Molecular beam-controlled nucleation and growth of vertically aligned single-wall carbon nanotube arrays

The main obstacle to widespread application of single-wall carbon nanotubes is the lack of reproducible synthesis methods of pure material. We describe a new growth method for single-wall carbon nanotubes that uses molecular beams of precursor gases that impinge on a heated substrate coated with a catalyst thin film. In this growth environment the gas and the substrate temperature are decoupled and carbon nanotube growth occurs by surface reactions without contribution from homogeneous gas-phase reactions. This controlled reaction environment revealed that SWCNT growth is a complex multicomponent reaction in which not just C, but also H, and O play a critical role. These experiments identified acetylene as a prolific direct building block for carbon network formation that is an order of magnitude more efficient than other small-molecule precursors. The molecular jet experiments show that with optimal catalyst particle size the incidence rate of acetylene molecules plays a critical role in the formation of single-wall carbon nanotubes and dense vertically aligned arrays in which they are the dominant component. The threshold for vertically aligned growth, the growth rate, the diameter, and the number of walls of the carbon nanotubes are systematically correlated with the acetylene incidence rate and the substrate temperature.     

Dendron growth from vertically aligned single-walled carbon nanotube thin layer arrays for photovoltaic devices

Single-walled carbon nanotube arrays attached to conductive transparent electrodes have previously shown promise for use in photovoltaic devices, whilst still retaining light transmission. Here, chemical modification of these thin (<200 nm) arrays with PAMAM-type dendrons has been undertaken to enhance the photoresponse of these devices. The effect of modification on the electrode was measured by differential pulse voltammetry to detect the dendrons, and the effect on the nanotubes was measured by Raman spectroscopy. Solar simulator illumination of the cells was performed to measure the effect of the nanotube modification on the cell power, and determine the optimal modification. Electrochemical impedance spectroscopy was also used to investigate the equivalent electronic circuit elements of the cells. The optimal dendron modification occurred with the second generation (G-2.0), which gave a 70% increase in power over the unmodified nanotube array.     

Modification of vertically aligned carbon nanotube arrays with palladium nanoparticles for electrocatalytic reduction of oxygen

A novel type of palladium nanoparticles-modified multiwalled carbon nanotubes composite-electrode with electrocatalytic activity for oxygen reduction is presented. The nanocomposite was prepared by magnetron sputtering deposition with Pd in Ar atmosphere on MWNTs, which were synthesized on Ta plates by chemical vapor deposition. Both scanning electron microscopy and transmission electron microscopy were employed to observe the surface morphology. The Pd nanoparticles, with diameters around 5 nm, are dispersed at the tips and on the sidewalls of the MWNTs. Voltammetry, amperometry and electrochemical impedance measurements were used to demonstrate the strong electrocatalytic activity of the nanocomposite in acid solution. Compared to the bare MWNT electrode, the PdNPs/MWNT nanocomposite shows a positive shift of the O₂ reduction current at onset potentials from +400 to +500 mV, a concurrent 1.5-fold increase in the O₂ reduction peak current with high stability. The successful preparation of PdNPs/MWNTs nanocomposite by magnetron sputtering deposition opens a new path for an efficient dispersion of promising nanoparticles for fuel cells and O₂ sensors.     

Protein electrochemistry using aligned carbon nanotube arrays

The remarkable electrocatalytic properties and small size of carbon nanotubes make them ideal for achieving direct electron transfer to proteins, important in understanding their redox properties and in the development of biosensors. Here, we report shortened SWNTs can be aligned normal to an electrode by self-assembly and act as molecular wires to allow electrical communication between the underlying electrode and redox proteins covalently attached to the ends of the SWNTs, in this case, microperoxidase MP-11. The efficiency of the electron transfer through the SWNTs is demonstrated by electrodes modified with tubes cut to different lengths having the same electron-transfer rate constant.     

A quantum dot sensitized solar cell based on vertically aligned carbon nanotube templated ZnO arrays

We report on a quantum dot sensitized solar cell (QDSSC) based on ZnO nanorod coated vertically aligned carbon nanotubes (VACNTs). Electrochemical impedance spectroscopy shows that the electron lifetime for the device based on VACNT/ZnO/CdSe is longer than that for a device based on ZnO/CdSe, indicating that the charge recombination at the interface is reduced by the presence of the VACNTs. Due to the increased surface area and longer electron lifetime, a power conversion efficiency of 1.46% is achieved for the VACNT/ZnO/CdSe devices under an illumination of one Sun (AM 1.5G, 100 mW/cm²).     

Photocatalytic methane decomposition over vertically aligned transparent TiO2 nanotube arrays

We report here on a study of vertically aligned TiO(2) nanotube arrays grown by the one-step anodic oxidation technique and their photocatalytic performance for methane decomposition. Quantitative activity data as a function of film thickness is obtained.     

