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.     

High-yield growth and morphology control of aligned carbon nanotubes on ceramic fibers for multifunctional enhancement of structural composites

We present an in-depth study of CNT growth on commercially-available woven alumina fibers, and achieve uniform growth of dense aligned CNTs on commercially-available cloths up to 5 × 10 cm in area. By systematically varying the catalyst concentration, catalyst pre-treatment time, and sample position within the tube furnace, we isolate key factors governing CNT morphology on fiber surfaces and classify these morphologies as related to the processing conditions. Synthesis employs a low-cost salt-based catalyst solution and atmospheric pressure thermal CVD, which are highly attractive approaches for commercial-scale processing. The catalyst solution concentration determines the uniformity and density of catalyst on the fibers, H₂ exposure mediates formation of catalyst clusters, and thermal decomposition of the reactant mixture activates the catalyst particles to achieve uniform aligned growth. Under conditions for aligned CNT growth, uniform radially-aligned coatings are achieved with shorter CNT length, and these split into “mohawks” as the CNT length increases. Radially-aligned growth for 5 min adds a typical CNT mass fraction of 3.8% to the initial sample mass, and a uniform morphology exists throughout the weave. Composites prepared by standard layup techniques using these CNT “fuzzy” alumina fibers are attractive as integral armor layers having enhanced ballistic and impact performance, and serve as a model system for later implementation of this technology using carbon fibers.     

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.     

Growth of conformal single-walled carbon nanotube films from Mo/Fe/Al2O3 deposited by electron beam evaporation

We discuss growth of high-quality carbon nanotube (CNT) films on bare and microstructured silicon substrates by atmospheric pressure thermal chemical vapor deposition (CVD), from a Mo/Fe/Al₂O₃ catalyst film deposited by entirely electron beam evaporation. High-density films having a tangled morphology and a Raman G/D ratio of at least 20 are grown over a temperature range of 750-900 °C. H₂ is necessary for CNT growth from this catalyst in a CH₄ environment, and at 875 °C the highest yield is obtained from a mixture of 10%/90% H₂/CH₄. We demonstrate for the first time that physical deposition of the catalyst film enables growth of uniform and conformal CNT films on a variety of silicon microstructures, including vertical sidewalls fabricated by reactive ion etching and angled surfaces fabricated by anisotropic wet etching. Our results confirm that adding Mo to Fe promotes high-yield SWNT growth in H₂/CH₄; however, Mo/Fe/Al₂O₃ gives poor-quality multi-walled CNTs (MWNTs) in H₂/C₂H₄. An exceptional yield of vertically-aligned MWNTs grows from only Fe/Al₂O₃ in H₂/C₂H₄. These results emphasize the synergy between the catalyst and gas activity in determining the morphology, yield, and quality of CNTs grown by CVD, and enable direct growth of CNT films in micromachined systems for a variety of applications.     

Growth and characterization of vertically aligned centimeter long CNT arrays

Record-long (21.7 mm) vertically aligned MWNT arrays were synthesized using water-assisted thermal CVD process. The catalyst lifetime was maintained for 790 min at optimized experimental condition. The growth of the centimeter long CNT was observed by real time photography at different growth conditions. The growth length increased linearly with increasing growth time followed by a sudden growth end. The ratio of ethylene and H₂ concentration as well as the water and ethylene concentration was studied and optimized which led to prolong catalyst lifetime. Transmission electron microscope images confirmed that most CNTs were double wall and the number of wall distribution was uniform along different height position. Raman spectra showed that the I_D/I_G ratio remained constant at the 3 studied positions along the CNT. TGA demonstrated negligible impurity incorporation in the CNT array.     

