Synthesis of carbon nanotubes on diamond-like carbon by the hot filament plasma-enhanced chemical vapor deposition method

Carbon nanotubes (CNTs) have attracted considerable attention as possible routes to device miniaturization due to their excellent mechanical, thermal, and electronic properties. These properties show great potential for devices such as field emission displays, transistors, and sensors. The growth of CNTs can be explained by interaction between small carbon patches and the metal catalyst. The metals such as nickel, cobalt, gold, iron, platinum, and palladium are used as the catalysts for the CNT growth. In this study, diamond-like carbon (DLC) was used for CNT growth as a nonmetallic catalyst layer. DLC films were deposited by a radio frequency (RF) plasma-enhanced chemical vapor deposition (RF-PECVD) method with a mixture of methane and hydrogen gases. CNTs were synthesized by a hot filament plasma-enhanced chemical vapor deposition (HF-PECVD) method with ammonia (NH₃) as a pretreatment gas and acetylene (C₂H₂) as a carbon source gas. The grown CNTs and the pretreated DLC films were observed using field emission scanning electron microscopy (FE-SEM) measurement, and the structure of the grown CNTs was analyzed by high resolution transmission scanning electron microscopy (HR-TEM). Also, using energy dispersive spectroscopy (EDS) measurement, we confirmed that only the carbon component remained on the substrate.     

微量水对碳纳米管形貌的影响及其机理研究

利用介质阻挡放电等离子体化学气相沉积技术,在蒸镀有25nm Ni催化剂层的Si基片上,以CH₄和H₂作为反应气体,在973K下制备了碳纳米管,并研究了微量水的引入对碳纳米管形貌的影响.场发射扫描电子显微镜结果表明,不加水时,制备出的碳纳米管直径不均匀,分布在40—90nm之间,呈链节状的结构;加入少量水时,制备出的碳纳米管直径比较均匀,集中在70nm左右,表面为瘤状结构;当水的流量进一步增加时,得到的碳纳米管表面光滑,出现了枝状结构.原位测量了加水前后等离子体区的发射光谱,分析了微量水的引入对于碳纳米管形貌变化的影响机理. 关键词： 碳纳米管 介质阻挡放电 水 发射光谱     

Temperature and carbon source effects on methane–air flame synthesis of CNTs

We have conducted experimental and numerical studies on flame synthesis of carbon nanotubes (CNTs) to investigate the effects of three key parameters – selective catalyst, temperature and available carbon sources – on CNT growth. Two different substrates were used to synthesize CNTs: Ni-alloy wire substrates to obtain curved and entangled CNTs and Si-substrates with porous anodic aluminum oxide (AAO) nanotemplates to grow well-aligned, self-assembled and size-controllable CNTs, each using two different types of laminar flames, co-flow and counter-flow methane–air diffusion flames. An appropriate temperature range in the synthesis region is essential for CNTs to grow on the substrates. Possible carbon sources for CNT growth were found to be the major species CO and those intermediate species C₂H₂, C₂H₄, C₂H₆, and methyl radical CH₃. The major species H₂, CO₂ and H₂O in the synthesis region are expected to activate the catalyst and help to promote catalyst reaction.     

Growth of carbon nanotubes using nanocrystalline carbon catalyst

The basic growth of carbon nanotubes (CNTs) involves dissociation of hydrocarbon molecules over a metal layer as a catalyst. Generally, the metals used for the catalyst include nickel, cobalt, gold, iron, platinum, and palladium. However, the metal catalyst used with CNTs could have a harmful influence on the electrical properties of electronic devices. Therefore, we propose the use of nanocrystalline carbon (nc-C) as the catalyst for the growth of CNTs. We used a nc-C catalyst layer deposited by the closed-field unbalanced magnetron (CFUBM) sputtering method, and CNTs were grown by the hot filament plasma-enhanced chemical vapor deposition (HF-PECVD) method with ammonia (NH₃) as a pretreatment and acetylene gas (C₂H₂) as a carbon source. The CNTs were grown on the nc-C layers pretreated with a variation of the pretreatment time. The characteristics of the pretreated nc-C layers and the grown CNTs were investigated by field emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM) measurements. Also, the structural variation of the pretreated nc-C layers was investigated by Raman measurement. We used the nc-C catalyst without metal, and we confirmed that our CNTs were composed with only carbon elements through an EDS measurement. Also, the pretreatment time was attributed to the growth of CNTs.     

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.     

