Flow-dependent directional growth of carbon nanotube forests by chemical vapor deposition

We demonstrated that the structural formation of vertically aligned carbon nanotube (CNT) forests is primarily affected by the geometry-related gas flow, leading to the change of growth directions during the chemical vapor deposition (CVD) process. By varying the growing time, flow rate, and direction of the carrier gas, the structures and the formation mechanisms of the vertically aligned CNT forests were carefully investigated. The growth directions of CNTs are found to be highly dependent on the nonlinear local gas flows induced by microchannels. The angle of growth significantly changes with increasing gas flows perpendicular to the microchannel, while the parallel gas flow shows almost no effect. A computational fluid dynamics (CFD) model was employed to explain the flow-dependent growth of CNT forests, revealing that the variation of the local pressure induced by microchannels is an important parameter determining the directionality of the CNT growth. We expect that the present method and analyses would provide useful information to control the micro- and macrostructures of vertically aligned CNTs for various structural/electrical applications.     

Multi-walled carbon nanotube growth on oxidized silicon substrates using cyclohexane precursor by chemical vapor deposition

Randomly oriented multi-walled nanotubes (MWNTs) are grown by a thermal chemical vapor deposition (CVD) process from cyclohexane precursor on a 20% copper-80% nickel (Cu-Ni) catalyst on oxidized silicon substrates. This combination of precursor and catalyst, to our knowledge, has been employed for the first time to demonstrate growth of multi-walled carbon nanotubes. The effects of annealing, gas ambient and catalyst layer thickness on the morphology of the grown carbon layers are discussed. The low resistivity values of the MWNTs grown on oxidized silicon substrates are attractive for their potential use in photonic devices and display applications.     

Synthesis-condition dependence of carbon nanotube growth by alcohol catalytic chemical vapor deposition method

We report the dependence of growth yield of single-walled carbon nanotubes (SWNTs) on heat-treatment time and catalyst film thickness by the alcohol catalytic chemical vapor deposition method. Three types of heat-treatment, synthesis of 30 min, synthesis of 30 min after annealing of 30 min, and synthesis of 60 min, were investigated. Thickness of Co catalyst film was varied from 1 to 10 nm. In the case of thinner Co film less than 3 nm, long synthesis time of 60 min is favorable for the effective SWNT growth, because of the small amount of Co catalyst. In the case of thicker Co film more than 3 nm, an amount of grown SWNTs by 30 min synthesis after 30 min annealing and by 60 min synthesis was much higher than that by 30 min synthesis without annealing, showing that total heat-treatment time of 60 min is important for the SWNT growth. Results suggest that the conversion from the thicker film of Co to nano-particle which acts as catalyst takes place during the first 30 min.     

Synthesis-condition dependence of carbon nanotube growth by alcohol catalytic chemical vapor deposition method

We report the dependence of growth yield of single-walled carbon nanotubes (SWNTs) on heat-treatment time and catalyst film thickness by the alcohol catalytic chemical vapor deposition method. Three types of heat-treatment, synthesis of 30 min, synthesis of 30 min after annealing of 30 min, and synthesis of 60 min, were investigated. Thickness of Co catalyst film was varied from 1 to 10 nm. In the case of thinner Co film less than 3 nm, long synthesis time of 60 min is favorable for the effective SWNT growth, because of the small amount of Co catalyst. In the case of thicker Co film more than 3 nm, an amount of grown SWNTs by 30 min synthesis after 30 min annealing and by 60 min synthesis was much higher than that by 30 min synthesis without annealing, showing that total heat-treatment time of 60 min is important for the SWNT growth. Results suggest that the conversion from the thicker film of Co to nano-particle which acts as catalyst takes place during the first 30 min.     

Modeling of the carbon nanotube chemical vapor deposition process using methane and acetylene precursor gases

Chemical vapor deposition of carbon nanotubes (CNTs) in a horizontal tube-flow reactor has been investigated with a fully coupled reactor-scale computational model. The model combined conservation of mass, momentum, and energy equations with gas-phase and surface chemical reactions to describe the evolution of a hydrogen and hydrocarbon feed-stream as it underwent heating and reactions throughout the reactor. Investigation was directed toward steady state deposition onto iron nanoparticles via methane and hydrogen as well as feed-streams consisting of acetylene and hydrogen. The model determines gas-phase velocity, temperature, and concentration profiles as well as surface concentrations of adsorbed species and CNT growth rate along the entire length of the reactor. The results of this work determine deposition limiting regimes for growth via methane and acetylene, demonstrate the need to tune reactor wall temperature to specific inlet molar ratios to achieve optimal CNT growth, and demonstrate the large effect that active site specification can have on calculated growth rate.     

