Radial growth of vertically aligned carbon nanotube arrays from ethylene on ceramic spheres

Vertically aligned carbon nanotube (VACNT) arrays grown on ceramic spheres are obtained from ethylene using a floating catalysis process. The exhaust gas mainly contains light gaseous hydrocarbons, which decreases the contamination at the outlet of the reactor. Linear synchronous growth of the VACNT arrays is demonstrated and the morphology evolution of VACNT array grown on spheres is shown. The VACNT arrays on the spheres crack radially into a flower-like structure when the length of CNT is above 400 μm. The VACNT arrays grown on spheres still possess good flowability even when the length of the array reaches 1100 μm after a 2-h growth at 800 °C. The arrays on the spheres show good alignment, high purity and good graphitization. Meanwhile, with a decrease in temperature, the diameter of CNTs in the array correspondingly decreases, the distribution becomes narrower, and the growth rate decreases. The apparent activation energy is 180 ± 8 kJ/mol, indicating that ethylene is a good carbon source for fast and continuous radial growth of millimeter VACNT arrays on ceramic spheres.     

Alcohol-assisted rapid growth of vertically aligned carbon nanotube arrays

Millimeter-to-centimeter scale vertically aligned carbon nanotube (VACNT) arrays are widely studied because of their immense potential in a range of applications. Catalyst control during chemical vapor deposition (CVD) is key to maintain the sustained growth of VACNT arrays. Herein, we achieved ultrafast growth of VACNT arrays using Fe/Al₂O₃ catalysts by ethanol-assisted two-zone CVD. One zone was set at temperatures above 850 °C to pyrolyze the carbon source and the other zone was set at 760 °C for VACNT deposition. By tuning synthesis parameters, up to 7 mm long VACNT arrays could be grown within 45 min, with a maximal growth rate of ∼280 μm/min. Our study indicates that the introduction of alcohol vapor and separation of growth zones from the carbon decomposition zone help reduce catalyst particle deactivation and accelerate the carbon source pyrolysis, leading to the promotion of VACNT array growth. We also observed that the catalyst film thickness did not significantly affect the CNT growth rate and microstructures under the conditions of our study. Additionally, the ultralong CNTs showed better processability with less structural deformation when exposed to solvent and polymer solutions. Our results demonstrate significant progress towards commercial production and application of VACNT arrays.     

High surface area diamond-like carbon electrodes grown on vertically aligned carbon nanotubes

Electrochemically active diamond-like carbon (DLC) electrodes featuring high specific surface area have been prepared by plasma-enhanced chemical vapour deposition (CVD) onto densely packed forests of vertically aligned multiwall carbon nanotubes (VACNTs). The DLC:VACNT composite film exhibits a complex topography with web like features and ridges generated by partial coalescence of the DLC over the CNT arrays. DLC:VACNT electrodes exhibit low background responses over a large potential window, low uncompensated resistance, as well as low charge-transfer impedance in the presence of ferrocyanide as a redox probe. The interfacial capacitance associated with the DLC:VACNT electrode is in the range of 0.6 mF cm⁻², a value two orders of magnitude larger than in conventional flat carbon electrodes. DLC films grown onto single-crystal Si(1 0 0) under identical conditions resulted in essentially insulating layers. Conducting-atomic force microscopy studies reveal that the film electro-activity does not arise from specific topographic features in the highly corrugated film. The ensemble of experimental results suggests that the enhanced electrochemical responses are not connected to areas in which the CNT support is exposed to the electrolyte solution. This is remarkable behaviour considering that no dopants have been included during the DLC film growth.     

Horizontally aligned single-walled carbon nanotube field emitters fabricated on vertically aligned multi-walled carbon nanotube electrode arrays

Vertically aligned multi-walled carbon nanotube (MWCNT) arrays were fabricated on an anodic aluminum oxide membrane bonded to a Si wafer. After obtaining a protruding tip for the MWCNTs by etching away some oxide, they were used as electrodes in the fabrication of carbon nanotube field emitters. Long single-walled carbon nanotubes (SWCNTs) were spin coated on the MWCNT arrays of uniform height. Clean SWCNTs were suspended by attaching them to the tips of the vertically aligned MWCNT arrays. The spin coated SWCNTs function as emitters, while the MWCNT arrays function as electrodes. The field emission was greatly improved by coating gold on the MWCNT arrays and annealing at 400 °C. Our field emitter exhibits good field emission properties such as a low turn-on field (1.4 V/μm), high current density (122 mA/cm²), and good stability (55 h for 10% degradation of current density from 400 μA/cm²).     

