Filling boron nitride nanotubes with metals

The authors’ endeavors over the last few years with respect to boron nitride (BN) nanotube metal filling are reviewed. Mo clusters of 1–2 nm in size and FeNi Invar alloy (Fe ∼60 at. %; Ni ∼40 at. %) or Co nanorods of 20–70 nm in diameter were embedded into BN nanotube channels via a newly developed two-stage process, in which multi-walled C nanotubes served as templates for the BN multi-walled nanotube synthesis. During cluster filling, low-surface-tension and melting-point Mo oxide first filled a C nanotube through the open tube ends, followed by fragmentation of this filling into discrete clusters via O₂ outflow and C→BN conversion within tubular shells at high temperature. During nanorod filling, C nanotubes containing FeNi or Co nanoparticles at the tube tips were first synthesized by plasma-assisted chemical vapor deposition on FeNi Invar alloy or Co substrates, respectively, and, then, the nanomaterial was heated to the melting points of the corresponding metals in a flow of B₂O₃ and N₂ gases. During this second stage, simultaneous filling of nanotubes with a FeNi or Co melt through capillarity and chemical modification of C tubular shells to form BN nanotubes occurred. The synthesized nanocomposites were analyzed by scanning and high-resolution transmission electron microscopy, electron diffraction, electron-energy-loss spectroscopy and energy-dispersive X-ray spectroscopy. The nanostructures are presumed to function as ‘nanocables’ having conducting metallic cores (FeNi, Co, Mo) and insulating nanotubular shields (BN) with the additional benefit of excellent environmental stability. Received: 10 October 2002 / Accepted: 25 October 2002 / Published online: 10 March 2003 RID="*" ID="*"Corresponding author. Fax: +81-298/51-6280, E-mail: golberg.dmitri@nims.go.jp     

Standing or lying C70s encapsulated in carbon nanotubes with different diameters

Single-walled carbon nanotubes (SWNTs) encapsulating C₇₀s, so-called C₇₀ peapods, were synthesized in high yield by a vapor-phase doping method. Raman spectra, high resolution transmission electron microscopy (HRTEM), and selected area electron diffraction (SAED) measurement indicate that the tube diameter is one of the important factors to determine the orientation of C₇₀ molecules inside the SWNTs. SWNTs with different diameters give different alignment of C₇₀ molecules. The lying orientation is favorable over the standing orientation in thin nanotube, i.e. 1.36 nm nanotubes, whereas the standing orientation is favorable in thick nanotubes, i.e. 1.49 and 1.61 nm nanotubes.     

Radio frequency characteristics of Fe-filled carbon nanotube film

The conduction noise suppression in radio frequency region using film type of the Fe-filled carbon nanotubes and its epoxy composite was evaluated on a coplanar waveguide. Fe in carbon nanotubes have shown α-Fe crystalline structure and had a coercivity of 650 Oe. The magnitudes of the signal attenuation of Fe-filled carbon nanotubes on coplanar waveguide were shown in the range of about 10–18 dB/cm at 20 GHz (the stop-band frequency region). The power losses of these films exhibited 65–85% at 20 GHz in the stop-band frequency.     

Electronic structure of BN nanotubes with intrinsic defects NB and BN and isoelectronic substitutional impurities PN, AsN, SbN, InB, GaB, and AlB

The effect of intrinsic defects and isoelectronic substitutional impurities on the electronic structure of boron-nitride (BN) nanotubes is investigated using a linearized augmented cylindrical wave method and the local density functional and muffin-tin approximations for the electron potential. In this method, the electronic spectrum of a system is governed by a free movement of electrons in the interatomic space between cylindrical barriers and by a scattering of electrons from the atomic centers. Nanotubes with extended defects of substitution N_B of a boron atom by a nitrogen atom and, vice versa, nitrogen by boron B_N with one defect per one, two, and three unit cells are considered. It is shown that the presence of such defects significantly affects the band structure of the BN nanotubes. A defect band π(B, N) is formed in the optical gap, which reduces the width of the gap. The presence of impurities also affects the valence band: the widths of s, sp, and p_π bands change and the gap between s and sp bands is partially filled. A partial substitution of the N by P atoms leads to a decrease in the energy gap, to a separation of the Ds(P) band from the high-energy region of the s(B, N) band, as well as to the formation of the impurity Dπ(P) and Dπ*(P) bands, which form the valence-band top and conduction-band bottom in the doped system. The influence of partial substitution of N atoms by the As atom on the electronic structure of BN nanotubes is qualitatively similar to the case of phosphorus, but the optical gap becomes smaller. The optical gap of the BN tubule is virtually closed due to the effect of one Sb atom impurity per translational unit cell, in contrast to the weak indium-induced perturbation of the band structure of the BN nanotube. Introduction of the one In, Ga or Al atom per three unit cells of the (5, 5) BN nanotube results in 0.6 eV increase of the optical gap. The above effects can be detected by optical and photoelectron spectroscopy methods, as well as by measuring electrical properties of the pure and doped BN nanotubes. They can be used to design electronic devices based on BN nanotubes.     

