Thickness-, alignment- and defect-tunable growth of carbon nanotube arrays using designed mechanical loads

We demonstrate the thickness-, morphology-, and defect-tunable growth and simultaneous integration of aligned carbon nanotube (CNT) arrays using a novel microscale platform. This platform consists of a micromechanical spring of desired stiffness, which applies a precise vertical load to a vertically aligned CNT array during its growth by chemical vapor deposition (CVD). The micromechanical spring is strained by the extrusive growth force output from the aligned CNT array during its growth and, at the same time, exerts a mechanical restoring force against the buckling resistance of the CNTs. This application of a designed vertical load on the CNTs allows modulation of the thickness and degree of alignment of the CNT array, as well as the structural quality of the individual CNTs. Consequently, the electrical resistance between two opposing CNT arrays can be tuned by adjusting the vertical load. In addition, their sensing responsiveness toward chemical species can also be enhanced by applying larger vertical load on the CNTs. In contrast to conventional growth methods for producing aligned CNT arrays, our approach offers an efficient way for the growth engineering and on-chip integration of aligned CNT arrays in a single step of the CVD.     

CVD growth of secondary carbon nanotubes and its effect on field electron emission

Secondary carbon nanotubes (CNTs) were grown on primary ones by simply changing the methane concentration. No additional catalyst was used throughout the whole deposition process. The CNT growth was carried out using hot filament chemical vapor deposition in a gas mixture of methane and hydrogen. The structure and surface morphology of the deposited CNTs were studied and the field emission properties of the CNTs were tested. It was found that synthesizing primary CNTs at extremely low methane concentration is the key for the secondary growth without additional catalyst. The CNT samples grown with secondary nanotubes exhibited improved field emission properties.     

Carbon nanotube junctions obtained by pulsed liquid injection chemical vapour deposition

The effect of substrate surface roughness on the synthesis of carbon nanotube (CNT) junctions is studied. CNTs were obtained by a pulsed liquid injection chemical vapour deposition system (PLICVD) and grown on quartz substrates with different roughnesses. Nickel particles were used as catalyst and acetone as the carbon precursor. Results shown that CNTs growth depend strongly on the substrate irregularity. When roughness is present, the presence of CNT junctions are increased. On the quartz surface, without any modification of roughness, CNTs are not obtained. Thus, a growth mechanism for CNT junctions, based on the substrate roughness is suggested. This method represents an important alternative to produce CNTs for applying them in nanoelectronic devices.     

Multiwalled carbon nanotube deposition profiles within a CVD reactor: An experimental study

A number of proposed applications of carbon nanotube (CNT) arrays require that uniform deposition of well-aligned CNTs is achieved. The CNT deposition profiles inside a chemical vapor deposition (CVD) reactor are strongly dependant on the reaction temperatures, feed gas flow rates, carrier gas flow rates and reactor geometry. In addition, objects placed in the path of the flow of feed material could affect the deposition patterns. In this paper, an experimental study aimed at achieving better control of the deposition patterns of CNTs is presented. Multiwalled CNTs were grown on a long substrate by the catalytic CVD of a xylene/ferrocene solution. The deposition patterns on the substrate were examined for different furnace temperatures, xylene/ferrocene feed rates and carrier gas flow rates. Small objects representative of electronic devices were placed at different locations on the substrate and their effect on the deposition patterns was explored. The effect of changing the height and the gap distance between these objects was also studied.     

Growth of carbon nanotube forests between a bi-metallic catalyst layer and a SiO2 substrate to form a self-assembled carbon–metal heterostructure

A special nanostructure was formed by the growth of carbon nanotubes (CNTs) between a substrate and a thin bi-metallic catalyst layer using a thermal chemical vapor deposition process. The catalyst layer is composed of adjacently disposed Cr and Ni phases formed prior to CNT growth. The Cr/Ni layer serves as a bi-metallic catalyst layer, which is pushed away from the substrate as a thin and continuous nanomembrane with the growth of CNTs. The self-assembled CNT–catalyst heterostructure possesses a smooth surface (RMS = 2.9 nm) with a metallic shine. Directly interlinked to the Cr/Ni layer, dense and vertically aligned multi-walled CNTs are found. Compared to conventional CNT films, the structure has significant advantages for CNT integration. From technology point of view, the structure allows further processing without impact on the CNTs as well as transfer of pristine vertically aligned CNTs to arbitrary substrates. Moreover, the as-grown CNT films provide an interface ideal for further electrical, thermal and mechanical contacting of CNT films. We present structural investigations of this special CNT–metal heterostructure. Furthermore, we discuss possible interface mechanisms during catalyst layer formation and CNT growth.     