Synthesis and crystallinity of carbon nanotubes produced by a vapor-phase growth method

We have studied the effect of temperature on the growth and crystallinity of carbon nanotubes (CNTs), synthesized by a vapor-phase growth method using a catalytic reaction of iron pentacarbonyl (Fe(CO)₅) and acetylene (C₂H₂) gas. By increasing the growth temperature from 750 °C to 950 °C, both the growth rate and the diameter of the CNTs increase. Moreover, the crystallinity of the graphite sheets improves progressively with increasing growth temperature. Adjustment of the growth temperature gives potential for controlled growth of CNTs in a large-scale synthesis of CNTs. PACS 61.46.+w; 68.37.-d; 81.07.De     

生长参数对碳纳米管阵列制备的影响

利用化学气相沉积法在沉积铁纳米颗粒的硅衬底上制备了垂直方向高度有序的碳纳米管阵列．扫描电子显微镜的观测发现，碳纳米管阵列的形貌受到若干生长参数的影响，包括催化剂颗粒大小、反应温度和反应气体的分压等．研究发现，当反应温度升高，或反应气体中碳源气体含量增加时，碳纳米管变粗、变短．当催化剂薄膜的厚度减小时，碳纳米管的直径随之减小而纳米管阵列的高度则先增后减，有一个最大值．这些结果表明，碳纳米管的直径和阵列的高度可通过选择合适的反应温度、匀胶机转速和反应气比率来调节．     

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.     

Synthesis of well-aligned carbon nanotubes by inductively coupled plasma chemical vapor deposition

Uniform and well-aligned carbon nanotubes (CNTs) have been grown using a high density inductively coupled plasma chemical vapor deposition (ICP-CVD) system. A gas mixture of methane-hydrogen was used as the source and Ni as the catalyst for the CNT growth. The effect of process parameters, such as inductive RF power, DC bias voltage and CH₄/H₂ ratio, on the growth characteristics of CNTs was investigated. It was found that both plasma intensity and ion flux to the substrate, as controlled by the inductive RF power and DC bias voltage, respectively, can greatly affect the growth of CNTs. The relative importance of the generation of ions and the subsequent transport of ions to the substrate as serial process steps are considered as the two underlying factors in determining the growth characteristics of CNTs. PACS 81.05.Uw; 81.07.De; 81.15.Gh     

Effects of total CH4/Ar gas pressure on the structures and field electron emission properties of carbon nanomaterials grown by plasma-enhanced chemical vapor deposition

The effects of total CH₄/Ar gas pressure on the growth of carbon nanomaterials on Si (1 0 0) substrate covered with CoO nanoparticles, using plasma-enhanced chemical vapor deposition (PECVD), were investigated. The structures of obtained products were correlated with the total gas pressure and changed from pure carbon nanotubes (CNTs) through hybrid CNTs/graphene sheets (GSs), to pure GSs as the total gas pressure changed from 20 to 4 Torr. The total gas pressure influenced the density of hydrogen radicals and Ar ions in chamber, which in turn determined the degree of how CoO nanoparticles were deoxidized and ion bombardment energy that governed the final carbon nanomaterials. Moreover, the obtained hybrid CNTs/GSs exhibited a lower turn-on field (1.4 V/μm) emission, compared to either 2.7 V/μm for pure CNTs or 2.2 V/μm for pure GSs, at current density of 10 μA/cm².     

Synthesis of carbon nanotubes by catalytic vapor decomposition (CVD) method: Optimization of various parameters for the maximum yield

This paper describes an effect of flow rate, carrier gas (H₂, N₂ and Ar) composition, and amount of benzene on the quality and the yield of carbon nanotubes (CNTs) formed by catalytical vapour dcomposition (CVD) method. The flow and mass control of gases and precursor vapors respectively were found to be interdependent and therefore crucial in deciding the quality and yield of CNTs. We have achieved this by modified soap bubble flowmeter, which controlled the flow rates of two gases, simultaneously. With the help of this set-up, CNTs could be prepared in any common laboratory. Raman spectroscopy indicated the possibilities of formation of single-walled carbon nanotubes (SWNTs). From scanning electron microscopy (SEM) measurements, an average diameter of the tube/bundle was estimated to be about 70 nm. The elemental analysis using energy dispersion spectrum (EDS) suggested 96 at.wt.% carbon along with ca. 4 at.wt.% iron in the as-prepared sample. Maximum yield and best quality CNTs were obtained using H₂ as the carrier gas.      

