Effect of the reaction atmosphere on the diameter of single-walled carbon nanotubes produced by chemical vapor deposition

The influence of the reaction atmosphere on the type of single-walled carbon nanotubes (SWNT) grown during chemical vapor deposition (CVD) was investigated. Methane decomposition was catalyzed by Fe/MgO and Fe-Mo/MgO catalysts in argon, nitrogen and their mixtures. Nitrogen influences the carbon species significantly. The aggregation of iron nanoparticles in nitrogen results in the growth of N-doped carbon nanofibers on the Fe/MgO catalyst. A limited iron nanoparticle aggregation in nitrogen occurred on a Fe-Mo/MgO catalyst, on which there was an increase in the diameter of the SWNTs as the reaction atmosphere was more enriched in nitrogen, which was characterized by Raman spectroscopy. These results provide an experimental basis for the rational selection of the reaction atmosphere, and suggest an approach to control the size of the SWNTs in a CVD method.     

A simple way to CNx/carbon nanotube intramolecular junctions and branches

Large quantities of CN_x/carbon nanotube intramolecular junctions were successfully synthesized on a silicon substrate via the chemical vapor deposition method by pyrolysis of ferrocene and melamine. The nanotubes have two apparently different sections, one made of carbon with an empty hollow cylinder structure, and the other made of carbon nitride with a bamboo-like structure. Three- and four-terminal CN_x/carbon nanotube intramolecular branches were also observed, and such multi-terminal structures offer potential applications for future nanodevices. A simple model is suggested for the synthesis of these CN_x/carbon nanotube intramolecular junctions and branches.     

Aligned carbon nanotubes by catalytic decomposition of C2H2 over Ni–Cr alloy

High density, well-aligned carbon nanotubes (CNTs) were prepared by thermally decomposing acetylene at 700 °C with the help of Ni–Cr alloy as catalyst in a thermal chemical vapor deposition system. The density and alignment of CNTs were characterized by scanning electron microscope (SEM). It was found that the density of the CNTs could be remarkably increased and the alignment could be improved with the decrease of the thickness ratio of Ni:Cr. Also found in our experiment was that the catalyst encapsulated in CNT was single crystal Ni, which was confirmed by high-resolution transmission electron microscopy (HRTEM) and electron dispersion X-ray spectrum (EDX). Finally, the growth mode of CNTs was discussed based on the Ni–Cr alloy catalysts under our experimental conditions. The results are helpful in providing a better understanding of the acting of catalyst and the controlling of the desirable density and alignment of CNTs for various applications.     

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.     

Mechanism of carbon nanotube growth from camphor and camphor analogs by chemical vapor deposition

Single walled nanotubes have been synthesized by chemical vapor deposition from camphor, camphor analogs (camphorquinone, norcamphor, norbornane, camphene, fenchone), and various other precursors (menthone, 2-decanone, benzene, methane). The high temperature conditions (865 °C) and Fe/Mo alumina catalyst used in the syntheses are archetypal conditions for the production of single walled carbon nanotubes. It has been shown that the mechanism of tube growth is unlikely to depend upon the production of reactive five- and six-member rings, as has been previously suggested. The results suggest that the presence of oxygen in the precursor does not significantly improve the quality of tubes by etching amorphous carbon: it is suggested that the control of the flux of the precursor to the catalyst is more important in the production of high quality tubes. There is, however, evidence for different distributions of tube diameter being produced from different precursors.     

Aligned millimeter-long carbon nanotube arrays grown on single crystal magnesia

Single crystal magnesium oxide (MgO) was found to be very beneficial to the growth of aligned carbon nanotube (CNT) arrays as long as 2.2 mm by chemical vapor deposition. Before growth, a thin film of catalyst (iron) was coated on the MgO by magnetron sputtering. Scanning electron microscopy was used to study the alignment and length, and transmission electron microscopy was used to exam the wall numbers, diameter, and graphitization. It was found that the number of walls as few as two can be controlled by the catalyst film thickness, whereas the length is a combined result of gas pressure, temperature, and time during growth. Water was found not to be a factor to the length of CNTs grown on MgO, but a significant factor when sapphire was used as the substrates.     

