reduction in the thermal conductivity with an increasing amount of nano‐structures. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

Direct writing of carbon nanotube patterns by laser-induced chemical vapor deposition on a transparent substrate

Dot array and line patterns of multi-walled carbon nanotubes (MWCNTs) were successfully grown by laser-induced chemical vapor deposition (LCVD) on a transparent substrate at room temperature. In the proposed technique, a Nd:YVO₄ laser with a wavelength of 532 nm irradiates the backside of multiple catalyst layers (Ni/Al/Cr) through a transparent substrate to induce a local temperature rise, thereby allowing the direct writing of dense dot and line patterns of MWCNTs below 10 μm in size to be produced with uniform density on the controlled positions. In this LCVD method, a multiple-catalyst-layer with a Cr thermal layer is the central component for enabling the growth of dense MWCNTs with good spatial resolution.     

Enhanced self‐ordering of anodic ZrO2 nanotubes in inorganic and organic electrolytes using two‐step anodization

This work reports on the optimized growth of self‐ordered ZrO₂ nanotubes in inorganic water‐based and organic electrolyte systems containing small amounts of fluoride employing a two‐step anodization process. We show how surface pretreatments of the metallic Zr substrate can drastically improve the growth and morphology of the resulting anodic ZrO₂ nanotube arrays. Using two step anodization and employing organic electrolytes, highly regular and ordered nanotubular ZrO₂ oxide layers can be grown to significantly increased tube lengths compared with aqueous electrolytes. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

In‐situ dispersion of ZrO2 nano‐particles coated with pentacene

Stable suspensions of pentacene functionalised ZrO₂ nano‐particles were synthesised using a microwave plasma process. The particles were dispersed in‐situ in ethylene glycol. The formation of coated particles with small cores and a well defined size in the range of 3–5 nm was shown by X‐ray diffraction. In difference to resublimed pure pentacene, suspensions of the coated nano‐particles remained stable for weeks, as confirmed by the observation of a small aggregate size in dynamic light scattering. Thin films of the particles on Si based substrates were obtained by drop‐casting. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

250 µm long anodic TiO2 nanotubes with hexagonal self‐ordering

In this work we show that the growth of more than 250 µm thick self‐organized TiO₂ nanotube layers is possible, using an electrochemical approach in organic electrolytes. The tubes can grow as a hexagonal close packed pore array. Crucial parameters that decide on the dimensions are the fluoride ion concentration, the voltage and the anodization time. Self‐organized tube formation is restricted to a critical parameter range. Highest aspect ratio tubes can be achieved under a set of very optimized conditions. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

     

Synthesis and gas sensing characteristic based on metal oxide modification multi wall carbon nanotube composites

A new type of gas sensing material based on metal oxide modification multi wall carbon nanotube (MO/MWCNT) composites is presented since the interface between the composites enhance the carrier density so as to improve the gas sensitivity. Three kinds of MO/MWCNT composite materials, such as ZnO/MWCNT, SnO₂/MWCNT and TiO₂/MWCNT, have been acquired in situ growth using catalytic pyrolysis method. The MO nano particles have decorated on side of MWCNTs, whereas the introduction of SnO₂ nano particles makes part of MWCNT showing two-dimensional form of carbon nano-wall structure. Among four kinds of cathode of ZnO/MWCNTs, SnO₂/MWCNTs, TiO₂/MWCNTs and pure MWCNT composite film, TiO₂/MWCNTs composite has the lowest threshold electric field required to draw current of 12 μA has been found to be ∼1.2 V/μm, and also TiO₂/MWCNTs composite has the highest sensitivity of 16% to ethanol. The TiO₂/MWCNTs composite is superior to the others both in vacuum electron transportation and gas sensitivity.     

Position-controlled synthesis of single-walled carbon nanotubes on a transparent substrate by laser-induced chemical vapor deposition

The synthesis of single-walled carbon nanotubes (SWCNTs) on a transparent substrate with multiple-catalyst layer (Fe/Al/Cr: 0.5/15/500 nm) using laser-induced chemical vapor deposition is reported. Ethylene (C₂H₄) mixed with hydrogen (H₂) and a continuous wave Nd:YVO₄ laser (532 nm) were used as the precursor gas and the irradiation source, respectively. It was found that the density and quality of the SWCNT dots varied sensitively to laser irradiance and chamber pressure. From subsequent micro-Raman analyses at different excitation sources (488, 514, 633, and 785 nm), the diameters of the SWCNTs were estimated to be within the range of 0.8-2 nm and that the SWCNT dots were composed of both semiconducting and metallic SWCNTs. It is demonstrated that an array of SWCNT dots can be fabricated at precisely controlled positions of a transparent substrate at room temperature with no need of catalysis patterning.     

Effect of temperature on growth and structure of carbon nanotubes by chemical vapor deposition

The effect of temperature on growth and structure of carbon nanotubes (NTs) using chemical vapor deposition (CVD) has been investigated. Iron embedded silica was used to grow NTs in large quantity at various temperatures from 600 to 1050 °C with gas pressure fixed at 0.6 and 760 Torr, respectively. The growth and structure of the NTs are strongly affected by the temperature. At low gas pressure, the NTs are completely hollow at low temperature and bamboo-like structure at high temperature. While at high gas pressure, all the NTs are bamboo-like structure regardless of temperature. The diameter of NTs increases significantly with temperature. At low gas pressure the diameter gets bigger by mainly increasing the number of graphene layers of the wall of NTs, whereas at high gas pressure the diameter gets bigger by increasing both the number of graphene layers of the wall and the inner diameter of the NTs. This result indicates that the growth temperature is crucial in synthesizing NTs with different structures. The findings here are important for realizing controlled growth of NTs for their applications in different fields. Received: 20 November 2001 / Accepted: 21 November 2001 / Published online: 4 March 2002     

Charge-carrier dynamics in single-wall carbon nanotube bundles: a time-domain study

We present a real-time investigation of ultra-fast carrier dynamics in single-wall carbon nanotube bundles using femtosecond time-resolved photoelectron spectroscopy. The experiments allow us to study the processes governing the sub-picosecond and the picosecond dynamics of non-equilibrium charge carriers. On the sub-picosecond time scale the dynamics are dominated by ultra-fast electron–electron scattering processes, which lead to internal thermalization of the laser-excited electron gas. We find that quasiparticle lifetimes decrease strongly as a function of their energy up to 2.38 eV above the Fermi level – the highest energy studied experimentally. The subsequent cooling of the laser-heated electron gas to the lattice temperature by electron–phonon interaction occurs on the picosecond time scale and allows us to determine the electron–phonon mass-enhancement parameter λ. The latter is found to be over an order of magnitude smaller if compared, for example, with that of a good conductor such as copper. Received: 4 March 2002 / Accepted: 7 March 2002 / Published online: 3 June 2002     

Large area metal dot matrices made by diffraction mask projection laser ablation

A route towards large area metal dot templates is presented. The templates are generated by diffraction mask projection laser ablation of thin metal films. The well ordered nanodot‐matrices are fast and easy to fabricate and show a high homogeneity over a large area. The metal nanodots are bound to the substrate, making them suitable for subsequent 3D nanostructure synthesis such as glancing angle deposition and nanowire growth mechanisms. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)