The formation mechanisms of multi-wall carbon nanotubes over the Ni modified MCM-41 catalysts

Multi-wall carbon nanotubes (MWCNTs) were grown by thermal chemical vapor deposition (thermal CVD) of CH₄ by using Ni-MCM-41 as the catalyst. Methane pyrolysis has been performed in a quartz tube reactor over the catalyst surface to form carbon atoms via dehydrogenation process. The migration and rearrangement of the surface carbon atoms result in the formation of MWCNTs. Transmission electron microscope (TEM) and scanning electron microscope (SEM) were used to determine the morphologies and structures of CNTs, and Raman spectroscopy was exploited to analyze their purity with the relative intensity between the D-band (Disorder band) in the vicinity of 1,350 cm⁻¹ which is characteristic of the sp³ structure and G-band (Graphitic band) in vicinity of 1,580 cm⁻¹ which is characteristic of the sp² structure. In addition, the controlling factors of methane pyrolysis such as the catalyst composition; the reaction temperature, and the methane flow rate on the formation of MWCNTs were investigated to optimize the structure and yield of MWCNTs. SEM/TEM results indicate that the yield of the CNTs increases with increasing Ni concentration in the catalyst. The optimized reaction temperature to grow CNT is located between 640 and 670 °C. The uniform and narrow diameter MWCNTs form at lower flow rate of methane (∼30 sccm), and non-uniform in diameter and disorder structure of MWCNTs are observed at higher flow rate of methane. This is consistent with Raman analysis that the relative intensity of I _D/I _G increases with increasing methane flow rate. The formation mechanisms of the MWCNTs on the Ni-MCM-41 catalyst have been determined to be a Tip-Growth mode with a nanoscale catalyst particle capsulated in the tip of the CNT.     

Effects of hydrogen on carbon nanotube formation in CH4/H2 plasmas

Carbon nanotubes (CNTs) were synthesized using CH₄/H₂ plasmas and plasmas simulated using a one-dimensional fluid model. The thinnest and longest CNTs with the highest number density were obtained using CH₄/H₂ = 27/3 sccm at 10 Torr. These conditions allowed CNTs to grow for 90 min without any meaningful loss of catalyst activity. However, an excess H₂ supply to the CH₄/H₂ mixture plasma made the diameter distribution of the CNTs wider and the yield lower. Hydrogen concentration is considered to affect catalyst particle size and activity during the time interval before starting CNT growth (=incubation period). With CH₄/H₂ = 27/3 sccm for a growth time of 10 min efficient CNT growth was achieved because the amount of carbon atoms in the CNTs and that calculated from simulation showed good agreement. The effect of hydrogen etching on CNTs was analyzed by scanning electron microscopy and X-ray photoelectron spectroscopy by observing CNTs treated by H₂ plasma after CNT growth. It was confirmed that (a) multi-walled CNTs were not etched by the H₂ plasma, (b) the C 1s XPS spectra of the CNTs showed no chemical shift after the treatment, and (c) C-H bonds were produced in CNTs during their growth.     

Purity-controllable growth of bamboo-like multi-walled carbon nanotubes over copper-based catalysts

The growth of bamboo-like multi-walled carbon nanotubes (CNTs) without the formation of amorphous carbons was performed using copper-based catalysts by catalytic chemical vapour deposition (CVD) with diluted ethylene at 700–900 °C. The as-grown CNT soot was characterised by transmission electron microscopy, thermogravimetric analysis and Raman spectroscopy. The weak metal–support interaction of a sulphate-assisted copper catalyst (CuSO₄/SiO₂) can provide high-purity growth with remarkable yields of CNTs (2.24–6.10 CNT/g Cu·h) at 850–900 °C. Additionally, hydrogen-assisted CVD can activate inert copper catalysts, e.g., Cu(NO₃)₂/SiO₂ or Cu(CH₃COO)_2/SiO₂, for the growth of CNTs.     

Co-Mo catalyzed growth of multi-wall carbon nanotubes from CO decomposition

We investigated the growth of multi-wall carbon nanotubes (CNTs) catalyzed by SiO₂-supported Co-Mo bi-metallic catalyst in flowing CO at 700 °C. We found that both Co and Mo are present in catalytic particles at the tips of CNTs, but their compositions vary from one catalytic particle to another and significantly deviate from the initial mixing composition. The Co concentration and distribution in the catalytic particle of a CNT largely determines the length of the CNT. The CNT growth process is carbon adsorption on exposed area of a catalytic particle and subsequent precipitation at the CNT-catalyst interface or open CNT wall edges. The encapsulation of a catalytic particle was found to occur by the growth of the open-edged graphene walls around the particle. Two types of long CNTs were observed: one with their CNT walls ended at the CNT-particle interface, and the other with their CNT walls open to the environment. The former have diameters similar to their catalytic particle size while the latter have larger diameters.     