Fluidized bed catalytic chemical vapor deposition synthesis of carbon nanotubes—A review

Carbon nanotubes (CNTs) are pure carbon in nanostructures with unique physico-chemical properties. They have brought significant breakthroughs in different fields such as materials, electronic devices, energy storage, separation, sensors, etc. If the CNTs are ever to fulfill their promise as an engineering material, commercial production will be required. Catalytic chemical vapor deposition (CCVD) technique coupled with a suitable reactor is considered as a scalable and relatively low-cost process enabling to produce high yield CNTs. Recent advances on CCVD of CNTs have shown that fluidized-bed reactors have a great potential for commercial production of this valuable material. However, the dominating process parameters which impact upon the CNT nucleation and growth need to be understood to control product morphology, optimize process productivity and scale up the process. This paper discusses a general overview of the key parameters in the CVD formation of CNT. The focus will be then shifted to the fluidized bed reactors as an alternative for commercial production of CNTs.     

Plasma-Assisted Synthesis of Carbon Nanotubes

The application of plasma-enhanced chemical vapour deposition (PECVD) in the production and modification of carbon nanotubes (CNTs) will be reviewed. The challenges of PECVD methods to grow CNTs include low temperature synthesis, ion bombardment effects and directional growth of CNT within the plasma sheath. New strategies have been developed for low temperature synthesis of single-walled CNTs based the understanding of plasma chemistry and modelling. The modification of CNT surface properties and synthesis of CNT hybrid materials are possible with the utilization of plasma.     

碳纳米管在炭纤维表面的可控自组装

采用催化化学气相沉积法将碳纳米管(CNTs)原位生长于炭纤维(CF)表面并自组装成不同形貌的CNTs/CF杂化结构。使用扫描电子显微镜、拉曼光谱仪对制备的纳米/微米杂化结构进行微观形貌分析和结构表征。结果显示,随着温度的升高,碳纳米管在炭纤维表面由均匀分布状态转变为取向生长状态,并且长度及石墨化程度均不断增加。结合碳纳米管结构参数的变化,使用纳米悬臂梁模型解释了这一杂化结构的形成机理。模型分析表明,杂化结构的形貌转变是由不同温度下在炭纤维表面生长的碳纳米管的结构参数不同所造成的,因此可以通过调整相关结构参数控制碳纳米管在炭纤维表面的自组装过程。     

Growth of bent carbon nanotubes by in-situ control of cantilever bending

A new and simple method for in-situ control of the growth direction of carbon nanotubes (CNTs) on cantilevers has been developed using plasma enhanced chemical vapor deposition (PECVD). Plasma-induced surface stresses in PECVD processes tend to cause bending of the cantilevers, which significantly changes the electric field distribution near the free-end of the cantilever. By adjusting the flow ratio of the feed gases during CNT growth, the degree of cantilever bending can be controlled due to the change in the plasma-induced surface stress, and in doing so manipulating the field line direction, as well as the growth direction of CNTs. Combining this in-situ tunable CNT growth technique with electron beam induced deposition of catalyst patterns, we have fabricated a bent CNT on a cantilever in one single, continuous deposition run.     

