Synthesis of vertically aligned, double-walled carbon nanotubes from highly active Fe-V-O nanoparticles

Monodispersed Fe-V-O nanoparticles were prepared by a liquid-phase synthesis to be used as catalysts for carbon nanotube (CNT) growth. Vertically aligned, dense CNTs have been grown from the highly active Fe-V-O nanoparticles by chemical vapor deposition. Diameter distribution of CNTs (3.7 ± 0.6 nm) was consistent with that of the original nanoparticles (3.1 ± 0.5 nm), and the value was smaller than those of other reported vertically aligned CNTs from as-prepared nanoparticles. TEM study showed that the CNTs consisted mainly of double-walled CNTs (single: 14%, double: 74%, and triple: 12%). The CNT diameter increased to 4.4 ± 0.8 nm as the growth temperature was increased from 810 to 870 °C. Energy dispersive X-ray spectroscopy of nanoparticles before and after the CNT growth revealed that the V content decreased from 7.2 to 2.7 at.%, suggesting that the segregation of Fe and V played an important role for the high activity of the Fe-V-O nanoparticles.     

Carbon Nanotube Growth on Calcium Carbonate Supported Molybdenum-Transition Bimetal Catalysts

A comparison of different catalyst systems (Fe–Mo, Co–Mo or Ni–Mo nanoparticles supported on calcium carbonate) has been performed in order to optimize the carbon nanotube (CNT) growth. The influences of the reaction temperature, metal loading and carbon source on the synthesis of CNTs were investigated. Dense CNT networks have been synthesized by thermal chemical vapor deposition (CVD) of acetylene at 720 °C using the Co–Mo/CaCO₃ catalyst. The dependence of the CNT growth on the most important parameters was discussed exemplarily on the Co catalyst system. Based on the experimental observations, a phenomenological growth model for CVD synthesis of CNTs was proposed. The synergy effect of Mo and active metals was also discussed.     

Multiple “optimum” conditions for Co-Mo catalyzed growth of vertically aligned single-walled carbon nanotube forests

Carbon nanotubes (CNTs) were grown directly on substrates by alcohol catalytic chemical vapor deposition using a Co-Mo binary catalyst. Optimum catalytic and reaction conditions were investigated using a combinatorial catalyst library. High catalytic activity areas on the substrate were identified by mapping the CNT yield against the orthogonal gradient thickness profiles of Co and Mo. The location of these areas shifted with changes in reaction temperature, ethanol pressure and ethanol flow rate. Vertically aligned single-walled CNT (SWCNT) forests grew in several areas to a maximum height of ca. 30 μm in 10 min. A pure Co catalyst yielded a vertically aligned SWCNT forest with a bimodal diameter distribution. The effects of Mo on the formation of catalyst nanoparticles and on the diameter distribution of SWCNTs are discussed and Mo as thin as a monolayer or thinner was found to suppress the broadening of SWCNT diameter distributions.     

Easy synthesis of a nanostructured hybrid array consisting of gold nanoparticles and carbon nanotubes

A nanostructured hybrid consisting of a high-density and uniform assembly of gold nanoparticles (AuNPs) on carbon nanotubes (CNTs) was prepared using easy methods. The pyrolysis of iron(II) phthalocyanine (FePc) on a Si substrate under an atmosphere of hydrogen/argon was used to produce multiwalled carbon nanotubes (MWCNTs) with 12 nm in diameter and 4 μm in length. Then, Au nanocolloid solution, which contained dodecanethiol-capped Au nanoparticles synthesized by solution chemical method, was deposited on the synthesized CNT array and heated at 300 °C for 1 h under Ar. The synthesis temperature of CNT governs the AuNP-CNT hybrid structure and surface nitrogen concentration from decomposition of FePC. CNTs synthesized at 800 °C exhibit the finest particle size and most homogeneous dispersity of assembled AuNPs in comparison to hybrids whose CNTs are synthesized at other temperatures. These features are considered to correlate with the surface nature of the grown CNT; good dispersity of AuNPs on CNT results from interaction between the thiolate molecules capped on the AuNPs and the N atoms doped into the grown CNT. Assembling AuNPs to CNT contributes the electrical conductivity enhancement of the CNT hybrid array.     

