Fabrication of carbon nanotube field effect transistors by AC dielectrophoresis method

Single wall carbon nanotubes (SWNTs) suspended in isopropyl alcohol have been placed between two electrodes by AC dielectrophoresis method. The number of SWNTs bridging the two electrodes is controlled by SWNT concentration of the suspension and deposition time. Through selectively burning off the metallic SWNTs by current induced oxidation, the back-gate carbon nanotube field effect transistors (CNTFETs) with a channel current on-off ratio of up to 7 × 10⁵ have been successfully fabricated. The success rate of the CNTFETs in 20 samples is 60%. These results suggest that AC dielectrophoresis placement method is an efficient technique to fabricate CNTFETs with some flexibilities of controlling CNT reconnection, length and orientation.     

Buckypaper-based catalytic electrodes for improving platinum utilization and PEMFC's performance

Platinum (Pt) catalytic electrode was developed by using carbon nanotube films (buckypaper) as supporting medium and electrodeposition method to deposit Pt catalyst. Buckypapers are free-standing thin films consisting of single-walled carbon nanotubes (SWNTs), multi-walled carbon nanotubes (MWNTs) and/or carbon nanofibers (CNFs) held together by van der Waals forces without any chemical binders. Special mixed buckypapers was developed by layered microstructures with a dense and high-conducting SWNT networks at the surface, as well as large porous structures of CNF networks as back supports. This unique microstructure can lead to improve Pt catalyst accessibility and mass exchange properties. Pt particles of about 6 nm were uniformly deposited in porous buckypapers. A promising electrochemical surface area of ∼40 m²/g was obtained from these electrodes. A Pt utilization as low as 0.28 g_Pt/kW was achieved for the cathode electrode at 80 °C. Pt utilization efficiency can be further improved by optimization of the electrodeposition condition in order to reduce the Pt particle size.     

Characterization of single wall carbon nanotubes by nonane preadsorption

The preferential blocking of the interior adsorption sites of single walled carbon nanotubes (SWNTs) by n-nonane is demonstrated. Following adsorption of n-nonane and evacuation for 24 h at 323 K, it was found that interior sites with diameters less than ∼14 Å remained filled with n-nonane, blocking the physical adsorption of N₂ on these sites at 77.3 K. We demonstrate that “nonane blocking” is a very useful technique for nanotube porosity characterization.     

Magnetic separation of Fe catalyst from single-walled carbon nanotubes in an aqueous surfactant solution

We report an efficient technique to separate ferromagnetic catalyst particles from an aqueous surfactant solution of single-walled carbon nanotubes (SWNTs) by the use of a 1.3 T permanent magnet. High resolution transmission electron microscopy (HRTEM) demonstrates that SWNTs are coated with a surfactant layer that stabilises the aqueous dispersions of SWNTs. The residual quantities of Fe catalyst (∼3%) can be effectively removed from a colloid solution of SWNTs in a magnetic field while absorbance spectra of the initial and purified solutions show that the nanotube diameter distribution remains unchanged.     

Lateral growth of single-walled carbon nanotubes across electrodes and the electrical property characterization

To realize the commercialization of single-walled carbon nanotube (SWNT)-based nanoelectronic and optoelectronic devices, the development of a fabrication process of catalytic chemical vapour deposition (CCVD) growth of SWNTs across electrodes is required. In this work, we report on the process of the lateral growth of SWNTs across catalytic pads. Using the conventional photolithography technique followed by thin film evaporation and lift off, the catalytic pads were prepared, consisting of nickel (Ni) and silicon dioxide (SiO₂) double layers, on the thermal silicon oxide substrate. The SWNTs were laterally grown across the catalytic pads in a thermal pyrolysis CVD system at 800–900 °C fed with a mixed gas flow of methane (CH₄) and hydrogen (H₂). The SiO₂, as the upper layer on Ni pads, not only plays a role as a barrier to prevent vertical growth but also serves as a porous medium that helps in forming smaller nano-sized Ni particles, so that the use of ultrathin Ni film would not be necessary for growth of SWNTs. Lateral growth across pads of various inter-spacing up to tens of microns was conducted for devices of different applications. The characterization by micro-Raman spectroscopy, atomic force microscopy and electron microscopy revealed the structure and diameters of the SWNTs and most importantly the SWNT density controlled by changing growth temperature. Following SWNTs growth, post-definition of metallic electrodes was conducted and the electrical properties were also measured.     