Synthesis of vertically aligned carbon nanotube arrays on polyhedral Fe/Al2O3 catalysts

Polyhedral Fe/Al(2)O(3) catalysts prepared by an impregnation method were used for the synthesis of vertically aligned carbon nanotube (CNT) arrays from the pyrolysis of ethylene at 800 °C.     

Transferred vertically aligned N-doped carbon nanotube arrays: use in dye-sensitized solar cells as counter electrodes

We prepared vertically aligned nitrogen doped carbon nanotubes (CNTs) on a rigid glass substrate or flexible plastic substrate via a 'growth-detachment-transfer' process and the vertically aligned N-doped CNT arrays are employed as counter electrodes for novel dye-sensitized solar cells.     

Electrochemical capacitive properties of CNT fibers spun from vertically aligned CNT arrays

Due to their lightweight, large surface area; excellent electrical conductivity; and mechanical strength, carbon nanotube (CNT) fibers show great potentials in serving as both electrode materials and current collectors in supercapacitors. In this paper, the capacitive properties of both as-spun CNT fibers and electrochemically activated CNT fibers have been investigated using cyclic voltammetry and electrochemical impedance spectroscopy. It is found that the as-spun CNT fibers exhibit a very low specific capacitance of 2.6 F g⁻¹, but electrochemically activated CNT fibers show considerably improved specific capacitance. The electrochemical activation has been realized by cyclic scanning in a wide potential window. Different electrolytes have also been examined to validate the applicability of our carbon materials and the activation mechanism. It is believed that such an activation process can significantly improve the surface wetting of the CNT fibers by electrolyte (aqueous Na₂SO₄ solution). The cycling stability and rate-dependence of the capacitance have been studied, and the results suggest practical applications of CNT fibers in electrochemical supercapacitors.     

Uniform, dense arrays of vertically aligned, large-diameter single-walled carbon nanotubes

Precisely controlled reactive chemical vapor synthesis of highly uniform, dense arrays of vertically aligned single-walled carbon nanotubes (SWCNTs) using tailored trilayered Fe/Al(2)O(3)/SiO(2) catalyst is demonstrated. More than 90% population of thick nanotubes (>3 nm in diameter) can be produced by tailoring the thickness and microstructure of the secondary catalyst supporting SiO(2) layer, which is commonly overlooked. The proposed model based on the atomic force microanalysis suggests that this tailoring leads to uniform and dense arrays of relatively large Fe catalyst nanoparticles on which the thick SWCNTs nucleate, while small nanotubes and amorphous carbon are effectively etched away. Our results resolve a persistent issue of selective (while avoiding multiwalled nanotubes and other carbon nanostructures) synthesis of thick vertically aligned SWCNTs whose easily switchable thickness-dependent electronic properties enable advanced applications in nanoelectronic, energy, drug delivery, and membrane technologies.     

Fast preparation of hydroxyapatite/superhydrophilic vertically aligned multiwalled carbon nanotube composites for bioactive application

A method for the electrodeposition of hydroxyapatite films on superhydrophilic vertically aligned multiwalled carbon nanotubes is presented. The formation of a thin homogeneous film with high crystallinity was observed without any thermal treatment and with bioactivity properties that accelerate the in vitro biomineralization process and osteoblast adhesion.     

Influence of polar groups on the wetting properties of vertically aligned multiwalled carbon nanotube surfaces

In this work, we have studied superhydrophilic and superhydrophobic transitions on the vertically aligned multiwalled carbon nanotube (VACNT) surfaces. As-grown, the VACNT surfaces were superhydrophobic. Pure oxygen plasma etching modified the VACNT surfaces to generate superhydrophilic behavior. Irradiating the superhydrophilic VACNT surfaces with a CO₂ laser (up to 50?kW?cm^?2) restored the superhydrophobicity to a level that depended on the laser intensity. Contact angle and surface energy measurements by the sessile drop method were used to examine the VACNT surface wetting. X-ray photoelectron spectroscopy (XPS) showed heavy grafting of the oxygen groups onto the VACNT surfaces after oxygen plasma etching and their gradual removal, which also depended on the CO₂ laser intensity. These results show the great influence of polar groups on the wetting behavior, with a strong correlation between the polar part of the surface energy and the oxygen content on the VACNT surfaces. In addition, the CO₂ laser treatment created an interesting cage-like structure that may be responsible for the permanent superhydrophobic behavior observed on these samples.     

Membranes of vertically aligned superlong carbon nanotubes

In the present work, we have developed a simple but effective method to prepare superlong vertically aligned carbon nanotubes (SLVA-CNT) and epoxy composite membranes, and we have demonstrated that various liquids, including water, hexane, and dodecane, can effectively pass through the SLVA-CNT membranes. These results were confirmed by molecular dynamics simulations. While the mechanical densification was used to further enhance the flow transport through the SLVA-CNT membranes, we developed in this study a magnetic-nanoparticle switching system to turn on and off the flow through the nanotube membrane by simply applying an alternating voltage. The methodologies developed in this study should have a significant implication to the development of various smart membranes for advanced intelligent systems.     

