Synthesis of vertically aligned carbon nanotubes using natural palm oil as carbon precursor

Vertically aligned carbon nanotubes (VACNTs) have been synthesized on silicon substrates in a thermal catalytic chemical vapor reactor using natural palm oil as the carbon source. Field Emission Scanning Electron Microscopy (FESEM) and microraman analysis revealed dense bundles of mixed multi-walled and single-walled carbon nanotubes (CNTs). The diameters of the single-walled carbon nanotubes (SWCNTs) were estimated to be between 0.6 nm and 1.2 nm. Thermogravimetric analysis (TGA) results showed that 90% purity was achieved at the expense of 4% weight catalyst material.     

High-performance supercapacitors based on vertically aligned carbon nanotubes and nonaqueous electrolytes

We demonstrate the high performance of supercapacitors fabricated with vertically aligned carbon nanotubes and nonaqueous electrolytes such as ionic liquids and conventional organic electrolytes. Specific capacitance, maximum power and energy density of the supercapacitor measured in ionic liquid were ~75 F g(-1), ~987 kW kg(-1) and ~27 W h kg(-1), respectively. The high power performance was consistently indicated by a fast relaxation time constant of 0.2 s. In addition, electrochemical oxidation of the carbon nanotubes improved the specific capacitance (~158 F g(-1)) and energy density (~53 W h kg(-1)). Both high power and energy density could be attributed to the fast ion transport realized by the alignment of carbon nanotubes and the wide operational voltage defined by the ionic liquid. The demonstrated carbon-nanotube- and nonaqueous-electrolyte-based supercapacitors show great potential for the development of high-performance energy storage devices.     

Growth of vertically aligned arrays of carbon nanotubes for high field emission

Vertically aligned multi-walled carbon nanotubes have been grown on Ni-coated silicon substrates, by using either direct current diode or triode plasma-enhanced chemical vapor deposition at low temperature (around 620 °C). Acetylene gas has been used as the carbon source while ammonia and hydrogen have been used for etching. However densely packed (∼ 10⁹ cm^− 2) CNTs were obtained when the pressure was ∼ 100 Pa. The alignment of nanotubes is a necessary, but not a sufficient condition in order to get an efficient electron emission: the growth of nanotubes should be controlled along regular arrays, in order to minimize the electrostatic interactions between them. So a three dimensional numerical simulation has been developed to calculate the local electric field in the vicinity of the tips for a finite square array of nanotubes and thus to calculate the maximum of the electron emission current density as a function of the spacing between nanotubes. Finally the triode plasma-enhanced process combined with pre-patterned catalyst films (using different lithography techniques) has been chosen in order to grow regular arrays of aligned CNTs with different pitches in the micrometer range. The comparison between the experimental and the simulation data permits to define the most efficient CNT-based electron field emitters.     

Fabrication of nanoparticles on vertically aligned multi-wall carbon nanotubes by e-beam evaporation

A novel composite electrode containing gold/platinum nanoparticles on the vertically aligned multi-wall nanotubes (MWCNTs) by electron beam evaporation (e-beam evaporation) is reported herein. The size of gold/platinum nanoparticles by e-beam evaporation was less than 10 nm, and distributed uniformly on the surface of vertically aligned MWCNTs. This straightforward process can fabricate high specific surface areas of gold/platinum nanoparticles on the MWCNTs, enhance the efficiency of organic fuel decomposition, and advance the sensor precision. In addition, the nanoparticles on the MWCNTs can also facilitate high electron mobility and chemical stability.     

Study on micro-patterning process of vertically aligned carbon nanotubes (VACNTs)

Vertically aligned carbon nanotubes (VACNTs) have drawn significant attention by the researchers because of their nanometric size and favorable material properties. Patterning of CNT forests in the micrometric domain is very important for their application in the area of microelectromechanical system (MEMS). For the first time this paper reports, detailed experimental investigation on a post growth μ-patterning process of VACNT forests. The micromechanical bending (M2B) process was locally applied at the targeted area in order to change the alignment of VACNT forests. Interestingly, the VACNT forest was transformed from typical black body absorber to reflective mirror as the M2B process was applied. Several parameters were identified that govern the resultant patterns such as rotational spindle speed, lateral bending speed, step size, tool morphology, and total depth of bend. Optimization of the parameters was carried out experimentally to obtain the best surface roughness and integrity of the microstructure. A minimum average surface roughness of Ra = 15 nm was achieved with 2000 rpm spindle speed, 1 mm/min bending speed and 1 µm step size.     

