Growth of single-walled carbon nanotubes on silicon nanowires

Single-walled carbon nanotubes (SWNTs) have been grown on silicon nanowires (SiNWs) by ethanol chemical vapor deposition (CVD) with Co catalysts. We have found that a surface SiO_x layer of SiNWs is necessary for the formation of active Co catalysts. In fact, the yield of the SWNT/SiNW heterojunctions gradually decreases as the thickness of the surface SiO_x layer decreases. Since thin SiNWs are transparent to an electron beam, the Co nanoparticles on SiNWs can be easily observed as well as SWNTs by TEM. Therefore, the relationship between the diameters of each SWNT and its catalyst nanoparticle has been investigated. The diameters of SWNTs are equal to or slightly smaller than those of the catalyst nanoparticles.     

Effect of temperature on growth and structure of carbon nanotubes by chemical vapor deposition

The effect of temperature on growth and structure of carbon nanotubes (NTs) using chemical vapor deposition (CVD) has been investigated. Iron embedded silica was used to grow NTs in large quantity at various temperatures from 600 to 1050 °C with gas pressure fixed at 0.6 and 760 Torr, respectively. The growth and structure of the NTs are strongly affected by the temperature. At low gas pressure, the NTs are completely hollow at low temperature and bamboo-like structure at high temperature. While at high gas pressure, all the NTs are bamboo-like structure regardless of temperature. The diameter of NTs increases significantly with temperature. At low gas pressure the diameter gets bigger by mainly increasing the number of graphene layers of the wall of NTs, whereas at high gas pressure the diameter gets bigger by increasing both the number of graphene layers of the wall and the inner diameter of the NTs. This result indicates that the growth temperature is crucial in synthesizing NTs with different structures. The findings here are important for realizing controlled growth of NTs for their applications in different fields. Received: 20 November 2001 / Accepted: 21 November 2001 / Published online: 4 March 2002     

Effect of gas pressure on the growth and structure of carbon nanotubes by chemical vapor deposition

The effect of gas pressure on the structure of carbon nanotubes (CNTs) has been systematically investigated in the chemical vapor deposition process. The yield of CNTs (defined as the weight ratio of CNTs vs. catalyst) increases significantly with the gas pressure, reaches 600% at 600 Torr, then decreases with further increase of gas pressure. At low reacting gas pressure the CNTs have completely hollow cores, whereas at high pressure the CNTs have a bamboo structure. The density of the compartments in the bamboo-structured CNTs increases dramatically with the increase of the gas pressure. This result shows that the structure and yield of carbon nanotubes are strongly affected by the growth gas pressure. Received: 10 May 2001 / Accepted: 10 May 2001 / Published online: 20 June 2001     

High-density and well-aligned carbon nanotubes formed by surface decomposition of SiC

The structure and diameter of the densely aligned carbon nanotubes (CNTs) by surface decomposition of C-face in vacuum were investigated by cross-sectional, plan-view transmission electron microscopy and electron diffraction methods. Zigzag-type CNTs were confirmed to be selectively formed and the formation mechanism was proposed from crystallographic analysis. Furthermore, the wall number of CNTs was found to be directly proportional to the diameter of CNTs. Comparing with the theoretical calculation, it was revealed that all of the carbon atoms remained on the surface after the selective evaporation of Si atoms by decomposition of each monolayer of , and then constructed the CNT walls with the minimum diffusion distance at the interface.     

Surface characteristics of Ni catalystic films on growth behavior of multi-walled carbon nanotubes

The effect of the surface characteristics of Ni catalyst films on the growth behavior of multi-walled carbon nanotubes (MWCNTs) were investigated using Ni catalyst films prepared by different physical vapor deposition methods, electron-beam evaporation and sputtering. The growth behavior of MWCNTs was dependent upon the surface roughness of the Ni films. After a pretreatment process with NH₃, the root mean squares of surface roughness of e-beam evaporated and sputtered Ni catalyst films increased to 16.6 and 3.2 nm, respectively. Curled-MWCNTs and carbon-encapsulated Ni nanoparticles were formed on the Ni film deposited by e-beam evaporation while vertically aligned-MWCNTs were grown on the sputter-deposited film. In addition, the surface roughness of the Ni films affected the field emission properties of the MWCNTs. This was considered to originate from the specific growth behavior of the MWCNTs which was primarily caused by the initial surface roughness of the Ni films.     