Tin oxide nanosensor fabrication using AC dielectrophoretic manipulation of nanobelts

Nanobelts are a new class of semiconducting metal oxide nanowires. The ribbon-like nanobelts are chemically pure and structurally uniform single crystals, with clean, sharp, smooth surfaces, and rectangular cross-sections. Positive and negative dielectrophoresis (DEP) was demonstrated for the first time on semiconducting oxide nanobelts. This effect was then used for the fabrication of a nanodevice, which consisted of SnO₂ nanobelts attached to castellated gold electrodes defined on a glass substrate, and covered by a microchannel. The SnO₂ nanobelts (width ∼ 100-300 nm, thickness ∼ 30-40 nm) were suspended in ethanol and introduced into the microchannel. An alternating (AC) voltage of ∼9.8 V peak to peak, with variable frequency, was applied between the electrodes (minimum electrode gap ∼ 20 μm), which corresponds to an average electric field strength of less than 2.5 × 10⁵ V/m. In the 10 Hz-1 kHz range, repulsion between the nanobelts and the electrodes occurred, while in the 1-10 MHz range, attraction was observed. Once the nanobelts touched the electrodes, those that were sufficiently long bridged the electrode gaps. The device was characterized and can potentially be used as a nanosensor.     

Photoluminescence intensity of single-wall carbon nanotubes

The photoluminescence (PL) intensity of a single-wall carbon nanotube (SWNT) is calculated for each (n, m) by multiplying the photon-absorption, relaxation and photon-emission matrix elements. The intensity depends on chirality and “type I vs type II” for smaller diameter semiconducting SWNTs (less than 1 nm). By comparing the calculated results with the experimental PL intensity of SWNTs prepared by chemical vapor deposition at different temperatures, we find that the abundance of (n, m) nanotubes with smaller diameters should exhibit a strong chirality dependence, which may be related to the stability of their caps.     

Low percolation threshold in single-walled carbon nanotube/high density polyethylene composites prepared by melt processing technique

A new method was developed to disperse carbon nanotubes (CNTs) in a matrix polymer and then to prepare composites by melt processing technique. Due to high surface energy and strong adsorptive states of nano-materials, single-walled carbon nanotubes (SWNTs) were adsorbed onto the surface of polymer powders by spraying SWNT aqueous suspected solution onto fine high density polyethylene (HDPE) powders. The dried SWNTs/powders were blended in a twin-screw mixture, and the resulting composites exhibited a uniformly dispersion of SWNTs in the matrix polymer. The electrical conductivity and the rheological behavior of these composites were investigated. At low frequencies, complex viscosities become almost independent of the frequency as nanotubes loading being more than 1.5 wt%, suggesting an onset of solid-like behavior and hence a rheological percolation threshold at the loading level. However, the electrical percolation threshold is ∼4 wt% of nanotube loading. This difference in the percolation thresholds is understood in terms of the smaller nanotube-nanotube distance required for electrical conductivity as compared to that required to impede polymer mobility. The measurements of mechanical properties indicate that this processing method can obviously improve the tensile strength and the modulus of the composites.     