Kinetic study of carbon nanotube synthesis over Mo/Co/MgO catalysts

The kinetics of carbon nanotube (CNT) synthesis by decomposition of CH₄ over Mo/Co/MgO and Co/MgO catalysts was studied to clarify the role of catalyst component. In the absence of the Mo component, Co/MgO catalysts are active in the synthesis of thick CNT (outer diameter of 7-27 nm) at lower reaction temperatures, 823-923 K, but no CNTs of thin outer diameter are produced. Co/MgO catalysts are significantly deactivated by carbon deposition at temperatures above 923 K. For Mo-including catalysts (Mo/Co/MgO), thin CNT (2-5 walls) formation starts at above 1000 K without deactivation. The significant effects of the addition of Mo are ascribed to the reduction in catalytic activity for dissociation of CH₄, as well as to the formation of Mo₂C during CNT synthesis at high temperatures. On both Co/MgO and Mo/Co/MgO catalysts, the rate of CNT synthesis is proportional to the CH₄ pressure, indicating that the dissociation of CH₄ is the rate-determining step for a catalyst working without deactivation. The deactivation of catalysts by carbon deposition takes place kinetically when the formation rate of the graphene network is smaller than the carbon deposition rate by decomposition of CH₄.     

Controlling the diameter distribution of carbon nanotubes grown from camphor on a zeolite support

Single-wall and multi-wall carbon nanotubes (SWNTs and MWNTs, respectively) of controlled diameter distribution were selectively grown by thermal decomposition of a botanical hydrocarbon, camphor, on a high-silica zeolite support impregnated with Fe-Co catalyst. Effects of catalyst concentration, growth temperature and camphor vapor pressure were investigated in wide ranges, and diameter distribution statistics of as-grown nanotubes was analyzed. High yields of metal-free MWNTs of fairly uniform diameter (∼10 nm) were grown at 600-700 °C, whereas significant amounts (∼30%) of SWNTs were formed at 850-900 °C within a narrow diameter range of 0.86-1.23 nm. Transmission electron microscopy and micro-Raman spectroscopy reveal that camphor-grown nanotubes are highly graphitized as compared to those grown from conventional CNT precursors used in chemical vapor deposition.     

Growth of self-aligned carbon nanotube for use as a field-effect transistor using cobalt silicide as a catalyst

The growth of carbon nanotube (CNT) using cobalt silicide as a catalyst and source/drain electrode is proposed to explore its feasibility for fabricating integrated-circuit process compatible, self-aligned CNT field-effect transistors (CNTFET). The silicide nanoparticles formed in the Ti/Co/poly-Si source/drain stack were used as a catalyst for CNT growth. Results show that single-walled CNTs have been synthesized between pre-defined catalytic cobalt silicide source/drain pairs by chemical vapor deposition at 800-900 °C. Preliminary transistor characteristics of the CNTFETs have also been achieved.     

Fabrication of CNTs with controlled diameters and their applications as electrocatalyst supports for DMFC

A facile synthesis procedure based on chemical vapor deposition (CVD) process has been developed to fabricate carbon nanotubes (CNTs) with controlled diameters and high yields utilizing Fe-containing ordered hexagonal mesoporous silicas (HMSs) such as MCM-41 and SBA-15 having varied pore sizes as the catalysts as well as the templates. It is found that unlike Fe/HMS catalysts prepared by co-precipitation method, samples prepared by the impregnation method gave rise to multi-wall CNTs with uniform diameters, which were largely dictated by the pore size of the Fe/HMS catalysts. Among these uniform MWCNTs, sample with a larger diameter (≥ 8 nm) was found to be more favorable as support for Pt catalyst, leading to a homogeneous dispersion of metal nanoparticles. Consequently, the Pt/CNT electrocatalysts so prepared gave rise to superior methanol oxidation activities as well as tolerances for CO poisoning compared to Pt supported on commercial single-wall CNT (Pt/SWCNT) and XC-72 activated carbon (Pt/XC-72) having a similar metal loading.     