Growth of Y-junction bamboo-shaped CNx nanotubes on GaAs substrate using single feedstock

Nitrogen-doped Y-junction bamboo-shaped carbon nanotubes were synthesized by chemical vapor deposition of monoethanolamine/ferrocene mixture on GaAs substrate at 950 °C. The use of monoethanolamine as the C/N feedstock simplifies the experimental arrangement by producing ammonia during the growth process. The structure, morphology and graphitization of as-grown nitrogen-doped carbon nanotubes (CN_x) were examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy analysis. TEM analysis indicates that nanotubes have a bamboo-like structure. The nitrogen concentration on as-grown CN_x nanotube was found to be 7.8 at.% by X-ray photoelectron spectroscopy (XPS) analysis. XPS analysis also indicated that there are two different types of nitrogen atoms (pyridinic and graphitic) in these materials. The possible growth mechanism of formation of Y-junction CN_x nanotubes was briefly discussed. Field emission measurement suggested that as-grown CN_x nanotubes are excellent emitters with turn-on and threshold fields of 1.6 and 2.63 V/μm, respectively. The result indicated that monoethanolamine proves to be an advantageous precursor to synthesize Y-junction nitrogen-doped carbon nanotubes and such nanotubes might be an effective material to fabricate various field emission devices.     

Selective growth of carbon nantoubes on SiO2/Si substrate

Three-step raising temperature process was employed to fabricate carbon nanotubes by pyrolysis of ferrocene/melamine mixtures on silica and single crystalline silicon wafers respectively. Then the morphologies, structures and compositions of obtained carbon nanotubes are investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscope (EDX) and electron energy-loss spectroscopy (EELS). TEM and SEM observation shows that on silica substrate, high-oriented carbon nanotube can grow compactly to form continuous film on both frontal and cross-section surfaces, but on silicon substrate, only can form on cross-section surface. These carbon nanotubes have much irregular cup-like structure, and with outer diameter varying from 25 nm to 35 nm. At the top end of carbon nanotube there is a catalyst particle. EDX analysis reveals that the particle are iron cluster, and EELS spectrum indicates that the nanotube is composed of pure carbon. Finally, the effect of substrate surface roughness on the growth behavior of carbon nanotubes has been discussed.     

Synthesis and field-emission of aligned SnO2 nanotubes arrays

Aligned tin dioxide (SnO₂) nanotubes have been synthesized by high-frequency inductive heating. Nanotubes with high yield were grown on silicon substrates in less than 5 min, using SnO₂ and graphite as the source powder. Scanning electron microscopy and transmission electron microscopy showed nanotube with diameters from 50 to 100 nm and lengths up to tens of mircrometers. The SnO₂ nanotubes synthesized under the optimum condition have better field-emission characteristics. The turn-on field needed to produce a current density of 10 μA/cm² is found to be 1.64 V/μm. The samples show good field-emission properties with a fairly stable emission current. This type of SnO₂ nanotubes can be applied as field emitters in displays as well as vacuum electric devices.     

Synthesis of lanthanum nickelate perovskite nanotubes by using a template-inorganic precursor

A new route to obtain metal oxide nanotubes is presented: an inorganic coordination complex precursor containing the metal ions and impregnated into alumina membrane templates yield hollow tubular nanostructures of LaNiO₃ by calcination at 600 °C as characterized by powder X-ray diffraction (XRD). Scanning electron microscopy (SEM) shows that the resulting nanotubes have 200 nm in diameter in good agreement with the template pore. Transmission electron microscopy (TEM) and dark field transmission electron microscopy (DF-TEM) show that the nanotubes with 10-20 nm walls and internal separations are composed of 3-5 nm crystals.     