Thermal desorption of deuterium from modified carbon nanotubes and its correlation to the microstructure

The process of deuterium desorption from single-wall carbon nanotubes (SWNTs) modified by atomic (D) and molecular (D₂) deuterium treatment was investigated in an ultrahigh vacuum environment using thermal desorption mass spectroscopy (TDMS). Microstructural and chemical analyses of SWNT material, modified by this deuterium interaction, were performed by means of a combination of scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results disclose characteristic features in the TDMS spectra of deuterium evolved from the SWNT material, which can be correlated to the microstructure of nanocarbon material modified by D-treatment. The TDMS spectra of deuterium originating from the large diameter rope type nanotube structures, resulting from a prolonged low-pressure (D + D₂) gas mixture treatment, exhibit three overlapping desorption peaks: a dominant one with a desorption activation energy (E_des) of approx. 2.86 eV and lower intensity peaks at E_des of ∼1.50 and 2.46 eV. On the other hand, the TDMS spectra of deuterium taken from the “coral reef”-like carbon nanostructures, obtained after prolonged treatment of SWNTs to a high-pressure (D + D₂) gas mixture produced at high temperature, reveal the coexistence of four superimposed desorption peaks with E_des ranging from 1.23 to 4.4 eV. A dominant desorption peak with E_des ≈ 4.4 eV, can be attributed to bulk diffusion of D trapped within this nanocapsule bulk structure.     

Electrochemical study of activated carbon-semiconducting oxide composites as electrode materials of double-layer capacitors

The energy storage of activated carbon modified with a semiconducting oxide TiO₂ is studied. The composite was prepared by mixing nanosize TiO₂ and activated carbon through a means of ultrasonic vibration in ethanol solution for 30 min. It was found that with modification of TiO₂, the specific capacitance of activated carbon measured at 0.65 mA/cm² was increased from 47.2 to 63.1 F g⁻¹. This method is unique in comparison the conventional method because it uses semiconducting TiO₂ other than electrochemically active materials such as RuO₂. The later has been adopted to make electrochemical-double-layer hybrid supercapacitors, however, the former is attributed to a pure double-layer supercapacitor.     

Fabrication of single-walled carbon nanotube Schottky diode with gold contacts modified by asymmetric thiolate molecules

We have fabricated single-walled carbon nanotube (SWCNT) Schottky diodes by asymmetrically modifying the two Au/SWCNT contacts using different thiolate molecules, methanethiol (CH₃SH) and trifluoroethanethiol (CF₃CH₂SH). Characterization has revealed that highly asymmetrical contacts with Schottky barrier heights of ∼190 and ∼40 meV (increased by over 70% and decreased by over 60%, respectively with respect to that of pristine Au/SWCNT contact of ∼110 meV) were achieved for the Au/SWCNT contacts modified by CH₃SH and CF₃CH₂SH, respectively. The performance of our SWCNT Schottky diodes is as follows: the forward and reverse current ratio (I_forward/I_reverse) higher than 10⁴, a forward current as high as ∼5 μA, a reverse leakage current as low as ∼100 pA, and a current ideality factor as low as ∼1.42. This is at least comparable to, if not better than SWCNT Schottky diodes fabricated with asymmetrical metals, where one contact is a metal with a work function lower than that of SWCNTs to yield a Schottky contact, while the other has a work function higher than that of SWCNTs to achieve an ohmic (more near ohmic) contact.     

Inter-tube bonding, graphene formation and anisotropic transport properties in spark plasma sintered multi-wall carbon nanotube arrays

Millimeter long, vertically oriented, multi-walled carbon nanotube (MWCNT) arrays were pre-aligned and densified using spark plasma sintering (SPS) technique to form aligned MWCNT bulk samples. The combined results of X-ray powder diffraction, Raman spectroscopy, scanning electron microscopy and high-resolution transmission electron microscopy show that the MWCNTs largely retain their orientation and individual tubular morphology in the aligned MWCNT bulk samples, and that the SPS process induces inter- and intra-tubular bonding as well as graphene formation. In view of the one-dimensional nature of individual MWCNTs, it is particularly noteworthy that the transverse electrical resistivity ρ_T is slightly lower than the longitudinal resistivity ρ_L, whereas the transverse thermal conductivity κ_T is ∼50% of κ_L. The room temperature κ_L is ∼31 W/(m K), one of the highest reported in MWCNT bulk samples. In addition, the thermopower measurements show anisotropy and features of phonon drag.     