Growth of high-quality carbon nanotubes on free-standing diamond substrates

Carbon nanotubes (CNTs) were grown on diamond-coated Si substrates and free-standing diamond wafers to develop efficient thermal interface materials for thermal management applications. High-quality, translucent, free-standing diamond substrates were processed in a 5 kW microwave plasma chemical vapor deposition (CVD) system using CH₄ as precursor. Ni and Ni-9%W-1.5%Fe catalyst islands were deposited to nucleate CNTs directly onto the diamond substrates. Randomly-oriented multi-walled CNTs forming a mat of ∼5 μm thickness and consisting of ∼20 nm diameter tubes were observed to grow in a thermal CVD system using C₂H₂ as precursor. Transmission electron microscopy and Raman analyses confirmed the presence of high-quality CNTs on diamond showing a D/G peak ratio of 0.2-0.3 in Raman spectra.     

Growth evolution of rapid grown aligned carbon nanotube forests without water vapor on Fe/Al2O3/SiO2/Si substrate

This paper presents the growth evolutions in terms of the structure, growth direction and density of rapid grown carbon nanotube (CNT) forests observed by scanning and transmission electron microcopies (SEM/TEM). A thermal CVD system at around 700 °C was used with a catalyst of Fe films deposited on thin alumina (Al₂O₃) supporting layers, a very fast raising time to the growth temperature below 25 °C/s, and a carbon source gas of acetylene diluted with hydrogen and nitrogen without water vapor. Activity of Fe catalyst nanoparticles was maintained for 5 min during CVD process, and it results in CNT forests with heights up to 0.6 mm. SEM images suggest that the disorder in CNT alignment at the initial stage of CNTs plays a critical role in the formation of continuous CNT growth. Also, the prolonged heating process leads to increased disorder in CNT alignment that may be due to the oxidation process occurring at the Fe nanoparticles. TEM images revealed that both double- and few-walled CNTs with diameters of 5-7 nm were obtained and the CNT density was controlled by thickness of Fe catalytic layer. The number of experiments at the same conditions showed a very good repeatability and reproducibility of rapid grown CNT forests.     

Synthesis of nitrogen-doped horn-shaped carbon nanotubes by reduction of pentachloropyridine with metallic sodium

Nitrogen-doped horn-shaped carbon nanotubes (CNTs) have successfully been prepared by reducing pentachloropyridine with metallic sodium at 350 °C. A typical CNT has an open-end diameter of ∼2 μm, a close-end diameter of ∼0.3 μm, a wall thickness of ∼30 nm, and a length up to 8 μm. TEM observation indicates that the CNTs account for ∼30% of the products, and the rest is solid and hollow carbon nanospheres (CNSs) with a diameter of about 50-290 nm. Elemental analysis shows that the N/C atomic ratio of the carbon nanostructures is about 0.0208. XRD and HRTEM measurements reveal that the CNTs are amorphous. To understand the growth process and refine the growth condition, various control experiments have been finished. At last, a sodium-catalysis-reduction solid-liquid-solid growth mechanism of the CNTs has been suggested on the basis of the experiments.     

Viscoelasticity and high buckling stress of dense carbon nanotube brushes

We report on the mechanical behavior of a dense brush of small-diameter (1-3 nm) non-catalytic multiwall (2-4 walls) carbon nanotubes (CNTs), with ∼10 times higher density than CNT brushes produced by other methods. Under compression with spherical indenters of different radii, these highly dense CNT brushes exhibit a higher modulus (∼17-20 GPa) and orders of magnitude higher resistance to buckling than vapor phase deposited CNT brushes or carbon walls. We also demonstrate the viscoelastic behavior, caused by the increased influence of the van der Waals’ forces in these highly dense CNT brushes, showing their promise for energy-absorbing coatings.     

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.     

Synthesis of patterned carbon nanotube arrays for field emission using a two layer Sn/Ni catalyst in an ethanol flame

Patterned carbon nanotube (CNT) arrays on Si substrate have been fabricated by using a two layer Sn/Ni catalyst in a diffusion ethanol flame. Vertically well-aligned CNT arrays were achieved on a Si substrate without any catalyst pretreatment. The Sn underlayer activated the substrates for CNT growth with Ni as catalyst, and provided a good contact between CNTs and the substrate, which is useful for field emission. Since the adhesion of Sn/Ni nanoparticles to the substrate is very strong, the growth of the CNTs follows a base-growth mode. The thickness of the Sn underlayer largely determines the diameter and diameter distribution of the as-grown CNTs. The morphologies and field electron emission properties of CNT arrays grown on Si substrates with different thicknesses of Sn and growth times have been investigated. The variation of emission current density was less than 5% during a 4 h test under a field of 1.77 V/µm.     