Possible tactics to improve the growth of single-walled carbon nanotubes by chemical vapor deposition

The growth time, growth mode and the method of preparing the supported catalysts play an important role in the growth of single-walled nanotubes (SWNTs). Their effects on the chemical vapor deposition (CVD) growth of SWNTs with MgO-supported catalysts were investigated in this study. It is shown that the growth rate of SWNTs was large during the initial few minutes of growth, however the quality of the tubes was low owing to the formation of many defects. Long term growth may favor the formation of tubes with high quality and high yield, but the introduction of other forms of carbon (impurities) is also unavoidable. There was a balance between the increase in yield and quality and sacrifice of the purity during growth of SWNTs. MgO-supported catalysts prepared by the co-precipitation method were found to be more effective for the synthesis of SWNTs than those prepared by the widely used impregnation method. The size and dispersion state of the catalyst were found to be crucial in enhancing the growth of SWNTs. In addition, growth on the surface of SWNTs over nanosized catalyst films was shown to be more favorable for the synthesis of tube products with higher quality, yield and purity.     

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.     

Study of color change and microstructure development of Al2O3–Cr2O3/Cr3C2 nanocomposites prepared by spark plasma sintering

The densification behaviors of Al₂O₃–Cr₂O₃/Cr₃C₂ nanocomposites prepared by a Spark Plasma Sintering (SPS) were investigated in this work. The initial powders used for sintering were Al₂O₃–Cr₂O₃, which were prepared by metal organic chemical vapor deposition (MOCVD) in a spout bed. Different colors of the compacts such as green, purple and black were observed after densification process at different SPS temperatures from 1200 °C to 1350 °C. These changes of color were relevant to the existence of secondary phase of green Cr₂O₃, pink solid solution of Cr₂O₃–Al₂O₃ and black Cr₃C₂, which were formed under the different SPS temperature. The secondary phase of Cr₂O₃ retarded the processing of densification for spark plasma sintering at 1200 °C. The Cr₂O₃ reacted with Al₂O₃ to form solid solution of Cr₂O₃–Al₂O₃ and with carbon to form Cr₃C₂ as sintering temperature increased to 1350 °C. The characteristics of high heating rate, shorter sintering time for SPS and the formation of secondary phase of Cr₃C₂ effectively reduced the substrate's grain growth, making Al₂O₃–Cr₂O₃/Cr₃C₂ nanocomposites with small grain size.     

Single-walled carbon nanotubes grown on natural minerals

Single-walled carbon nanotubes (SWNTs) are successfully grown on magnesite crystal by pyrolysis of methane gas under moderate conditions, demonstrating the possibility of naturally occurring SWNTs.The obtained SWNTs were analyzed by Raman scattering, transmission electron microscope (TEM), and thermogravimetric (TG) measurements. These measurements revealed that high purity SWNTs having diameters of about 1-1.8 nm occur on the surface of natural magnesite sample by the pyrolysis of methane gas at 1073-1173 K. Structural properties and formation mechanism of the obtained SWNTs were discussed.     

Modulation of electrical properties in single-walled carbon nanotube/conducting polymer composites

The preparation and electrical characterization of a new class of composite layers formed by dispersing single-walled carbon nanotubes (SWNT) in 1,8-diaminonaphthalene polymer, the poly(1,8-DAN), are described.The material was grown on the surface of Pt plates by electropolymerization of 1,8-diaminonaphthalene (1,8-DAN) monomer in the presence of nanotubes. This synthesis method allows the simultaneous deposition of both the host polymer matrix and the filler nanotubes. A series of composite films were prepared using untreated nanotubes as well as nanotubes treated with KOH, HNO₃ and HNO₃/H₂SO₄ solutions. The structural features of the nanotubes and of the films produced have been investigated using Raman spectroscopy. Insight into the nature of nanotube dispersion and nanotube-polymer association was gained by AFM and STM analysis and by FE-SEM inspection after removing the outermost portion of composite films.The charge transport in composite films is found to be strongly enhanced by the nanotube insertion. Depending on the SWNTs processing, currents up to 30 mA, higher by a factor of about 140 than those of the pure poly(1,8-DAN) films, were measured with an applied voltage of 250 mV.     

Mass production of high-quality multi-walled carbon nanotube bundles on a Ni/Mo/MgO catalyst

A new catalyst (Ni/Mo/MgO) is reported, with which one can synthesize multi-walled carbon nanotube (MWNT) bundles with a yield of more than 45 times the amount of the pristine catalyst, using a methane-hydrogen mixture as precursor. Powder X-ray diffraction, Raman spectroscopy and thermal gravimetric analysis show that the purity of the as-prepared MWNTs is over 97%. The diameter of the carbon nanotubes is 9-20 nm, measured by high-resolution electron microscopy on 421 individual MWNTs. The high purity of the as-prepared MWNTs allows us to omit the usual complex purification process required for carbon nanotubes synthesized by chemical vapor deposition. Because of its durable high activity, the Ni/Mo/MgO catalyst in its pristine state is ideal for mass production of high-quality MWNTs. The synergism of nickel and molybdenum is considered the main reason for the high yield of carbon nanotubes.     