Laterally organized carbon nanotube arrays based on hot-filament chemical vapor deposition

Lateral porous anodic alumina (PAA) templates were used to organize carbon nanotubes (CNTs) grown by a hot-filament assisted chemical vapor deposition (HFCVD) process. For the CNT growth, we used a modified “home-made” HFCVD system with two independently powered filaments which are fitted respectively on the methane (CH₄) gas line, which serves as a carbon precursor and on the hydrogen (H₂) gas line, which acts as an etching agent for the parasitic amorphous carbon. Various activation powers of the hot filaments were used to directly or indirectly decompose the gas mixtures at relatively low substrate temperatures. A parametric study of the HFCVD process has been carried out for optimizing the confined CNTs growth inside the lateral PAA templates.     

Structure control of carbon nanotubes using radio-frequency plasma enhanced chemical vapor deposition

Carbon nanotube structures such as tube diameter, growth site, and formation density are controlled using radio-frequency (RF, 13.56 MHz) plasma enhanced chemical vapor deposition (RF-PECVD) method. We have produced uniformly well-aligned multi-walled carbon nanotubes (MWNTs) grown over the large scale area and linearly arrayed MWNTs grown in a selected area without any highly-sophisticated patterning process. In our RF-PECVD experiment, furthermore, individually grown single-walled carbon nanotubes (SWNTs) or their thin bundles are synthesized for the first time within the scope of the PECVD methods. These results indicate that PECVD method provides the high potential for the further development of nano-technology.     

Plasma-enhanced chemical vapor deposition of carbon films using dibromoadamantane

Carbon thin films are prepared from adamantane and dibromoadamantane by using a plasma-enhanced chemical vapor deposition method. Deposition rate for dibromoadamantane is approximately two times higher than that for pure adamantane. Infrared spectra of the films indicate that adamantane units are incorporated in the films, although higher electron temperature results in disorder in the films. The films prepared from dibromoadamantane have higher thermal stability, higher hardness and Young modulus than those from pure adamantane. Permittivity (= 3-4) of the dibromoadamantane films is higher than that (= 2-3) of pure adamantane films, which is regarded as a result of incorporation of bromine atoms and C=C bonds having higher polarizability according to the structural analysis of the films. Possible solution methods are proposed for reducing inclusion of such unfavorable chemical species and chemical bonds.     

Growth of ultra long multiwall carbon nanotube arrays by aerosol-assisted chemical vapor deposition

Using a home-made aerosol nebulizer, we developed a new aerosol-assisted chemical vapor deposition (AACVD) process that made it possible to synthesize vertically-aligned carbon nanotube (VACNT) arrays with heights over a few millimeters routinely. An essential part of this technique was in-situ formation of metal catalyst nanoparticles via pyrolysis of ferrocene-ethanol aerosol right before CNT synthesis. Through the optimization of aerosol supply and CVD process parameters, we were able to synthesize clean VACNT arrays as long as 4.38 mm with very low metal contents in 20 min. Furthermore, it is worthy noting that such an outstanding height is achieved very quickly without supporting materials and water-assistance. By taking advantage of almost complete inhibition of CNT growth on low melting-temperature metals, we were able to fabricate patterned VACNT arrays by combining AACVD process with a conventional photolithograpic patterning of gold lines. Characterizations of as-grown nanotubes such as morphology, purity, and metal contents are presented.     

The evolution of carbon nanotubes during their growth by plasma enhanced chemical vapor deposition

During the growth of carbon nanotubes (CNTs) by plasma enhanced chemical vapor deposition (PECVD), plasma etching is the crucial factor that determines the growth mode and alignment of the CNTs. Focusing on a thin catalyst coating (Ni = 5 nm), this study finds that the CNT growth by PECVD goes through three stages from randomly entangled (I-CNTs) to partially aligned (II-CNTs) to fully aligned (III-CNTs). The I-CNTs and II-CNTs are mostly etched away by the plasma as time goes by ending up with III-CNTs as the only product when growth time is long enough. However, with a thickness of the catalyst coating of 10 nm or more, neither I-CNTs nor II-CNTs are produced, but III-CNTs are the only type of CNTs grown during the whole growth process. During the growth of III-CNTs, the catalyst particles (Ni) stay on the tips of each of the aligned CNTs and act as a 'safety helmet' to protect the CNTs from plasma ion bombardment. On the other hand, it is also the plasma that limits the growth of III-CNTs, since the plasma eventually etches all the catalytic particles out and stops the growth.     