The effects of hydrogen plasma pretreatment on the formation of vertically aligned carbon nanotubes

The effects of H₂ plasma pretreatment on the growth of vertically aligned carbon nanotubes (CNTs) by varying the flow rate of the precursor gas mixture during microwave plasma chemical vapor deposition (MPCVD) have been investigated in this study. Gas mixture of H₂ and CH₄ with a ratio of 9:1 was used as the precursor for synthesizing CNTs on Ni-coated TiN/Si(1 0 0) substrates. The structure and composition of Ni catalyst nanoparticles were investigated by using scanning electron microscopy (SEM) and cross-sectional transmission electron microscopy (XTEM). Results indicated that, by manipulating the morphology and density of the Ni catalyst nanoparticles via changing the flow rate of the precursor gas mixture, the vertically aligned CNTs could be effectively controlled. The Raman results also indicated that the intensity ratio of the G and D bands (I_D/I_G) is decreased with increasing gas flow rate. TEM results suggest H₂ plasma pretreatment can effectively reduce the amorphous carbon and carbonaceous particles and, thus, is playing a crucial role in modifying the obtained CNTs structures.     

Growth of vertically aligned carbon-nanotube array on large area of quartz plates by chemical vapor deposition

A simple method has been developed for growth of well-aligned carbon nanotubes (CNTs) on nickel-film quartz plates by chemical vapor deposition (CVD) with organic ethylenediamine as a precursor. High-density carbon nanotubes were vertically aligned on a large area of the quartz plates. The height of the nanotube array could be controlled by varying the CVD time. High-resolution transmission electron microscopy analysis revealed that the multiwalled CNTs were composed of crystalline graphitic sheets with a bamboo structure. Received: 28 May 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

Growth of multiwalled carbon nanotube arrays by chemical vapour deposition over iron catalyst and the effect of growth parameters

Multiwalled carbon nanotube (CNT) arrays were grown by catalytic thermal decomposition of acetylene, over Fe-catalyst deposited on Si-wafer in the temperature range 700-750 °C. The growth parameters were optimized to obtain dense arrays of multiwalled CNTs of uniform diameter. The vertical cross-section of the grown nanotube arrays reveals a quasi-vertical alignment of the nanotubes. The effect of varying the thickness of the catalyst layer and the effect of increasing the growth duration on the morphology and distribution of the grown nanotubes were studied. A scotch-tape test to check the strength of adhesion of the grown CNTs to the Si-substrate surface reveals a strong adhesion between the grown nanotubes and the substrate surface. Transmission electron microscopy analysis of the grown CNTs shows that the grown CNTs are multiwalled nanotubes with a bamboo structure, and follow the base-growth mechanism.     

Bundles and foils of WS2 nanotubes

In this paper, the synthesis of multigram portions of WS₂ nanotubes and large foils consisting of aligned nanotubes is described. For this purpose, a fluidized bed reactor, in which WO₃ powder is fed from the top and the reaction gases are blown from below maintaining the powder aloft, is described. The reaction mechanism is briefly discussed. Received: 20 August 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

Integration and characterization of aligned carbon nanotubes on metal/silicon substrates and effects of water

We report here a facile way to grow aligned multi-walled carbon nanotubes (MWCNTs) on various metal (e.g. gold, tungsten, vanadium and copper)/silicon electrically conductive substrates by aerosol-assisted chemical vapor deposition (AACVD). Without using any buffer layers, integration of high quality MWCNTs to the conductive substrates has been achieved by introducing appropriate amount of water vapor into the growth system. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) determination indicate tidy morphology and narrow diameter distribution of the nanotubes as well as promising growth rate suitable for industrial applications. Raman spectra analysis illustrates that the structural order and purity of the nanotubes are significantly improved in the presence of water vapor. The growth mechanism of the nanotubes has been discussed. It is believed that water vapor plays a key role in the catalyst-substrate interaction and nucleation of the carbon nanotubes on the conductive substrates. This synthesis approach is expected to be extended to other catalyst-conductive substrate systems and provide some new insight in the direct integration of carbon nanotubes onto conductive substrates, which promises great potential for applications in electrical interconnects, contacts for field emitters, and other electronic nanodevices.     