High temperature rearrangement of disordered nanoporous carbon at the interface with single wall carbon nanotubes

Composites of nanoporous carbon and single wall carbon nanotubes were heat treated in vacuum at temperatures ranging from 1200 to 2000 °C. The resultant interface between the two allotropes of carbon was characterized using high resolution transmission electron microscopy and Raman spectroscopy. At the interface between the nanoporous carbon and the nanotube, the nanotube served as a template for ordering and orientation of the normally disordered nanoporous carbon along the nanotube axis during high temperature treatment. When annealed at 2000 °C, the nanoporous carbon transformed to graphitic nanoribbon which in turn crushed the nanotube to form a nanoscale carbon “bulb”. This result is interesting since at these temperatures, the native nanoporous carbon is well known to resist ordering and is therefore referred to as being a “non-graphitizing” carbon. That the nanotube should act as a template for the incipient graphitization suggests that bonding and strength for load transfer may be developed at these interfaces.     

Microstructure and mechanical properties of hot-pressed carbon nanotubes compacted by spark plasma sintering

Bulk carbon nanotube samples were prepared by spark plasma sintering. The as-prepared bulk carbon nanotube material exhibited brittle fracture similar to that of common ceramics. Its fracture toughness was around 4.2 MPa m^1/2 while flexural strength was 50 MPa due to the weak bonding between carbon nanotubes. Obvious carbon nanotube bridging was found during the development of the crack induced by an indenter, which provides a possibility of carbon nanotube tough material.     

Energetics and stability of C60 molecules encapsulated in carbon nanotubes

An energetic analysis was performed to study the interactions of C₆₀ molecules encapsulated in carbon nanotubes. Both direct interaction between C₆₀ molecules through van der Waals forces and indirect interaction between encapsulated C₆₀ molecules through the elastic deformation of their host carbon nanotubes were considered. For C₆₀s encapsulated in a (9, 9) nanotube, the indirect interaction dominates and a relatively large energy barrier exists for the formation of a uniform, stable, one-dimensional (1-D) C₆₀ array. For a (10, 10) nanotube, the indirect interaction leads to a small energy barrier to form a 1-D C₆₀ array, while for a (11, 11) nanotube the influence of the indirect interaction is negligible. Molecular dynamics simulations were performed to confirm the present energetic analysis, suggesting that the indirect interaction between encapsulated molecules/particles through the elastic deformation of their host nanotubes may affect the stability of nanotube-based structures.     

Controlling the diameter distribution of carbon nanotubes grown from camphor on a zeolite support

Single-wall and multi-wall carbon nanotubes (SWNTs and MWNTs, respectively) of controlled diameter distribution were selectively grown by thermal decomposition of a botanical hydrocarbon, camphor, on a high-silica zeolite support impregnated with Fe-Co catalyst. Effects of catalyst concentration, growth temperature and camphor vapor pressure were investigated in wide ranges, and diameter distribution statistics of as-grown nanotubes was analyzed. High yields of metal-free MWNTs of fairly uniform diameter (∼10 nm) were grown at 600-700 °C, whereas significant amounts (∼30%) of SWNTs were formed at 850-900 °C within a narrow diameter range of 0.86-1.23 nm. Transmission electron microscopy and micro-Raman spectroscopy reveal that camphor-grown nanotubes are highly graphitized as compared to those grown from conventional CNT precursors used in chemical vapor deposition.     

Effect of synthesis temperature on hardness of carbon phases prepared from C60 and nanosized diamonds under pressure

Vicker’s hardness and Raman scattering spectra have been studied for carbon phases prepared from C₆₀ fullerene and nanosized diamonds at high temperatures and a pressure of 6 GPa. It was found that the hardness dependence on annealing temperature has a maximum near ∼1100 K for both fullerene and nanosized diamonds as initial materials. This temperature is only slightly higher than the temperature at which the C₆₀ cage collapses, and appears to correspond to the termination of intercluster bonding in the case of nanosized diamonds. The hardness maximum is interpreted as a result of competition between an increase in intercluster/intercage bonding and local instability for graphitic-like ordering.     