Influence of Ni Catalyst Layer and TiN Diffusion Barrier on Carbon Nanotube Growth Rate

Dense, vertically aligned multiwall carbon nanotubes were synthesized on TiN electrode layers for infrared sensing applications. Microwave plasma-enhanced chemical vapor deposition and Ni catalyst were used for the nanotubes synthesis. The resultant nanotubes were characterized by SEM, AFM, and TEM. Since the length of the nanotubes influences sensor characteristics, we study in details the effects of changing Ni and TiN thickness on the physical properties of the nanotubes. In this paper, we report the observation of a threshold Ni thickness of about 4 nm, when the average CNT growth rate switches from an increasing to a decreasing function of increasing Ni thickness, for a process temperature of 700°C. This behavior is likely related to a transition in the growth mode from a predominantly “base growth” to that of a “tip growth.” For Ni layer greater than 9 nm the growth rate, as well as the CNT diameter, variations become insignificant. We have also observed that a TiN barrier layer appears to favor the growth of thinner CNTs compared to a SiO₂ layer.     

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 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.     

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.     

Direct growth of carbon nanotubes on carbon fibers: Effect of the CVD parameters on the degradation of mechanical properties of carbon fibers

Grafting carbon nanotubes (CNTs) directly on carbon fibers represents a promising approach in order to strengthen the weak interface between carbon fibers and polymer matrix in carbon fiber reinforced polymer composites (CFRCs). We have carried out direct growth of CNTs on carbon fibers by using two different catalytic chemical vapor deposition (CVD) processes, namely the conventional CVD process based on catalytic thermal decomposition of ethylene and the oxidative dehydrogenation reaction between acetylene and carbon dioxide. The effect of various CVD growth parameters, such as temperature, catalyst composition and process gas mixture, was for the first time systematically studied for both processes and correlated with the mechanical properties of carbon fibers derived from single-fiber tensile tests. The growth temperature was found to be the most critical parameter in the presence of catalyst particles and reactive gasses for both processes. The oxidative dehydrogenation reaction enabled decreasing CNT growth temperature as low as 500 °C and succeeded to grow CNTs without degradation of carbon fiber's mechanical properties. The Weibull modulus even increased indicating partial healing of present defects during the CVD process. The new insights gained in this study open a way towards simple, highly reproducible and up-scalable process of grafting CNTs on carbon fibers without inducing any damages during the CVD process. This represents an important step towards CNT-reinforced CFRCs with higher damage resistance.     

Thermal and mechanical properties of carbon nanotube/epoxy nanocomposites reinforced with pristine and functionalized multiwalled carbon nanotubes

In this study, the effects of functionalization and weight fraction of mutliwalled carbon nanotubes (CNTs) were investigated on mechanical and thermomechanical properties of CNT/Epoxy composite. Epoxy resin was used as matrix material with pristine‐, COOH‐, and NH₂‐functionalized CNTs as reinforcements in weight fractions of 0.1, 0.5, and 1.0%. Varying (increasing) the weight fraction and changing type (pristine or functionalized) of CNTs caused increment in Young's modulus and tensile strength as observed during mechanical tests. CNT reinforcement improved thermal stability of the nanocomposites as observed by thermogravimetric analysis. Thermomechanical analysis showed a slight reduction in free volume of the polymer, that is a drop in coefficient of thermal expansion, prior to glass transition temperature (T_g) beside a slight increase in T_g value. Dynamic mechanical analysis indicated an increase in storage modulus and T_g owing to the strength addition of CNT to the matrix alongside the hardener. Scanning electron microscopy analysis of the fractured surface(s) revealed that CNTs were well dispersed with no agglomeration and resulted in reinforcing the matrix. POLYM. COMPOS., 36:1891–1898, 2015. © 2014 Society of Plastics Engineers     

Important parameters for the catalytic nanoparticles formation towards the growth of carbon nanotube aligned arrays

Presented here is a systematic study on the experimental parameters involved in the formation of catalytic nanoparticles from homogeneous Ni films deposited by dc sputtering towards carbon nanotube (CNT) production on Si/SiO₂. We have found a critical temperature and time for the thermal and reduction pre-treatment processes to obtain catalyst nanoparticles with the appropriate size and high density suitable for CNT growth. From such nanoparticles, densely-packed aligned CNT arrays were successfully grown at 750–800°C by thermal CVD.     