Optimizing reaction condition for synthesizing spinnable carbon nanotube arrays by chemical vapor deposition

Compared with the ordinary vertically aligned carbon nanotube (VACNT) arrays, the carbon nanotubes in spinnable VACNT arrays have better alignment, higher density, and narrower diameter distribution. The synthesis of spinnable VACNT arrays is sensitive to the reaction condition and the repeatable prepared of spinnable VACNT arrays still need improvement. In this paper, spinnable VACNT arrays were grown by chemical vapor deposition from C₂H₂/Ar using Fe coated on Si wafers as a catalyst. With the aim of improving the yield and reproducibility of spinnable VACNT arrays, the reaction conditions were systematically investigated. The growth kinetics of VACNT arrays was also investigated. The rate of growth of VACNT arrays can reach 465 μm/min at the initial growth stage and the activation energy of VACNT array growth is determined to be 112.2 kJ/mol. Meanwhile, a collective growth model for the evolution of spinnable VACNT arrays is also proposed.     

Catalytic chemical vapor deposition of carbon nanotubes using Ni-La-O precursors

Carbon nanotubes (CNT) are synthesized by catalytic chemical vapor deposition with different compositions of Ni-La-O catalyst precursors obtained by citric acid complexometry. Only two compounds: LaNiO₃ (perovskite-type crystal structure, hexagonal system) and La₂NiO₄ (spinel-type crystal structure, orthorhombic system) in the obtained Ni-La-O catalyst precursors have the ability to grow CNT. Moreover, CNT obtained with the two different crystal structure catalyst precursors have different characteristics: different yield, pattern and oxidation resistance performance.     

Synthesis of phosphorus doped carbon nanotubes using chemical vapor deposition

Phosphorous-doped carbon nanotubes (PCNTs) was prepared via two-step methodology employing chemical vapor deposition, by using available starting materials and catalyst. First, CNTs was produced from acetylene gas at 750 ºC and then, PCNTs have been prepared with total yield of 44% by recooking of the prepared CNT with Ph₃P at 600 ºC. The product was characterized with FESEM, TEM and EDS analyses, which confirmed its nanotube shape and the presence of phosphorous atom. The high thermal stability of the product was obtained from TGA analysis, showing only 16.5% weight loss up to 890 ºC. The Raman spectrum of the product showed the I_D/I_G ration equal to 0.84. Moreover, the catalytic potency of the product has been examined in ORR electrochemical reaction using CV and LSV diagrams. The results confirmed appropriate catalytic activity and high stability of the product for this process.     

A vapor-liquid-solid model for chemical vapor deposition growth of carbon nanotubes

Although carbon nanotubes (CNTs) with a variety of morphologies have been successfully synthesized, there is no clear physical picture of the growth process. Correspondingly, the growth mechanism is still not clear up to now. Here we suggest a VLS model for the growth process of CNTs, which involves a liquid or liquid-like state catalyst. The basic idea is that, due to the high thermal conductivity and nanometer size of the catalyst and the fast diffusion of carbon atoms in it, both the temperature and the carbon atom distribution across it are uniform. The supersaturation level can be expressed as a function of the carbon concentration and temperature, which determines the nucleation dynamics and growth kinetics. Based on this model, the growth rate equation was obtained to describe the growth kinetics of carbon nanotubes, which shows good accordance with the experimental results.     

Electrical properties of carbon nanotube thin-film transistors fabricated using plasma-enhanced chemical vapor deposition measured by scanning probe microscopy

The electrical properties of carbon nanotube thin-film transistors (CNT-FETs) fabricated using plasma-enhanced chemical vapor deposition (PECVD) were studied by scanning probe microscopy. The measured results suggest the formation of an island structure in the subthreshold regime and the disappearance of the island structure at the ON state. These results were explained by the change in the effective number of CNTs that contributed to the electrical conduction due to the gate-bias-dependent resistance of the semiconducting CNTs. The results obtained by Monte Carlo simulation revealed similar results. The effects of metallic CNTs with defects and the scatter of the drain current in the subthreshold regime were also examined.     