Synthesis of a composite consisting of carbon nanotubes and graphite shell-encapsulated cobalt nanoparticles using plasma-enhanced chemical vapor deposition

We report a simple and effective one-step synthesis route for synthesizing a composite consisted of carbon nanotubes (CNTs) and graphite shell-encapsulated cobalt nanoparticles using plasma-enhanced chemical vapor deposition on Si (1 0 0) substrate covered with catalyst Co particles, discharging a mixture of H₂ and CH₄ gas, and characterize the obtained composite by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high resolution transmission electron microscope, and X-ray photoelectron spectroscopy. The results show that CNTs align perpendicularly to the substrate and graphite shell-encapsulated Co nanoparticles clung to the external surfaces of aligned CNTs. The diameter of the graphite shell-encapsulated Co nanoparticles increases with increasing the H₂ content in H₂ and CH₄ carbonaceous gas. A possible growth mechanism of the CNTs and graphite shell-encapsulated cobalt nanoparticles composite has been explored.     

Optimization of a thermal-CVD system for carbon nanotube growth

We illustrate the optimization of the operation of a thermal chemical vapor deposition (CVD) system for the growth of carbon nanotubes (CNT). We have studied the deposition parameters using the Taguchi matrix robust design approach. The CVD system, which employs solid precursors (camphor and ferrocene) carried by nitrogen gas flow through a hot deposition zone, where the deposition of carbon nanostructures takes place, involves a large number of tunable parameters that have to be optimized.With the aim of getting the best configuration for the development of massive and well-oriented CNT carpets, the Taguchi method allowed us to improve our system leading to the growth of extremely long CNTs (few millimeters) at a high deposition rate (500 nm/s) and yield (30% in weight of the carbon precursors feedstock), which were characterized by electron microscopy.We found that the growth temperature had the most important influence on the CNT diameter, whereas the substrate tilt wit respect to gas flow did not influence their growth (i.e. CNTs grow on every side of the silicon wafer substrates, always normal to the substrate surface). The carrier gas flow and catalyst concentration both showed a secondary impact on CNT growth, though they showed a consistent correlation to the growth temperature.     

Detailed profiling of CNTs arrays along the growth window in a floating catalyst reactor

We report a detailed longitudinal and depth profiles of multi-wall carbon nanotubes (CNTs) arrays synthesized using xylene and ferrocene in a floating catalyst reactor. Point to point analyses of the CNTs grown in a “growth window” with CNTs arrays longer than 0.5 mm were performed using optical microscopy, Raman spectroscopy, FESEM, high-resolution TGA/DTA, and TEM techniques. The heights of the CNTs arrays show a maximum at a mid point of the growth window, while a reverse trend of minimum is observed for iron-to-CNTs atomic ratios. The ratio of amorphous carbon to CNTs sharply increases along the growth window and from the bottom to top of CNTs arrays. The CNTs diameter also increases along the growth window, due to deposition of the amorphous carbon, which can be almost removed by temperature programmed oxidation up to around 500 °C. A base growth mechanism, the variations of catalyst content, residence time and temperature profile along the growth window, the adsorption and decomposition of polycyclic aromatic hydrocarbons to amorphous carbon, and a limited diffusion of hydrocarbon species through the arrays covered by excessive amorphous carbon may explain the results.     

Application of dielectrophoresis to fabrication of carbon nanohorn gas sensor

This paper describes an electrokinetic fabrication method for a gas sensor composed of single-wall carbon nanohorns (SWCNHs) using dielectrophoresis (DEP). The authors have previously demonstrated that DEP manipulation of carbon nanotubes (CNTs) can be applied to the fabrication of a CNT gas sensor. In the present study, we further explored the possibility of electrokinetic manipulation of SWCNHs. The latter have different structures and properties compared to CNTs. The SWCNHs were synthesized using the ‘arc in water with gas injection’ method. The SWCNH aggregates were dispersed in ethanol and trapped in an interdigitated microelectrode gap under the action of positive DEP. After the DEP process, the ethanol was evaporated and the microelectrode retaining the SWCNHs was exposed to nitrogen dioxide (NO₂) or ammonia (NH₃) gas while the electrode impedance was monitored. It was found that conductance of the DEP-fabricated SWCNH sensor increased or decreased upon exposure to ppm-levels of NO₂ or NH₃, respectively. These results were similar to those previously obtained for CNT gas sensors and suggest that the SWCNH aggregate behaves as a p-type semiconductor. The comparison reveals that intrinsic NO₂ sensitivity of the SWCNHs is lower than that of single-wall CNTs (SWCNTs) but comparable with the intrinsic sensitivity of multiple-wall CNTs (MWCNTs).     