Fabrication, morphology and structural characterization of ordered single-crystal Ag nanowires

Highly aligned Ag nanowires have been synthesized by dc electrodeposition within a hexagonal close-packed nanochannel anodic aluminum oxide template. The pore diameter varies from 20 nm to 50 nm depending on the anodization voltage and temperature for the two types of aqueous solutions, sulphuric and oxalic acids, respectively. The size and morphology of the Ag nanowire arrays were measured by scanning electron microscopy and transmission electron microscopy. The images indicate that the highly aligned Ag nanowires grow in the uniform nanochannels of the anodic alumina template and that the size of the nanowires depends on the size of the nanochannels. X-ray diffraction, selected area electron diffraction pattern and high-resolution transmission electron microscopy images show that the Ag nanowires are single-crystal. The temperature coefficient of resistivity (temperature range from 4.2 K to 300 K) of the Ag nanowire arrays decreases with decreasing diameter of the nanowires. Received: 5 November 2001 / Revised version: 12 March 2002 / Published online: 6 June 2002     

Synthesis of carbon nanotubes by CVD: Effect of acetylene pressure on nanotubes characteristics

The effect of acetylene partial pressure on the structural and morphological properties of multi-walled carbon nanotubes (MWCNTs) synthesized by CVD on iron nanoparticles dispersed in a SiO₂ matrix as catalyst was investigated. The general growing conditions were: 110 cm³/min flow rate, 690 °C synthesis temperature, 180 Torr over pressure and two gas compositions: 2.5% and 10% C₂H₂/N₂. The catalyst and nanotubes were characterized by HR-TEM, SEM and DRX. TGA and DTA were also carried out to study degradation stages of synthesized CNTs. MWCNTs synthesized with low acetylene concentration are more regular and with a lower amount of amorphous carbon than those synthesized with a high concentration. During the synthesis of CNTs, amorphous carbon nanoparticles nucleate on the external wall of the nanotubes. At high acetylene concentration carbon nanoparticles grow, covering all CNTs’ surface, forming a compact coating. The combination of CNTs with this coating of amorphous carbon nanoparticles lead to a material with high decomposition temperature.     

催化剂对碳纳米管产率及质量的影响

本文研究了添加钴/二茂铁、镍/二茂铁、钴、镍/钴不同催化剂对高温热解法制备碳纳米管质量、产率等的影响。高分辨率透射电镜图象显示在800℃左右,镍/二茂铁、钴/二茂铁和钴催化条件下,有多壁碳纳米管生成,而用镍/钴作催化剂时,只有直径在0 5μm左右,长度十几个微米的非晶态棒状物生成。通过对生成碳纳米管的质量和产量进行比较,催化剂的催化活性满足二茂铁>钴>镍。简单分析了在碳源高温热解环境下不同金属催化剂的性能差异,并对不同催化条件下生成物的拉曼光谱进行了分析。     

Fabrication and characterization of suspended single-walled carbon nanotubes

Suspended single-walled carbon nanotubes (SWCNTs) between SiO₂ pillars via a direct lithographic route using a simple mixture of catalyst precursor [Co(III) acetylacetonate, Co(acac)₃] and conventional electron beam resist (ma-N2403) were fabricated. The catalytic electron beam resist (Cat-ER) layer plays dual roles as a catalyst and a resist layer for the growth and alignment of CNTs, respectively. The structure of the grown nanotube was characterized by Raman spectroscopy (633 nm laser excitation). Nanotubes grown from Cat-ER with Co(acac)₃ show the typical Raman spectra of SWCNTs which are characterized by the strong tangential bands near to 1590 cm⁻¹ and radial breathing modes (RBMs) in the low frequency region (<300 cm⁻¹). The calculated diameter of the probed nanotubes individually corresponds to the range 0.86-1.77 nm.     

Highly selective growth of vertically aligned double‐walled carbon nanotubes by a controlled heating method and their electric double‐layer capacitor properties

Vertically aligned double‐walled carbon nanotubes (DWCNTs) with the highest selectivity of 90% were synthesized by a controlled heating method and their electric double‐layer capacitor characteristics were evaluated. DWCNT arrays had a specific capacitance of 83 F/g, which is one of the highest values among CNT arrays in a nonaqueous solution and is almost equivalent to that for single‐walled CNT (SWCNT) arrays reported previously. At the same specific capacitance, DWCNTs with superior structural properties are more promising for practical capacitors than SWCNTs. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Hot filament effects on CVD of carbon nanotubes