Real-time imaging of vertically aligned carbon nanotube array growth kinetics

In situ time-lapse photography and laser irradiation are applied to understand unusual coordinated growth kinetics of vertically aligned carbon nanotube arrays including pauses in growth, retraction, and local equilibration in length. A model is presented which explains the measured kinetics and determines the conditions for diffusion-limited growth. Laser irradiation of the growing nanotube arrays is first used to prove that the nanotubes grow from catalyst particles at their bases, and then increase their growth rate and terminal lengths.     

One-step catalytic growth of carbon nanofiber arrays vertically aligned on carbon substrate

Vertically aligned carbon nanofiber (VA-CNF) arrays on carbon substrate have been synthesized via one-step chemical vapor deposition process on copper foil, by using acetylene as carbon resource. Three types of carbon nanostructures, viz. bare carbon films, CNFs and VA-CNFs grown on carbon substrate, could be selectively synthesized by only modulating the concentration of C₂H₂ and NH₃ in the feeding gases. It was found that NH₃ was a key factor in the growth of VA-CNF arrays, which could increase the diffusion capability of copper atoms in carbon materials, therefore promote forming larger spherical Cu NPs catalysts for the growth of VA-CNFs. Furthermore, a growth mechanism in different feeding gas compositions was proposed.     

Quantitative elucidation of the rapid growth and growth saturation of millimeter-scale vertically aligned carbon nanotubes by hot-filament chemical vapor deposition

We report the rapid synthesis of millimeter-long vertically-aligned carbon-nanotubes (VACNTs) by hot-filament chemical-vapor-deposition without the use of water vapor. The growth rate increased initially up to ~ 190 μm/min but decreased thereafter resulting in the growth of up to 2.2 ± 0.2 mm in 23 ± 2 min. A thermodynamic model driven by a carbon-concentration gradient can account for very rapid initial growth with Arrhenius-type exponential temperature dependence. Another model devised for the quantitative elucidation of the monotonic decrease in growth-rate and quasi saturation of VACNT growth confirmed that the growth kinetics of VACNTs are controlled by the concomitant contribution of a diffusion-limited precursor supply and reaction-driven catalyst deactivation.     

Field emission characteristics from tapered ZnO nanostructures grown onto vertically aligned carbon nanotubes

Zinc oxide (ZnO) nanostructures were grown on vertically aligned carbon nanotubes (CNTs) using thermal chemical vapor deposition (CVD) to enhance the field emission characteristics. The shape of ZnO nanostructure was tapered. Scanning electron microscopy (SEM) image showed the ZnO nanostructures were grown onto CNT surface uniformly. The field electron emission of pristine CNTs and ZnO-coated CNTs were measured. The results showed that ZnO nanostructures grown onto CNTs could improve the field emission characteristics. The ZnO-coated CNTs had a threshold electric field at about 3.1 V/μm at 1.0 mA/cm². The results demonstrated that the ZnO-coated CNT is an ideal field emitter candidate material. The stability of the field emission current was also tested.     

Solution chemistry approach to fabricate vertically aligned carbon nanotubes on gold wires: towards vertically integrated electronics

A monolayer of hexadecyltrichlorosilane, 3-aminopropyltriethoxysilane or 3-mercaptopropyltrimethoxysilane was self-assembled onto a p-type silicon (100) substrate to provide a resist for electrochemical anodization with an atomic force microscope cantilever. Silane treatment of the oxide nanostructures created by anodization lithography allowed for the creation of a chemically heterogeneous surface, containing regions of -NH(2) or -SH surrounded by -CH(3) functionality. These patterned regions of -NH(2) or -SH provided the point of attachment for citrate-stabilized gold colloid nanoparticles, which act as 'seed' particles for the electro-less deposition of gold. This has allowed the creation of gold wires on a silicon surface. Carbon nanotubes, with high carboxylic acid functionality, were vertically immobilized on the patterned gold wires with the use of a cysteamine monolayer and a condensation reaction. Such a material may prove useful in the creation of future vertically integrated electronic devices where it is desirable for electron transport to be in three dimensions and this electron transport is demonstrated with cyclic voltammetry.     