Optimization of water assisted chemical vapor deposition parameters for super growth of carbon nanotubes

The optimization of water assisted chemical vapor deposition (WA-CVD) was carried out to synthesize ultra long, vertically aligned, densely packed carbon nanotube (CNT) forests. The effect of various WA-CVD parameters (viz. the flow rate of the reactant gas mixture and its injection temperature, growth kinetics, ramp rate and growth temperature) on the height of the CNTs was studied. A hypothesis for catalytic activity is proposed on the basis of the X-ray photoelectron spectroscopic analysis of the CNT grown substrates and further verified at the optimum condition. The effect of temperature on the growth of the CNTs is studied. The gas flow rate and injection temperature influence the onset of oxidation of the substrates, which in turn affects the CNT growth rate. A growth kinetics study is performed in order to monitor the growth temperature. The role of the onset of oxidation of the iron catalyst in the growth of the CNTs is studied by varying the ramp rate. The precise CNT growth temperature for WA-CVD is determined by growth temperature studies. The optimum condition allows ∼2.2 ± 0.002 mm long CNTs to be obtained.     

Controllable deposition of Ag nanoparticles on carbon nanotubes as a catalyst for hydrazine oxidation

A simple method is devised to deposit highly monodispersed Ag nanoparticles (about 5 nm) on multi-walled carbon nanotubes (CNTs), which started from an initial modification of Ag nanoparticles with benzyl mercaptan molecules. By simply tuning the relative ratio of Ag catalyst to CNTs in solution, Ag/CNT composite with different Ag content can be achieved. The as-prepared Ag/CNT composite materials showed high electrocatalytic activity towards hydrazine oxidation, which was ascribed to the high dispersion of Ag nanoparticles on CNT surface.     

Thin-walled carbon nanotubes grown using a zirconium catalyst

Thin-walled carbon nanotubes (TWCNTs) were synthesized using a zirconium (Zr) plate by cold-wall chemical vapor deposition of a mixture gas consisting of C₂H₂ and H₂ under a pressure of 1.20 torr. The Zr plate was used for the formation of Zr nanocatalysts during the thermal process and used as substrate to eliminate the effects of interactions between catalyst and substrate during CNT synthesis. The TWCNTs were 4-9 nm in diameter and a few micrometers long. Nanometer-sized defects on the Zr bulk material may have a low melting temperature, allowing them to form droplet-like catalysts and achieve high carbon solubility for the formation of CNTs.     

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.     

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.     

Impact of nanometal catalysts on the laser vaporization synthesis of single wall carbon nanotubes

The effects of catalyst particle size on the purity, yield, and purification efficiency of single wall carbon nanotubes (SWCNTs) synthesized via pulsed laser vaporization were investigated. The purity of as-produced SWCNT material synthesized using Ni and Co nanometal (∼13 nm diameter) catalyst particles was compared to material synthesized using conventional micronmetal (2-3 μm diameter) particles. The SWCNT material from nanometal catalysts demonstrated a 50% increase in SWCNT purity as assessed by optical absorption spectroscopy and thermogravimetric analysis (TGA). A change in the thermal oxidation properties was also observed with the nanometal-SWCNTs exhibiting a suppression of the exothermic oxidation of post-synthesis catalyst. Statistical analysis of the TGA residue yielded mean post-synthesis catalyst particle diameters of 18 ± 6 nm and 3 ± 1 nm for the micronmetal and nanometal produced material, respectively. When a thermal oxidation profile was performed, the micronmetal-produced material showed the typical decrease in SWCNT purity with increasing oxidation temperature while the nanometal-produced material showed increasing SWCNT purity with increasing temperature. Overall, the use of nanometal catalysts significantly increases synthesis yield and offers novel thermal oxidation procedures to thermally remove carbonaceous impurities without the aid of acid treatments for the development of potential large-scale purification processing.