High growth of SWNTs and MWNTs from C2H2 decomposition over Co-Mo/MgO catalysts

A series of MgO supported catalysts having Co and Mo metals 5-40 wt.% in a ratio of 1:1 was prepared by impregnation method. Carbon nanotubes (CNTs) were grown over the catalysts by decomposition of C₂H₂ at 800 °C for 30 min. It was found that 5 and 10 wt.% Co-Mo/MgO catalysts produced single-wall nanotubes (SWNTs), whereas 20, 30 and 40 wt.% Co-Mo/MgO catalysts produced multi-wall nanotubes (MWNTs). The catalyst Mo/MgO was inactive in growing CNTs. In Co-Mo/MgO catalysts, however Mo generated a favorable environment to grow SWNTs. The growth of SWNTs was strongly dependent on the formation of small clusters of cobalt, which may generate from the decomposition of CoMoO₄ species during the nanotube growth. MWNTs were produced over comparatively larger cobalt clusters generated from Co₃O₄ phase during the nanotube growth stage. The yields of SWNTs were about 6% and 27% over 5 and 10 wt.% Co-Mo/MgO catalysts, respectively. MWNTs yield (576%) was observed over 40 wt.% Co-Mo/MgO catalyst. Carbon yield (%) highly varied with acetylene concentration.     

Well-dispersed single-walled carbon nanotube/polyaniline composite films

Single-walled carbon nanotube (SWNT)/polyaniline (PANI) composite films with good uniformity and dispersion were prepared by electrochemical polymerization of aniline containing well-dissolved SWNTs. The results of atomic force microscopy (AFM) and UV-Vis adsorption spectroscopy show that aniline can be used to solubilize SWNTs via formation of donor-acceptor complexes. The electrochemical deposition of SWNT-aniline solutions have been investigated by cyclic voltammetry. The results show that SWNT-based aniline solutions exhibit a drastic increase in peak current within the potential scanning region. The doping effect of SWNTs on PANI films was investigated by electrochemistry and FTIR spectroscopy. The results indicate that the enhanced electroactivity and conductivity of the SWNT/PANI composite films may be due to the strong interaction between SWNTs and PANI, which facilitates the effective degree of electron delocalization.     

SiCl3CCl3 as a novel precursor for chemical vapor deposition of amorphous carbon films

Amorphous carbon films, characterized by XRD, AFM, SEM and Raman, were deposited from SiCl₃CCl₃ on quartz substrates at 773-1273 K by low pressure chemical vapor deposition using a hot-wall reactor. XPS studies showed that the films grown at 773 K contained 90% C and 10% Cl, while the films grown at 1273 K contained 100% C. SiCl₄, CCl₄ and Cl₂CCCl₂ were detected by on-line FT-IR studies. The extrusion of dichlorocarbene, :CCl₂, from SiCl₃CCl₃ should provide the source of carbon in the reaction. On Si substrates, an etching process at the film-substrate interface assisted the lift-off of the films from the substrates. The C films curled and formed rolls.     

Nanocrystalline TiO2 on single walled carbon nanotube arrays: Towards the assembly of organized C/TiO2 nanosystems

Arrays of single walled carbon nanotube bundles organized following different architectures have been coated by a homogeneous deposit of nanocrystalline titania. The nanotubes were grown treating nanosized C powders with atomic H in a purpose-designed chemical vapor deposition (CVD) reactor, the subsequent TiO₂ deposition was performed at 400 °C using the metal-organic CVD (MOCVD) technique and titanium tetraisopropoxide Ti(OⁱPr)₄ as a precursor. X-ray diffraction and Raman spectroscopy evidence the anatase structure of the TiO₂ coatings, formed by grains with an average size of about 55 nm. The structural and compositional characteristics of the TiO₂ deposits are not sensitive to the organization of the nanotube arrays, which maintain their pristine architectures. The adopted synthetic procedure opens a new route for the immobilization of anatase-type TiO₂ nanocrystallites onto geometrically varied structures and for the integration of composite nanotube/TiO₂ systems in effective devices.