Effects of vertically aligned carbon nanotubes on shear performance of laminated nanocomposite bonded joints

Abstract

The main objective is to improve the most commonly addressed weakness of the laminated composites (i.e. delamination due to poor interlaminar strength) using carbon nanotubes (CNTs) as reinforcement between the laminae and in the transverse direction. In this work, a chemical vapor deposition technique has been used to grow dense vertically aligned arrays of CNTs over the surface of chemically treated two-dimensionally woven cloth and fiber tows. The nanoforest-like fabrics can be used to fabricate three-dimensionally reinforced laminated nanocomposites. The presence of CNTs aligned normal to the layers and in-between the layers of laminated composites is expected to considerably enhance the properties of the laminates. To demonstrate the effectiveness of our approach, composite single lap-joint specimens were fabricated for interlaminar shear strength testing. It was observed that the single lap-joints with through-the-thickness CNT reinforcement can carry considerably higher shear stresses and strains. Close examination of the test specimens showed that the failure of samples with CNT nanoforests was completely cohesive, while the samples without CNT reinforcement failed adhesively. This concludes that the adhesion of adjacent carbon fabric layers can be considerably improved owing to the presence of vertically aligned arrays of CNT nanoforests.     

Preferential syntheses of semiconducting vertically aligned single-walled carbon nanotubes for direct use in FETs

We have combined fast heating with plasma enhanced chemical vapor deposition (PECVD) for preferential growth of semiconducting vertically aligned single-walled carbon nanotubes (VA-SWNTs). Raman spectroscopic estimation indicated a high yield of up to 96% semiconducting SWNTs in the VA-SWNT array. The as-synthesized semiconducting SWNTs can be used directly for fabricating FET devices without the need for any postsynthesis purification or separation.     

Direct growth of aligned carbon nanotubes on bulk metals

There are several advantages of growing carbon nanotubes (CNTs) directly on bulk metals, for example in the formation of robust CNT-metal contacts during growth. Usually, aligned CNTs are grown either by using thin catalyst layers predeposited on substrates or through vapour-phase catalyst delivery. The latter method, although flexible, is unsuitable for growing CNTs directly on metallic substrates. Here we report on the growth of aligned multiwalled CNTs on a metallic alloy, Inconel 600 (Inconel), using vapour-phase catalyst delivery. The CNTs are well anchored to the substrate and show excellent electrical contact with it. These CNT-metal structures were then used to fabricate double-layer capacitors and field-emitter devices, which demonstrated improved performance over previously designed CNT structures. Inconel coatings can also be used to grow CNTs on other metallic substrates. This finding overcomes the substrate limitation for nanotube growth which should assist the development of future CNT-related technologies.     

Oxygen plasma assisted end-opening and field emission enhancement in vertically aligned multiwall carbon nanotubes

This paper highlights the changes in micro-structural and field emission properties of vertically aligned carbon nanotubes (VACNTs) via oxygen plasma treatment. We find that exposure of very low power oxygen plasma (6 W) at 13.56 MHz for 15–20 min, opens the tip of vertically aligned CNTs. Scanning electron microscopy and transmission electron microscopy images were used to identify the quality and micro-structural changes of the nanotube morphology and surfaces. Raman spectra showed that the numbers of defects were increased throughout the oxygen plasma treatment process. In addition, the hydrophobic nature of the VACNTs is altered significantly and the contact angle decreases drastically from 110° to 40°. It was observed that the electron field emission (EFE) characteristics are significantly enhanced. The turn-on electric field (ETOE) of CNTs decreased from ∼0.80 V μm⁻¹ (untreated) to ∼0.60 V μm⁻¹ (oxygen treated). We believe that the open ended VACNTs would be immensely valuable for applications such as micro/nanofluidic based filtering elements and display devices.     