Synthesis of multi-walled carbon nanotubes for NH3 gas detection

It has been recently demonstrated that carbon nanotubes (CNTs) represent a new type of chemical sensor capable of detecting a small concentration of molecules such as CO, NO₂, NH₃.In this work, CNTs were synthesized by chemical vapor deposition (CVD) on the SiO₂/Si substrate by decomposition of acetylene (C₂H₂) on sputtered Ni catalyst nanoparticles. Their structural properties are studied by atomic force microscopy, high-resolution scanning electron microscopy (HRSEM) and Raman spectroscopy. The CNTs grown at 700 °C exhibit a low dispersion in size, are about 1 μm long and their average diameter varies in the range 25–60 nm as a function of the deposition time. We have shown that their diameter can be reduced either by annealing in oxygen environment or by growing at lower temperature (less than 600 °C).We developed a test device with interdigital Pt electrodes on an Al₂O₃ substrate in order to evaluate the CNTs-based gas sensor capabilities. We performed room temperature current–voltage measurements for various gas concentrations. The CNT films are found to exhibit a fast response and a high sensitivity to NH₃ gas.     

Synthesis of carbon nanotubes on Ni-alloy and Si-substrates using counterflow methane–air diffusion flames

We have conducted an experimental study to investigate the synthesis of multi-walled carbon nanotubes (CNTs) in counterflow methane–air diffusion flames, with emphasis on effects of catalyst, temperature, and the air-side strain rate of the flow on CNTs growth. The counterflow flame was formed by fuel (CH₄ or CH₄ + N₂) and air streams impinging on each other. Two types of substrates were used to deposit CNTs. Ni-alloy (60% Ni + 26% Cr + 14% Fe) wire substrates synthesized curved and entangled CNTs, which have both straight and bamboo-like structures; Si-substrates with porous anodic aluminum oxide (AAO) nanotemplates synthesized well-aligned, self-assembled CNTs. These CNTs grown inside nanopores had a uniform geometry with controllable length and diameter. The axial temperature profiles of the flow were measured by a 125 μm diameter Pt/10% Rh–Pt thermocouple with a 0.3 mm bead junction. It was found that temperature could affect not only the success of CNTs synthesis, but also the morphology of synthesized CNTs. It was also found, against previous general belief, that there was a common temperature region (1023–1073 K) in chemical vapor deposition (CVD) and counterflow diffusion flames where CNTs could be produced. CNTs synthesized in counterflow flames were significantly affected by air-side strain rate not through the residence time, but through carbon sources available for CNTs growth. Off-symmetric counterflow flames could synthesize high-quality CNTs because with this configuration carbon sources at the fuel side could easily diffuse across the stagnation surface to support CNTs growth. These results show the feasibility of using counterflow flames to synthesize CNTs for particular applications such as fabricating nanoscale electronic devices.     

Thermal and optical study of semiconducting CNTs-doped nematic liquid crystalline material

We report the thermal and spectroscopic analysis of the carbon nanotubes (CNTs)-doped nematic liquid crystal (NLC) material. The CNTs have been oriented in the p-ethoxybenzylidene p-butylaniline NLC. The thermal study of the CNTs doped nematic mixtures shows a significant decrease in the isotropic to nematic phase transition temperature. However higher doping concentration of CNTs has led to the further increase in transition temperature. The UV-Visible spectroscopy has been attempted on the CNTs/NLC mixtures at room temperature. The investigated NLC present one absorption band corresponding to π–π* electronic transition. A red shift of λ_max with the increasing concentration of CNTs in the mixture has been observed. The band gap of NLC has been found to decrease after the doping of CNTs. The absorbance was measured for the UV light, polarized parallel and perpendicular to the LC director in the planar aligned cell.     

Fabrication of completely filled carbon nanotubes with copper nanowires in a confined space

Carbon nanotubes (CNTs) filled completely with polycrystalline Cu nanowires were synthesized by laser vaporization of Cu and graphite under high-pressure Ar gas atmosphere. Depending on the Ar gas pressure (0.1–0.9 MPa) and the Cu content (1–40 at.%) in graphite targets for laser vaporization, various products with different morphologies were observed by scanning and transmission electron microscopy. The ratios of the Cu-filled CNTs and carbon nanocapsules particularly increased as Ar gas pressure was increased. The maximum ∼60% fraction of Cu-filled CNTs with outer diameter of 10–50 nm and length of 0.3–3 μm was achieved at 0.9 MPa from graphite containing 20 at.% Cu. Most of the encapsulated Cu-nanowires were surrounded by single, double, or triple graphitic layers. Although the yield of the Cu-filled CNTs was also dependent on the Cu content in the graphite targets, no unfilled CNTs were produced even for low Cu content. The growth of Cu-filled CNTs is explained by the formation of molten Cu–C composite particles with an unusually C-rich composition in a space confined by high-pressure Ar gas, followed by precipitating Cu and C from the particles and subjecting them to phase separation.     

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