Catalyst-free,self-assembly,and controllable synthesis of graphene flake–carbon nanotube composites for high-performance field emission

Catalyst-free and self-assembled growth of graphene flakes (GFs) on carbon nanotube (CNT) arrays have been realized by using microwave plasma enhanced chemical vapor deposition. The shape of GFs was highly manipulated by adjusting the growth time, C concentration, and microwave power. We qualitatively discussed the nucleation and growth mechanism of GFs based on the growth parameter–GF shape studies. The field emission (FE) properties of graphene flake–carbon nanotube (GF–CNT) composites for different GF shapes were measured and found to be strongly influenced by the GF distribution. The optimal shape of GFs for FE had small scales, sharp edges, and sparse distribution on CNTs. The best FE properties with the optimal shape were observed with a low turn-on electric field of 0.73 V/μm and excellent stability, which are superior to those of the as-grown CNT arrays and GF–CNT composites covered by densely distributed GFs. We consider that the large aspect ratio of CNTs and the unique FE stability of GFs play a synergetic effect on the improved FE properties.     

One-step growth of graphene–carbon nanotube hybrid materials by chemical vapor deposition

Graphene–carbon nanotube (CNT) hybrid materials were synthesized by simple one-step chemical vapor deposition (CVD) using ethanol as precursor. On a copper foil decorated with silicon nanparticles (Si NPs), a graphene film grows uniformly on the substrate while CNTs sprout out from Si NPs to form a network on top. The density of CNTs can be controlled by the CVD growth temperature. As measured by scanning and transmission electron microscopy, the obtained CNTs exhibit bamboo-like multiple-wall structures. Electrical characterization shows that the graphene–CNT hybrids exhibit p-type field-effect characteristics and a significantly higher conductivity compared to a CVD grown pure graphene film.     

Dry spinning yarns from vertically aligned carbon nanotube arrays produced by an improved floating catalyst chemical vapor deposition method

Carbon nanotube (CNT) yarn was drawn directly from super aligned CNT arrays synthesized by an improved floating catalyst chemical vapor deposition method. The synthesis of aligned CNT was performed as a multi-step interim reactant supply reaction to produce a double-layered CNT array in a horizontal quartz tube reactor. During the growth period, most impurities were blocked on the top surface of the first layer and therefore the top aligned CNT layer was unspinnable. However, the bottom CNT layer was super aligned CNTs, which were with clean surface and a tortuosity factor of 1.07. During the dry spinning process, the tangles, friction, and van der Waals interaction between CNTs served to hold them into CNT yarns. The tensile strength of the as-obtained CNT yarn can be further improved from 0.24 to 0.30 GPa by twisting.     

Fabrication of polypyrrole (PPy)/carbon nanotube (CNT) composite electrode on ceramic fabric for supercapacitor applications

Polypyrrole (PPy)/carbon nanotube (CNT) composite electrodes are fabricated on ceramic fabrics for electrochemical capacitor applications. The CNTs are grown on the ceramic fabrics by the chemical vapor deposition (CVD) method and PPy is subsequently coated on them by chemical polymerization. The large surface area and high conductivity of the CNTs on the porous ceramic fabrics enhance their energy storage capacity. PPy provides not only additional capacitance as an active material, but also enhances the adhesion between the CNTs and ceramic fabrics. Furthermore, PPy acts as a conducting binder for connecting every individual CNT to increase the capacitance. The morphology of the PPy–CNTs on the ceramic fabrics is confirmed by SEM and TEM, and the electrochemical characteristics are investigated by cyclic voltammetry and galvanostatic charge–discharge tests.     

Synthesis of carbon nanotubes on graphene quantum dot surface by catalyst free chemical vapor deposition

The growth of carbon nanotubes (CNTs) on graphene quantum dot surface has been explored using acetylene as the carbon source in a catalyst free chemical vapor deposition process. Dynamic studies were conducted to observe the CNT growth. The obtained nanotubes have a diameter distribution of 10–30 nm and show medium graphitic quality. Transmission electron microscopy observations and dynamic studies indicate that the formation of CNTs follows a different mechanism from traditional growth models, in which a wire-to-tube process and self-assembling of CNTs are involved. On the basis of these observations, a tentative continuous growth model is proposed for the CNT growth.     