We grew vertically aligned CNTs via HFCVD using mixtures of methane and hydrogen as feedstock, and investigated the dependence of CNT growth on feedstock composition, filament temperature, and filament types. At the filament temperature of 2050 °C tungsten filaments were more efficient for CNT growth than tantalum ones, and higher CNT growth rates were observed when tungsten filaments were operated at 1900 °C. Regardless of filament temperatures and types, monotonic increase in growth rate of vertically aligned CNTs was observed as we increased the methane concentration in the feedstock. In‐situ investigation of feedstock dissociation revealed the generation of various radical species, and, moreover, a strong correlation between CNT growth rates and relative mole fractions of single‐carbon radicals. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Study on effects of substrate temperature on growth and structure of alignment carbon nanotubes in plasma-enhanced hot filament chemical vapor deposition system

Alignment carbon nanotubes (ACNTs) were synthesized on silicon substrate coated with Ni catalyst film and Ta buffer layer by plasma-enhanced hot filament chemical vapor deposition using CH₄, NH₃, and H₂ as the reaction gas, and they were investigated by scanning electron microscopy and transmission electron microscopy. It is found that the diameter of the bamboo-structured ACNTs is increased from 62 to 177 nm when the substrate temperature was changed from 626 to 756 °C. Their growth rate is enhanced by the substrate temperature in a range of 626-683 °C and it is reversely reduced with the substrate temperature after the substrate temperature is over 683 °C. Beginning with wetting phenomenon, the effects of the substrate temperature on the structure and growth rate of the ACNTs are analyzed.     

Individuals, grasses, and forests of single- and multi-walled carbon nanotubes grown by supported Co catalysts of different nominal thicknesses

The relationships among the nominal thickness of Co catalyst, the structure of the catalyst particles, and the structure of carbon nanotubes (CNTs) growing from the catalyst during chemical vapor deposition were investigated. Various morphologies of CNTs such as individuals, random networks parallel to the surface of the substrate (‘grasses’), and vertically aligned forests of single- and multi-walled carbon nanotubes were grown by only varying the nominal thickness of catalyst under the same reaction condition. These different morphologies at the same growth time were due to the different areal density rather than to the length of CNTs. With increasing nominal thickness of catalyst, the catalyst particles changed in diameter while their areal density remained relatively almost constant. The change in diameter possibly affected the number ratio of active catalyst particles to the whole particles, which in turn affected the areal density of CNTs and yielded the various morphologies. Longer growth time increased the CNT length, which caused further change in CNT morphologies from individuals to grasses and grasses to forests.     

Altering the catalytic activity of thin metal catalyst films for controlled growth of chemical vapor deposited vertically aligned carbon nanotube arrays

The growth rate and terminal length of vertically aligned carbon nanotube arrays (VANTAs) grown by chemical vapor deposition have been dramatically improved through pulsed KrF excimer laser pretreatments of multilayer metal catalyst films. Silicon wafers coated with Al, Mo, and Fe layers were laser processed in air with single laser shots of varying fluence through circular apertures, then heated to ∼750°C and exposed to acetylene and ferrocene containing gas mixtures typically used to grow vertically aligned nanotube arrays. In situ videography was used to record the growth kinetics of the nanotube arrays in both patterned and unpatterned regions to understand the changes in catalytic activity, growth rates, and termination of growth. The height of the patterned regions varied with fluence, with the most successful treatment resulting in 1.4 cm tall posts of nanotubes embedded in a 0.4 cm tall nanotube carpet. High-resolution transmission electron microscopy images from the nanotubes in the posts revealed fewer walls, smaller diameters, and a much narrower distribution of diameters compared to the nanotubes grown in the carpet. This information, along with data obtained from weighing the material from each region, suggests that pulsed laser processing can also significantly increase the areal density of VANTAs. Research sponsored by the Division of Materials Sciences and Engineering, U.S. Department of Energy.     

Causes of different catalytic activities of metals in formation of single-wall carbon nanotubes

When single-wall carbon nanotubes (SWNTs) were formed by pulsed Nd:YAG laser ablation or arc discharge, the yield depended on the metal catalyst: NiCo> Ni∼NiFe≫Co∼Fe>Pd∼Pt. It appears that an effective catalyst for SWNT growth must satisfy three conditions: it must be a good graphitization catalyst, have low solubility in carbon, and have a stable crystallographic orientation on graphite. NiCo, Ni, and NiFe satisfy these three conditions. The poor catalytic activities of Co, Fe, Pd, and Pt for SWNT formation would be explained by the ineffectiveness of Pt and Pd as graphitization catalysts, crystallographic orientation instability of Co crystals on graphite, and high solubility of Fe in graphite. Received: 29 October 2001 / Accepted: 7 November 2001 / Published online: 23 January 2002