Effective growth of vertically aligned carbon nanotube turfs on flexible Al foil

Vertically aligned multi-walled carbon nanotube turfs (VACNTs) have been synthesized onto commercially available aluminum foil without the use of a pre-deposited catalyst. We used ferrocene as a precursor powder catalyst and acetylene as a carbon source to grow VACNTs using three-temperature-zone chemical vapor deposition at 550–950 °C. The greatest average height of the VACNTs was 124.5 ± 1.7 μm, attained with heating at 750 °C for 10 min. The diameters of the VACNTs were in the range of 5.25–11.85 nm with growth at temperatures of 600–850 °C. The scalable deposition method allows large area coverage on flexible metal foils, which is well suited for integration of vertically aligned carbon nanotubes into plastic electronics.     

Controlled density of vertically aligned carbon nanotubes in a triode plasma chemical vapor deposition system

We report on the growth mechanism and density control of vertically aligned carbon nanotubes using a triode plasma enhanced chemical vapor deposition system. The deposition reactor was designed in order to allow the intermediate mesh electrode to be biased independently from the ground and power electrodes. The CNTs grown with a mesh bias of + 300 V show a density of ∼ 1.5 μm^− 2 and a height of ∼ 5 μm. However, CNTs do not grow when the mesh electrode is biased to − 300 V. The growth of CNTs can be controlled by the mesh electrode bias which in turn controls the plasma density and ion flux on the sample.     

Purification process for vertically aligned carbon nanofibers

Individual, free-standing, vertically aligned multiwall carbon nanotubes or nanofibers are ideal for sensor and electrode applications. Our plasma-enhanced chemical vapor deposition techniques for producing free-standing and vertically aligned carbon nanofibers use catalyst particles at the tip of the fiber. Here we present a simple purification process for the removal of iron catalyst particles at the tip of vertically aligned carbon nanofibers derived by plasma-enhanced chemical vapor deposition. The first step involves thermal oxidation in air, at temperatures of 200-400 degrees C, resulting in the physical swelling of the iron particles from the formation of iron oxide. Subsequently, the complete removal of the iron oxide particles is achieved with diluted acid (12% HCl). The purification process appears to be very efficient at removing all of the iron catalyst particles. Electron microscopy images and Raman spectroscopy data indicate that the purification process does not damage the graphitic structure of the nanotubes.     

喷雾热解法在硅衬底上生长定向碳纳米管阵列(英文)

以向日葵油的甲基酯为碳源,二茂铁为催化剂前驱体,Ar为载气,通过喷雾热解法在硅衬底上合成定向碳纳米管阵列。结果表明,在硅衬底上原位形成Fe催化剂纳米颗粒。由拉曼光谱、透射电镜图和X-射线衍射谱图显示所制定向碳纳米管阵列具有较好的石墨化程度,其直径为1 0～3 0 nm,管壁约为1 0 nm。所制定向碳纳米管阵列中残留的催化剂含量可以忽略。     

Fabrication and characterization of vertically aligned carbon nanotubes on silicon substrates using porous alumina nanotemplates

An ethylene-air laminar diffusion flame successfully provided silicon substrates of anodic aluminum oxide (AAO) template with vertically oriented well-aligned carbon nanotubes. Field emission scanning electron microscopy (SEM) showed that open-tipped carbon nanotubes consisting of tube elements with the same length and diameter uniformly coated the template. High-resolution transmission electron microscopy (TEM) analyses revealed these nanotubes to be multiwalled carbon nanotubes, some well graphitized. It was found that cobalt catalyst particles, but not the porous aluminum templates, helped the growth of carbon nanotubes through graphitization and bonding of carbon nanotubes to the silicon substrates.     

直接在金属基片上生长超长宏观定向碳纳米管

在水辅助氧化作用下，直接在金属镍片上生长出宏观上定向生长的螺旋状碳纳米管，其长度达到7mm，直径在100-200nm，测试其场发射特性，开启场强为1．6V／μm，最大发射电流密度可达6mA／cm^2。