The mechanism of the sudden termination of carbon nanotube supergrowth

The effect of growth conditions and catalyst lifetime on the supergrowth of carbon nanotubes (CNTs) through a water assisted chemical vapor deposition has been investigated. The reasons behind the observed sudden termination of the CNT growth were explored. A proper amount of water was found to improve the activity of the catalyst and enhance the growth rate of CNTs. However, the introduction of water did not extend the catalyst lifetime leading to unavoidable termination of the CNT growth. Further experiments demonstrated that in addition to catalyzing the CNT growth, catalyst particles can also decompose/etch the C sp2/sp3 bonds including those in the CNTs. The existing termination mechanism for the CNT growth fails to explain this. We therefore propose a model based on the catalyst phase transformation using the Johnson–Mehl–Avrami–Kolmogorov theory to predict the growth rate and termination of the CNT growth.     

Synthesis,microstructure and electrical conductivity of carbon nanotube–alumina nanocomposites

Carbon nanotube–alumina (CNT–Al₂O₃) nanocomposites have been synthesized by direct growth of carbon nanotubes on alumina by chemical vapor deposition (CVD) and the as-grown nanocomposites were densified by spark plasma sintering (SPS). Surface morphology analysis shows that the CNTs and CNT bundles are very well distributed between the matrix grains creating a web of CNTs as a consequence of their in situ synthesis. Even after the SPS treatment, the CNTs in the composite material are still intact. Experimental result shows that the electrical conductivity of the composites increases with the CNT content and falls in the range of the conductivity of semiconductors. The nanocomposite with highest CNT content has electrical conductivity of 3336 S/m at near room temperature, which is about 13 orders of magnitude increase over that of pure alumina.     

Low temperature, non-isothermal growth of carbon nanotubes

Non-isothermal growth of carbon nanotubes (CNTs) was studied in order to obtain the activation energy. CNTs were grown on an Fe-Si catalyst using microwave plasma-enhanced chemical vapor deposition of CH₄. During the growth, the substrate was heated by the plasma such that its temperature increased with the growth until equilibrium was reached. In other words, the CNT growth took place under simultaneously increased time and temperature. This has resulted in different growth kinetics from previously published studies. We have therefore examined the growth kinetics using an empirical function for CNTs grown on three different substrates and derived the relevant activation energies based on the empirical function.     

Fabrication of patterned carbon nanotube thin films using electrophoretic deposition and ultrasonic radiation

A simple wet-deposition method for preparing patterned carbon nanotube (CNT) thin films is reported. Using electrophoretic deposition (EPD), CNTs were deposited over indium tin oxide (ITO) plates that had been patterned with a photoresist; consequently, CNTs covered not only the exposed ITO areas but also the photoresist areas because thinness of the photoresists could not prevent the transverse deposition of CNTs over the photoresist areas. The ultrasonic treatment for the samples removed only CNTs on the photoresist areas, resulting in the formation of patterned CNT thin films, because Ni metal formed during EPD connects CNTs to ITO plates.     

Effect of gas phase oxidation on the structure and intertube adhesion force of a brush-like assembly of carbon nanotubes

Brush-like assemblies of carbon nanotubes produced using chemical vapor deposition were oxidized in stationary air in different oxidation conditions. Effects of oxidation on their structural properties were examined using microscopy and spectroscopy to evaluate changes in mass, CNT diameter, and the amount of disorder in samples. Separation force spectroscopy was also used, indicating a 50% increase in the adhesion force between CNTs in a mild oxidation regime, and indicating a sharp decrease in harsh oxidation conditions. By analyzing the relation between structural and chemical changes of CNT surfaces, we explored reasons for such trends in the forces interacting between CNTs.     

Carbon nanotubes/SiC whiskers composite prepared by CVD method

Selective growth of carbon nanotubes (CNTs) on silicon carbide (SiC) substrate will create some new applications in composites and electronic devices by combining their mechanical and physical properties. Multi-walled CNTs were successfully grown on SiC whiskers using a conventional xylene–ferrocene chemical vapor deposition process. A thin oxide layer was created on the surface of the SiC whiskers by high-temperature annealing in air before CNT growth. The effect of catalyst morphology and chemistry on the growth of CNTs was analyzed. Our technique may be further applied to the controlled growth of CNTs on any other SiC substrates.