Vertically aligned carbon nanotube film electrodes for bioelectrocatalytic dioxygen reduction

We have prepared vertically aligned carbon nanotube (VACNT) film electrodes for bioelectrocatalytic dioxygen reduction. The electrodes were prepared by a CNT-transfer technique attaching the as-grown VACNTs to an ITO electrode with a conductive CNT/epoxy glue. The VACNTs greatly enhance the active electrode area as shown by the substantial current increase of the slow electroreduction of hydrogen peroxide as well as the increase of the efficiency of the oxidation and reduction of the water-insoluble redox probe t-butylferrocene. Several methods for immobilisation of the multicopper enzyme laccase, both with and without mediator, were evaluated. Very high non-mediated catalytic dioxygen reduction current was measured using VACNTs functionalised with 1-pyrenesulfonic acid. The VACNT electrodes were successfully applied as cathode in a zinc–oxygen battery, reaching a power density of 275 μW cm⁻² at 1.5 V with pyrene-functionalised VACNTs and 115 μW cm⁻² at 0.9 V with syringaldazine as a mediator in oxygen saturated buffer.     

Sputter deposition of highly dispersed platinum nanoparticles on carbon nanotube arrays for fuel cell electrode material

Vertically aligned carbon nanotube (VACNT) arrays were synthesized using a microwave-plasma-enhanced chemical vapor deposition (MPECVD) system for polymer electrolyte fuel cell (PEMFC) electrode applications. Platinum nanoparticles (Pt NPs) were deposited on as grown VACNT arrays by a DC sputtering system. Pt NPs in the size range of 3–5 nm were formed on the CNT surfaces. X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy and electron microscopy were employed to study the structural and chemical bonding changes post deposition of Pt NPs. Variable particle density along the nanotube length was observed with cluster formation on tip ends and individual Pt NPs forming farthest away from tip ends. Change observed in the C1s and N1s core level spectra and its possible implications on the Pt/VACNT properties were also discussed.     

Effects of nanotube size and roof-layer coating on viscoelastic properties of hybrid diamond-like carbon and carbon nanotube composites

Hybrid carbon nanobuffers are developed by exploiting the ultra-hardness and wear-resistant properties of diamond-like carbon (DLC) coatings and the inherent viscoelasticity properties of vertically aligned carbon nanotubes (VACNTs). The viscoelastic properties of carbon nanobuffers incorporating thin-walled and thick-walled CNTs, respectively, are characterized by means of nanoindentation dynamic mechanical analysis tests. It is shown that the thin-walled nanobuffer has a better damping performance than the thick-walled nanobuffer due to its buckling-driven friction and post-buckling behaviors; particularly under large displacements. In addition, it is shown that under large indenter displacements, the VACNT arrays with DLC coatings display the improved stress distributions and enhanced strain energy dissipation performances due to the load transfer on the top of VACNTs. Molecular dynamics (MD) simulations are performed to investigate the roof-layer effect on damping behavior and structural deformation of the coated and uncoated VACNTs under nanoindentation. The results confirm that the VACNT with a DLC coating exhibits the significantly damping characterizations than the non-coated VACNT. Overall, the results presented in this study reveal the potential for tuning the damping performance of CNT-based nanobuffers through a careful control of the CNT size.     

垂直碳纳米管阵列的生长控制研究进展

垂直碳纳米管（VACNT）阵列由于具有良好的排列、优异的导电导热能力、高比表面积、高纯度等优点而得到广泛应用。本文概述了用于碳纳米管阵列生长的热化学气相沉积（CVD）制备方法的最新进展,重点阐述了CVD法生长碳纳米管阵列的动力学与生长终止机理,指出CVD过程中的催化剂形貌演化是引发碳纳米管阵列生长停止的重要原因。介绍了人们通过生长条件控制与催化剂设计等方法调控碳纳米管阵列结构（包括管壁数、管径和密度）方面取得的进展,指出碳纳米管阵列的大批量制备及结构参数的精确调控是未来发展的 重点。     

Effect of sidewall modification in the determination of friction coefficient of vertically aligned carbon nanotube films using friction force microscopy

The significance of the sidewall surface of vertically aligned carbon nanotubes (VACNTs) and the effect of humidity in the determination of VACNT film friction coefficient have been investigated. VACNT films of 2 μm thick were sidewall-modified by means of CF₄ and O₂ plasma treatments, and verified for the functionalization of the sidewalls. They were then characterized for wettability properties, as well as friction coefficient using friction force microscopy at different humidity levels. It was found that humidity had insignificant effect on the friction coefficient, and sidewall friction formed a major component of the friction force experienced by the tip. Sidewall modifications resulted in friction coefficient changes of up to 50%.     