High rate performance of highly dispersed C60 on activated carbon capacitor

Fullerene-activated carbon composite electrodes were prepared and their charge/discharge characteristics were studied for use in a high power electric double-layer capacitor. The capacitance of the C₆₀-loaded activated carbon fiber (ACF) electrodes became greater than that of the unloaded ACF at charge/discharge current densities above 50 mA/cm². In order to obtain a highly dispersed C₆₀-loaded electrode, an ultrasonic treatment was performed. The size of the C₆₀ agglomerate decreased from 1-2 to 0.1 μm or less, and the capacitance of the C₆₀-loaded ACF electrodes increased with an increase in the ultrasonic treatment time. A higher capacitance of 172 F/g was obtained at 50 mA/cm² on a 1 wt% C₆₀-loaded electrode with ultrasonic treatment, and the C₆₀-loaded ACF electrode also showed a higher cycle performance.     

Synthesis and Raman characterization of boron-doped single-walled carbon nanotubes

A systematic study was carried out to dope single-walled carbon nanotube (SWNT) bundles with varying amounts of boron using the pulsed laser vaporization technique. Targets containing boron concentrations ranging from 0.5 to 10 at.% boron were prepared by mixing elemental boron with carbon paste and the Co/Ni catalysts. The laser-generated products that were obtained from these targets were characterized by high resolution transmission electron microscopy, electron energy loss spectroscopy (EELS), thermoelectric power (TEP) measurements, and Raman scattering experiments. Electron microscopy and Raman studies revealed that the presence of various levels of boron concentration in the target strongly affected the products that were prepared. SWNTs were found in the products prepared from targets containing up through 3 at.% boron, and high resolution EELS estimated that less than 0.05-0.1 at.% boron is present in the SWNT lattice. The absence of SWNT bundles in the products derived from targets containing more than 3 at.% boron implies that the presence of excess boron in the carbon plume severely inhibits the carbon nanotube growth. The overall effect of the boron incorporation primarily leads to: (i) a systematic increase in intensity of the disorder-induced band (D-band) upon boron doping, with increasing D-band intensity observed for higher doping levels, (ii) a systematic downshift in the G′-band frequency due the relatively weaker C-B bond, and (iii) a non-linear variation in the RBM and G′-band intensities which is attributed to shifts in resonance conditions in the doped tubes. Resonant Raman spectroscopy thus provides large changes in the intensity of prominent features even when the dopant concentration is below the detectable limit of EELS (0.05-0.1 at.%). Thermoelectric power data also provide complementary evidence for the presence of a small boron concentration in the SWNT lattice which transforms the SWNTs into a permanently p-type material.     

Enhanced inactivation of E. coli bacteria using immobilized porous TiO2 photoelectrocatalysis

Immobilized TiO₂ nanotube electrodes with high surface areas were grown via electrochemical anodization in aqueous solution containing fluoride ions for photocatalysis applications. The photoelectrochemical properties of the grown immobilized TiO₂ film were studied by potentiodynamic measurements (linear sweep voltammetry), in addition to the calculation of the photocurrent response. The nanotube electrode properties were compared to mesoporous TiO₂ electrodes grown by anodization in sulfuric acid at high potentials (above the microsparking potential) and to 1 g/l P-25 TiO₂ powder. Photocatalyst films were evaluated by high resolution SEM and XRD for surface and crystallographic characterization. Finally, photoelectrocatalytic application of TiO₂ was studied via inactivation of E. coli. The use of the high surface area TiO₂ nanotubes resulted in a high photocurrent and an extremely rapid E. coli inactivation rate of ∼10⁶ CFU/ml bacteria within 10 min. The immobilized nanotube system is proven to be the most potent electrode for water purification.