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.     

Characteristics of carbon nanotubes grown by mesh-inserted plasma-enhanced chemical vapor deposition

Plasma-enhanced chemical vapor deposition (CVD) has the advantages of low temperature and vertical growth in synthesizing carbon nanotubes (CNTs), but has generally produced stubby CNTs, probably due to an ion bombardment effect. To suppress the ion bombardment, a metal mesh with the same electrical potential as that of the cathode was placed just above the substrate on the cathode. The anode was electrically grounded while the cathode and the mesh were both negatively biased, causing no plasma to occur below the mesh. The substrate was therefore separated from the plasma by the mesh so that the ion bombardment was suppressed. CNTs were grown on a 2 nm-thick Invar catalyst with different DC plasma powers of 0–112 W at 500 °C, 3.3 torr for 10 min, using C₂H₂ (28 sccm) and NH₃ (172 sccm). Compared to CNTs grown with no mesh, these CNTs showed smaller diameters and greater lengths. As the plasma power decreased, the CNTs grown with mesh were thinner and longer and resembled those grown at a higher temperature by thermal CVD. Etching these CNTs by N₂ plasma reduced their population density and considerably improved their field emission characteristics.     

Scaled-up self-assembly of carbon nanotubes inside long stainless steel tubing

The self-assembly of carbon nanotubes (CNTs) on the inside wall of a relatively long stainless steel tubing for applications such as separations and chromatography, is reported in this paper. The CNTs were deposited by the chemical vapor deposition (CVD) using ethylene as the carbon source and the iron nanostructures in the stainless steel as the catalyst. The coating consisted of a layer of CNTs aligned perpendicular to the circumference of the tubes, often with an overcoat of disordered carbonaceous material, which could be selectively oxidized by exposing the CNT layer below to pure O₂ at 375 °C. Variation in uniformity in terms of the thickness and morphology of the deposited film and surface coverage were studied along the length of a tube by scanning electron microscopy (SEM). The effects of process conditions, such as flow rate and deposition time on the coating thickness, were studied. The catalytic effect of the iron nanostructures depended on surface conditioning of the tubing. It was found that the pretreatment temperature influenced the quality of the nanotube coating. The morphology of the CNT deposit supported the base-growth scheme and VLS (vapor-liquid-solid) growth mechanisms of CNTs.     

Precursor gas chemistry determines the crystallinity of carbon nanotubes synthesized at low temperature

Despite significant progress in carbon nanotube (CNT) synthesis by thermal chemical vapor deposition (CVD), the factors determining the structure of the resulting carbon filaments and other graphitic nanocarbons are not well understood. Here, we demonstrate that gas chemistry influences the crystal structure of carbon filaments grown at low temperatures (500 °C). Using thermal CVD, we decoupled the thermal treatment of the gaseous precursors (C₂H₄/H₂/Ar) and the substrate-supported catalyst. Varying the preheating temperature of the feedstock gas, we observed a striking transition between amorphous carbon nanofibers (CNFs) and crystalline CNTs. These results were confirmed using both a hot-wall CVD system and a cold-wall CVD reactor. Analysis of the exhaust gases (by ex situ gas chromatography) showed increasing concentrations of specific volatile organic compounds (VOCs) and polycyclic aromatic hydrocarbons (PAHs) that correlated with the structural transition observed (characterized using high-resolution transmission electron microscopy). This suggests that the crystallinity of carbon filaments may be controlled by the presence of specific gas phase precursor molecules (e.g., VOCs and PAHs). Thus, direct delivery of these molecules in the CVD process may enable selective CNF or CNT formation at low substrate temperatures. The inherent scalability of this approach could impact many promising applications, especially in the electronics industry.