Biomineralization of superhydrophilic vertically aligned carbon nanotubes

Vertically aligned carbon nanotubes (VACNT) promise a great role for the study of tissue regeneration. In this paper, we introduce a new biomimetic mineralization routine employing superhydrophilic VACNT films as highly stable template materials. The biomineralization was obtained after VACNT soaking in simulated body fluid solution. Detailed structural analysis reveals that the polycrystalline biological apatites formed due to the -COOH terminations attached to VACNT tips after oxygen plasma etching. Our approach not only provides a novel route for nanostructured materials, but also suggests that COOH termination sites can play a significant role in biomimetic mineralization. These new nanocomposites are very promising as nanobiomaterials due to the excellent human osteoblast adhesion.     

A novel catalyst-free synthesis of vertically aligned silicon nanowire-carbon nanotube heterojunction arrays for high performance electron field emitters

A novel, catalyst-free strategy for the direct synthesis of vertically aligned silicon nanowire-carbon nanotube (SiNW-CNT) heterojunction arrays is presented. Such a heterojunction with the junction area in the nanoscale displays enhanced field emission characteristics at low turn-on field, with a nearly three times increase in the field enhancement factor.     

Electrowetting of aligned carbon nanotube films

Electrowetting is one approach to reducing the interfacial tension between a solid and a liquid. In this method, an electrical potential is applied across the solid/liquid interface which modifies the wetting properties of the liquid on the solid without changing the composition of the solid and liquid phases. Electrowetting of aligned carbon nanotube (CNT) films is investigated by the sessile drop method by dispensing deionized (DI) water or 0.03 M NaCl droplets (contacted by Au wire) onto aligned CNT films assembled on a copper substrate. The results demonstrate that electrowetting can greatly reduce the hydrophobicity of the aligned CNTs; the contact angle saturation for DI water and 0.03 M NaCl droplets occurs at 98 and 50 degrees , respectively. The combined effects of the geometrical roughness and the electrical potential on the contact angle are briefly discussed and modeled. Such a strategy may be invoked to controllably reduce the interfacial tension between carbon nanotubes (CNTs) and polymer precursors when infiltrating the monomers into the prealigned nanotube films.     

Growth mechanism of long aligned multiwall carbon nanotube arrays by water-assisted chemical vapor deposition

Highly aligned arrays of multiwalled carbon nanotube (MWCNT) on layered Si substrates have been synthesized by chemical vapor deposition (CVD). The effect of the substrate design and the process parameters on the growth mechanism were studied. Adding water vapor to the reaction gas mixture of hydrogen and ethylene enhanced the growth which led to synthesis of longer CNT arrays with high density. Environmental scanning electron microscopy (ESEM), energy-dispersive spectroscopy (EDS), and atomic force microscopy (AFM) were used to analyze the CNT morphology and composition. Quadrupole mass spectroscopy (QMS) provided in-situ information on the gas spices within the reaction zone. On the basis of results, we verified the top growth mechanism and evaluated the reason of decline and stoppage of the CNT growth after extended period of deposition. Multilayered Si substrates with a top film of Al2O3, having appropriate roughness, provide favorable conditions to form catalyst islands with uniform distribution and size. Using water-assisted CVD process and optimized substrate design, our group succeeded to grow vertically aligned, patterned MWCNT up to 4-mm long. The arrays were of high purity and weak adhesion which allowed to be peeled off easily from the substrate.     

Self-assembly of vertically aligned gold nanorod arrays on patterned substrates

Nanorods standing at attention! A self-assembly technique based on convective and capillary forces was used for the direct fabrication of standing arrays of gold nanorods on lithographically predefined areas. The hexagonal close-packed structure of gold nanorods creates an ideal substrate for surface-enhanced Raman spectroscopy.     

Reversible electrowetting of vertically aligned superhydrophobic carbon nanofibers

Reversible electrostatically induced wetting (electrowetting) of vertically aligned superhydrophobic carbon nanofibers has been investigated. Carbon nanofibers on a 5 x 5 microm pitch were grown on Si substrates, electrically insulated with a conformal dielectric, and hydrophobized with fluoropolymer. This nanostructured scaffold exhibited superhydrophobic behavior for saline (theta approximately 160 degrees). Electrowetting induced a contact angle reduction to theta approximately 100 degrees. Competitive two-liquid (dodecane/saline) electrowetting exhibited reversibility on the same nanostructured scaffold. Without applied bias, ultra-fine-point tip (approximately 25 nm radius) nanofibers result in effectively zero capacitance with the overlying saline layer. Complete electrowetting of the substrate is confirmed as capacitance values increase by several orders of magnitude with increased wetting. These results demonstrate the applicability of reversible electrowetting on nanostructured scaffolds and use of nanofabricated structures that can be integrated with various micro- and nanoelectronic technologies.