Vertically aligned carbon nanotube arrays grown on a lamellar catalyst by fluidized bed catalytic chemical vapor deposition

Large amount of vertically aligned carbon nanotube (CNT) arrays were grown among the layers of vermiculite in a fluidized bed reactor. The vermiculite, which was 100-300 μm in diameter and merely 50-100 μm thick, served as catalyst carrier. The Fe/Mo active phase was randomly distributed among the layers of vermiculite. The catalyst shows good fluidization characteristics, and can easily be fluidized in the reactor within a large range of gas velocities. When ethylene is used as carbon source, CNT arrays with a relatively uniform length and CNT diameter can be synthesized. The CNTs in the arrays are with an inner diameter of 3-6 nm, an outer diameter of 7-12 nm, and a length of up to several tens of micrometers. The as-grown CNTs possess good alignment and exhibit a purity of ca. 84%. Unlike CNT arrays grown on a plane or spherical substrate, the CNT arrays grown in the fluidized bed remain their particle morphologies with a size of 50-300 μm and the good fluidization characteristics were preserved accordingly.     

Processing and properties of aligned multi-walled carbon nanotube/aluminoborosilicate glass composites made by sol-gel processing

We describe a novel sol-gel based approach for producing aluminoborosilicate glass composites containing continuous, aligned carbon nanotubes. The process involves the production of aligned carbon nanotubes (ACNT) via aerosol chemical vapour deposition (CVD), followed by infiltration of the ACNT with aluminoborosilicate sol. The advantages of this process are three fold: (1) aerosol CVD is an efficient method of producing clean, aligned arrays of CNTs, (2) sol-gel chemistry provides a simple route to infiltration of the ACNTs, and (3) carbon nanotube (CNT) agglomeration problems associated with CNT composites are circumvented. ACNTs (carpets) with heights of up to 4.4 mm were grown with areas of 10 mm × 20 mm for composite fabrication. The composite showed extensive pullout of the CNTs on a fracture surface and improved thermal and electrical conductivities of 16 Wm⁻¹ K⁻¹ and 5-8 × 10² S m⁻¹ respectively compared with only 1.2 W m⁻¹ K⁻¹ and 10⁻¹³ S m⁻¹ for the monolithic glass.     

Synthesis of millimeter-long vertically aligned carbon nanotube arrays on aluminum oxide buffer prepared by layer-by-layer assembly of boehmite nanoplates

To synthesize vertically aligned carbon nanotube (VA-CNT) arrays longer than a millimeter using chemical vapor deposition (CVD), aluminum oxide buffer has to be deposited on supporting substrates to prevent diffusion and aggregation of catalyst nanoparticles. Currently, reliable deposition has to be made using expensive and time-consuming e-beam evaporation or thermal sputtering. Here, we report a simple, low-cost, and scalable method for buffer preparation using layer-by-layer assembly of boehmite nanoplates followed by thermal annealing. On top of buffer prepared using this method, we have grown VA-CNT arrays consisting of CNTs with a length of 1.3(±0.1) mm, an inner diameter of 5.6(±1.3) nm, and a wall number of 4(±1) by using CVD with iron as catalyst and ethylene as carbon source.     

Millimeter-tall single-walled carbon nanotube forests grown from ethanol

Millimeter-tall vertically-aligned carbon nanotubes (VA-CNTs) were grown from ethanol under ambient pressure by Co-catalyzed chemical vapor deposition (CVD), with systematic optimization of the CVD temperature and catalytic conditions using combinatorial catalyst libraries. We investigated the use of both aluminum oxide and silicon oxide as underlayers for the Co catalyst and found that VA-CNTs grew to millimeter heights in 15-30 min when the pyrolysis of ethanol was carried out at high temperatures (?850 °C) and long residence times (?10 s). Thick Co catalytic layers (?1.3 nm) produced (sub)millimeter-tall multi-walled VA-CNTs on both the aluminum oxide and silicon oxide underlayers. However, thin Co catalytic layers (0.62-1.0 nm) produced (sub)millimeter-tall VA-CNTs, which consisted mainly of single-walled CNTs, only on the aluminum oxide underlayers. Stripe patterns were found in the VA-CNTs near the substrate on both aluminum oxide and silicon oxide, indicating some instability prior to growth termination. The possible roles of aluminum oxide in growing millimeter-tall single-walled VA-CNTs were discussed.     