Atomic structure of boron nitride nanotubes with an armchair-type structure studied by HREM

Hexagonal networks of boron nitride (BN) nanotubes were investigated by high-resolution electron microscopy (HREM) and image simulation. From HREM images, lattice planes of {002} and hexagonal rings of a BN nanotube were confirmed. Asymmetrical layer arrangements were found, and a structure model for double-walled BN nanotube with an armchair-type structure has been proposed.     

Production and characterization of polymer nanocomposite with aligned single wall carbon nanotubes

We reported a simple method to fabricate polymer nanocomposites with single-walled carbon nanotubes (SWNTs) having exceptional alignment and improved mechanical properties. The composite films were fabricated by casting a suspension of single walled carbon nanotubes in a solution of thermoplastic polyurethane and tetrahydrofuran. The orientation as well as dispersion of nanotubes was determined by scanning electron microscopy, transmission electron microscopy and polarized Raman spectroscopy. The macroscopic alignment probably results from solvent-polymer interaction induced orientation of soft segment chain during swelling and moisture curing. The tensile behavior of the aligned nanotube composite film was also studied. At a 0.5 wt.% nanotube loading, a 1.9-fold increase in Young's modulus was achieved.     

Catalytic activity of Fe, Co and Fe-Co-MCM-41 for the growth of carbon nanotubes by chemical vapour deposition method

Iron, cobalt and a mixture of iron and cobalt incorporated mesoporous MCM-41 molecular sieves were synthesised by hydrothermal method and used to investigate the rules governing their nanotube producing activity. The catalysts were characterised by XRD and N₂ sorption studies. The effect of the catalysts has been investigated for the production of carbon nanotubes at an optimised temperature 750 °C with flow rate of N₂ and C₂H₂ is 140 and 60 ml/min, respectively for a reaction time 10 min. Fe-Co-MCM-41 catalyst was selective for carbon nanotubes with low amount of amorphous carbon with increase in single-walled carbon nanotubes (SWNTs) yield at 750 °C. Formation of nanotubes was studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. Transmission electron microscope and Raman spectrum was used to follow the quality and nature of carbon nanotubes formed and the graphitic layers and disordered band, which shows the clear evidence for the formation of SWNTs, respectively. The result propose that the diameter of the nanotubes in the range of 0.78-1.35 nm. Using our optimised conditions for this system, Fe-Co-MCM-41 showed the best results for selective SWNTs with high yield when compared with Fe-MCM-41 and Co-MCM-41.     

Carbon nanotube synthesis on oxidized porous silicon

Carbon nanotubes were grown on thermally oxidized porous silicon by catalytic chemical vapor deposition from the mixture of ferrocene and xylene precursor. The growth rate of carbon nanotubes showed dependence on the oxidation extent of porous silicon. On pristine porous silicon surfaces, only poor nanotube growth was observed, whilst samples oxidized in air at 200, 400, 600 and 800 °C prior to the deposition process proved to be suitable substrates for carbon nanotube synthesis. Networks of carbon tubes with diameter of ∼40 and ∼10 nm observed on the surfaces of samples were investigated by electron microscopy and by energy dispersive X-ray analysis.     

Effect of calcination temperature on the morphology and surface properties of TiO2 nanotube arrays

Well-ordered TiO₂ nanotube arrays were prepared by electrochemical anodization of titanium in aqueous electrolyte solution of H₃PO₄ + NH₄F at a constant voltage of 20 V for 3 h, followed by calcined at various temperatures. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and Photoluminescence (PL) were used to characterize the samples. The results showed that the as-prepared nanotube arrays before being calcined were amorphous and could transform to anatase phase at a heat treatment temperature higher than 400 °C. As the calcination temperatures increased, crystallization of anatase phase enhanced and rutile phase appeared at 600 °C. However, further increasing the calcination temperature would cause the collapse of nanotube arrays. PL intensity of the nanotube arrays annealed at 500 °C was the lowest, which was probably ascribed to better crystallization together with fewer surface defects of the nanotube arrays.     