Growth control of carbon nanotubes by plasma enhanced chemical vapor deposition

Plasma enhanced chemical vapor deposition (PECVD), which enables growth of vertically aligned carbon nanotubes (CNTs) directly onto a solid substrate, is considered to be a suitable method for preparing CNTs for nanoelectronics applications such as electron sources for field emission displays (FEDs). For these purposes, establishment of an efficient CNT growth process has been required. We have examined growth characteristics of CNTs using a radio frequency PECVD (RF-PECVD) method with the intention to develop a high efficiency process for CNT growth at a low enough temperature suitable for nanoelectronics applications. Here we report an effect of pretreatment of the catalyst thin film that plays an important role in CNT growth using RF-PECVD. Results of this study show that uniform formation of fine catalyst nanoparticles on the substrate is important for the efficient CNT growth.     

Hot-wire chemical vapor deposition of carbon nanotubes

Hot-wire chemical vapor deposition (HWCVD) has been employed for the continuous gas-phase generation of both carbon multi-wall and single-wall nanotube (MWNT and SWNT) materials. Graphitic MWNTs were produced at a very high density at a synthesis temperature of 600 °C. SWNTs were deposited at a much lower density on a glass substrate held at 450 °C. SWNTs are typically observed in large bundles that are stabilized by tube–tube van der Waals’ interactions. However, transmission electron microscopy analyses revealed only the presence of isolated SWNTs in these HWCVD-generated materials.     

Optimization of the chemical vapor deposition process for fabrication of carbon nanotube/Al composite powders

In order to optimize the chemical vapor deposition process for fabrication of carbon nanotube/Al composite powders, the effect of different reaction conditions (such as reaction temperature, reaction time, and reaction gas ratio) on the morphological and structural development of the powder and dispersion of CNTs in Al powder was investigated using transmission electron microscope. The results showed that low temperatures (500-550 °C) give rise to herringbone-type carbon nanofibers and high temperatures (600-630 °C) lead to multi-walled CNTs. Long reaction times broaden the CNT size distribution and increase the CNT yield. Appropriate nitrogen flow is preferred for CNT growth, but high and low nitrogen flow result in carbon nanospheres and CNTs with coarse surfaces, respectively. Above results show that appropriate parameters are effective in dispersing the nanotubes in the Al powder which simultaneously protects the nanotubes from damage.     

Patterned arrays of vertically aligned carbon nanotube microelectrodes on carbon films prepared by thermal chemical vapor deposition

A straightforward procedure is described for preparation of arrays of microdisk electrodes comprising bundles of vertically aligned carbon nanotubes (VACNTs). The arrays are fabricated by thermal chemical vapor deposition synthesis directly on a planar carbon film support. Use of standard micro- and nanolithography procedures for patterning the bilayer catalyst spots enables arrays to be grown with controlled electrode diameters and spacings. The minimum accessible VACNT bundle diameter, and hence microelectrode diameter, is 2 microm. After insulating the arrays with SU-8 epoxy and exposing the VACNT ends by polishing or treating with O2 plasma, the microdisk electrodes exhibit attractive electrochemical properties.     

Surface morphology and preferential orientation growth of TaC crystals formed by chemical vapor deposition

TaC film was deposited on (002) graphite sheet by isothermal chemical vapor deposition using TaCl₅-Ar-C₃H₆ mixtures, with deposition temperature 1200 °C and pressure about 200 Pa. The influence of deposition position (or deposition rate) on preferential orientation and surface morphology of TaC crystals were investigated by X-ray diffraction and scanning electron microscopy methods. The deposits are TaC plus trace of C. The crystals are large individual columns with pyramidal-shape at deposition rate of 32.4-37.3 μm/h, complex columnar at 37.3-45.6 μm/h, lenticular-like at 45.6-54.6 μm/h and cauliflower-like at 54.6-77.3 μm/h, with <001>, near <001>, <110> and no clear preferential orientation, respectively. These results agree in part with the preditions of the Pangarov's model of the relationship between deposition rate and preferential growth orientation. The growth mechanism of TaC crystals in <001>, near <001>, <111> and no clear preferential orientation can be fairly explained by the growth parameter α with Van der Drift's model, deterioration model and Meakin model. Furthermore, a nucleation and coalescence model is also proposed to explain the formation mechanism of <110> lenticular-like crystals.