Fluffy carbon nanotubes produced by shearing vertically aligned carbon nanotube arrays

Fluffy carbon nanotubes (CNTs), which are cotton-like macroscopic structures, are obtained by simple high-speed shearing of vertically aligned CNT (VACNT) arrays. The fluffy CNTs are composed of CNT bundles with a diameter of several micrometers, and have an extremely low apparent density of 3-10 g/L. A requisite for their formation is the alignment of CNTs in the initial array. The shear between the rotor and the arrays tears the arrays along the axial direction and this results in their dispersion into low density fluffy CNTs.     

Nucleation and aligned growth of multi-wall carbon nanotube films during thermal CVD

The development during early growth of a multi-wall carbon nanotube film by thermal CVD with acetylene (C₂H₂) and hydrogen at 750 °C has been characterized in detail by cross-section transmission electron microscopy. The studies provide information on the nanotube growth mechanisms and the complex catalyst transformations that are essential for the onset of different growth stages. An initial random growth catalysed by supported particles is followed by aerosol growth of aligned tubes. This results in a two-layered film structure, where a film of aligned nanotubes is lifting up an initially formed nanotube network from the substrate.     

Selective growth of carbon nanotube at low temperate using triode type plasma enhanced CVD method

The low temperature growth and the selective growth of the carbon nanotube (CNT) were studied using the triode-type radio frequency plasma enhanced chemical vapor deposition (RF-PECVD) equipment. The aligned CNTs −2.6 μm in length and −10¹¹/cm² in density were vertically grown at 550 °C on the Si substrate. Moreover, the selective growth of the CNT was performed using the photolithography method.     

Wafer‐Scale Vertically Aligned Carbon Nanotubes Locked by In Situ Hydrogelation toward Strengthening Static and Dynamic Compressive Responses

Wafer‐scale vertically aligned carbon nanotube/poly(vinyl alcohol) (VACNT/PVA) hydrogels are fabricated by infiltration of PVA among VACNTs and subsequent in situ hydrogelation. Owing to the homogeneous PVA infiltration, uniform distribution and orientation of the carbon nanotubes (CNTs) are well retained, which in turn provide large CNT‐PVA interfaces throughout the resulting hydrogels. Compared to bare PVA hydrogels, such composite hydrogels perform significantly enhanced longitudinal compressive responses upon both static and dynamic loadings, achieving improvements of up to 25.2‐ and 9.0‐fold in strength and loss modulus, respectively. The novel scalable fabrication of VACNT/PVA hydrogels and their attractive performances hold great potential for a wide range of applications.     

Growth and electrical characterization of high-aspect-ratio carbon nanotube arrays

The remarkable properties of carbon nanotubes (CNTs) make them attractive for microelectronic applications, especially for interconnects and nanoscale devices. In this paper, we describe a microelectronics compatible process for growing high-aspect-ratio CNT arrays with application to vertical electrical interconnects. A lift-off process was used to pattern catalyst (Al₂O₃/Fe) islands to diameters of 13 or 20 μm. After patterning, chemical vapor deposition (CVD) was involved to deposit highly aligned CNT arrays using ethylene as the carbon source, and argon and hydrogen as carrier gases. The as-grow CNTs were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The results demonstrated that the CNTs have high purity, and form densely-aligned arrays with controllable array size and height. Two-probe electrical measurements of the CNT arrays indicate a resistivity of ∼0.01 Ω cm, suggesting possible use of these CNTs as interconnect materials.     

Terahertz time-domain spectroscopy characterization of vertically aligned carbon nanotube films

Terahertz time-domain spectroscopy measurements were made for vertically aligned multi-walled carbon nanotube (VACNT) films. We obtained the frequency dependent complex permittivity and conductivity (on the assumption that permeability μ = 1) of several samples exhibiting Drude behaviour for lossy metals. The obtained material properties of VACNT films provide information for potential microwave and terahertz applications.     

Thermal and electrical conductivity of tall, vertically aligned carbon nanotube arrays

Vertically aligned multi-walled carbon nanotube (MWCNT) arrays up to ∼6 mm high with an array density of 0.06 g cm⁻³ have been grown by chemical vapor deposition. Thermal conductivities (κ) and electrical conductivities (σ) were determined from 5 K to 390 K. The range for κ at 300 K is 0.5-1.2 W m⁻¹ K⁻¹ along the tube growth direction, with the shortest array having the highest κ, and an order of magnitude lower in the direction perpendicular to the tubes. The same trends also were evident for electrical conductivity, i.e., decreasing values with increasing array height and conductivity an order of magnitude lower in the perpendicular direction. Values of σ ranged from 7 to 14 S cm⁻¹ along the array at 300 K. The Seebeck coefficient is ∼20 μV K⁻¹ at 300 K. The effective Lorentz number indicates that thermal conductivity in the carbon nanotube arrays is phonon dominated over the full temperature range.