Selective growth, characterization, and field emission performance of single-walled and few-walled carbon nanotubes by plasma enhanced chemical vapor deposition

Single-walled carbon nanotubes (SWCNTs) and few-walled carbon nanotubes (FWCNTs) have been selectively synthesized by plasma enhanced chemical vapor deposition at a relative low temperature (550 °C) by tuning the thickness of iron catalyst. The parametric study and the optimization of the nanotube growth were undertaken by varying inductive power, temperature, catalyst thickness, and plasma to substrate distance. When an iron film of 3-5 nm represented the catalyst thickness for growing FWCNT arrays, SWCNTs were synthesized by decreasing the catalyst thickness to 1 nm. The nanotubes were characterized by field emission scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. Electron field emission properties of the nanotubes indicate that the SWCNTs exhibit lower turn-on field compared to the FWCNTs, implying better field emission performance.     

Fabrication of well-aligned CdS nanotubes by CVD-template method

Well-aligned CdS nanotubes have been synthesized within the nanochannels of the porous anodic alumina (PAA) membranes by pyrolyzing cadmium bis(diethyldithiocarbamate) [Cd(S₂CNEt₂)₂] at 400 °C. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the CdS nanotubes are highly ordered with uniform diameter in range of 80-150 nm and the length up to tens of microns. X-ray diffraction (XRD), Raman spectrum, energy-dispersive spectroscopy (EDS) and selected-area electron diffraction (SAED) demonstrate that the nanotubes are composed of pure hexagonal phase polycrystalline CdS. The synthetic route can, in principle, be extended to fabricate other nanotubes of a wide range of semiconductors.     

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.     

Synthesis, characterization and electrochemical behavior of polypyrrole/carbon nanotube composites using organometallic-functionalized carbon nanotubes

Thorn-like, organometallic-functionalized carbon nanotubes were successfully developed via a novel microwave hydrothermal route. The organometallic complex with methyl orange and iron (III) chloride served as reactive seed template, resulting in the oriented polymerization of pyrrole on the modified carbon nanotubes without the assistance of other oxidants. Morphological and structural characterizations of the carbon nanotube/methyl orange-iron (III) chloride and polypyrrole/carbon nanotube composites were examined using transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), infrared spectroscopy and X-ray diffraction (XRD). The electrochemical property of the polypyrrole/carbon nanotube composite was elucidated by cyclic voltammetry and galvanostatic charge-discharge. A specific capacitance of 304 F g⁻¹ was obtained within the potential range of −0.5-0.5 V in 1 M KCl solution.     

Synthesis and electrochemical properties of Ni doped titanate nanotubes for lithium ion storage

Ni doped titanate nanotubes were synthesized by hydrothermal method using Ni doped rutile TiO₂ nanopowders as a starting material. The electrochemical properties were investigated by cyclic voltammmetric methods. The microstructure and morphology of the synthesized powders were characterized by XRD (X-ray diffraction), and HRTEM (high resolution transmission electron microscopy). Ni doped nanotubes were composed of H₂Ti₂O₅·H₂O with outer and inner diameter of ∼10 nm and 6 nm and showed a initial discharge capacity of 305 mAh/g with poor cycling performance. However, after firing, the Ni doped nanotubes revealed better cycling performance due to lower reaction with hydrate and smaller diameter of the tubes.     

A room-temperature approach to boron nitride hollow spheres

Boron nitride hollow spheres were synthesized by the reaction of BBr₃ and NaNH₂ at room temperature; X-ray powder diffraction pattern could be indexed as hexagonal BN with the lattice constants of a=2.482 and c=6.701 Å; high-resolution transmission electron microscopy image showed the hollow spheres consisted of BN nanoparticles, with diameter between 80 and 300 nm; a possible formation mechanism of BN hollow spheres was discussed.     

Anatase type titania nanotube arrays direct fabricated by anodization without annealing

In this paper, anatase type titania nanotube arrays were direct fabricated by anodization in dimethyl sulfoxide electrolyte containing 1 wt% HF solution at above 50 °C without subsequently annealing. The length of the nanotubes decreases with increasing anodization temperature from about approximately 15 μm at 40 °C to approximately 4.5 μm at 60 °C. High resolution transmission electron microscope images and selected area electron diffraction pattern confirm the polycrystalline anatase specimen consisting of many nanocrystals with a random orientation.