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.     

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     

Effects of N2 and glow discharge on growth behaviours of carbon nanotubes prepared by the hot filament chemical vapour deposition method

Carbon nanotubes (CNTs) are prepared by the hot filament chemical vapour deposition method using CH4 and H2 as reaction gases, and the growth behaviours are investigated by scanning electron microscopy and transmission electron microscopy. The results indicate that the CNTs prepared in the absence of N2 or glow discharge are bent; however, they are in an aligned state after introducing N2 into the chamber or forming glow discharge under a negative biased voltage. The results also indicate that the CNTs are of a bamboo-like structure when N2 is intruded as a reaction gas and the alignment degree of the CNTs grown under glow discharge is higher than that grown in N2. This illustrates that the nitric environment and glow discharge play important roles in the growth of CNTs. Combining with the theory related to alloy thermodynamics and collisions, we have analysed the growth mechanism of the CNTs in nitric environment and glow discharge.     

Matchstick-like carbon nanotube synthesis and structure

Matchstick-like carbon nanotubes (CNTs) have been synthesized by catalytic pyrolysis of thiophene, using a mixture of cobalt nitrate and calcium nitrate as a catalyst. The nanotubes thus grown are aligned, straight, and short, and have spherical heads at their tips. High resolution transmission electron microscopy, selected area electron diffraction, and energy dispersive X-ray spectroscopy results indicate that the spherical heads of the matchstick-like CNTs are crystalline Co₉S₈ nanoparticles and the CNTs have herringbone-type graphite structure. The effect of temperature on the formation of the matchstick-like CNTs has been investigated. A simple growth model is proposed to describe the growth process of the matchstick-like CNTs. PACS 81.05.Uw; 61.46 Fg; 81.15.Gh; 68.37.Hk; 68.37.Lp     

Lateral growth of aligned mutilwalled carbon nanotubes under electric field

In this work we report laterally aligned multi-walled carbon nanotube (MWNT) by an electric field during growth. The MWNTs were selectively grown between lateral sides of the catalytic metals on predefined electrodes by chemical-vapor deposition. The electric field distribution for various geometries was simulated using Maxwell 2D simulation in order to realize better alignment of laterally grown carbon nanotubes (CNTs). The experimental results show that the electric field direction at the vicinity of catalyst and nanotubes-substrate interactions are principal factor in aligning CNTs laterally.     

Synthesis and growth mechanism of carbon nanotubes and nanofibers from ethanol flames

The ethanol flame was successfully used to synthesize highly graphitic hollow-cored carbon nanotubes (CNTs) and novel disorder solid-cored carbon nanofibers (CNFs). Their morphologies were characterized by using scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy and Raman spectroscopy. It was found that the mixture of CNTs and CNFs were grown on Ni-contained substrates, whereas only the CNFs were produced on carbon steel and low alloy steel substrates. It has been established that Ni and its compounds play a key role in CNTs growth and Fe and its compounds in CNFs growth. The models of 'hollow-cored mechanism' and 'solid-cored mechanism' were proposed to explain the present CNTs and CNFs formations, based on the theory that 'Fe has a strong affinity for carbon and Ni has a weak affinity for carbon'. It is expected that the present ethanol flame may provide a much simpler and more economic approach for mass-production of CNTs and CNFs by using large flame or multi-flames.     

Hot filament CVD of Fe-Cr catalyst for thermal CVD carbon nanotube growth from liquid petroleum gas

A hot filament chemical vapor deposition (HFCVD) method was used to prepare Fe-Cr thin film on Si substrate. The produced layers were used as catalysts for growing carbon nanotubes (CNTs) from liquid petroleum gas (LPG) at 825 °C by thermal CVD (TCVD) method. To characterize the obtained catalysts or CNTs, X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Raman spectroscopy were used. CNTs were grown on HFCVD derived Fe-Cr catalyst with the LPG as carbon source successfully. It was found that an annealing process on catalysts enhances the surface concentration of Cr atoms and reduces the sizes of catalyst particles. The grown CNTs on annealed sample were morphologically denser with smaller diameters compared to the as deposited one. In addition, the effect of filament temperature on CNTs was investigated. By increasing the filament temperature from 850 to 1050 °C the surface density and diameters of CNTs were improved.     

Physics and applications of aligned carbon nanotubes

Ever since the discovery of carbon nanotubes (CNTs) by Iijima in 1991, there have been extensive research efforts on their synthesis, physics, electronics, chemistry, and applications due to the fact that CNTs were predicted to have extraordinary physical, mechanical, chemical, optical, and electronic properties. Among the various forms of CNTs, single-walled and multi-walled, random and aligned, semiconducting and metallic, aligned CNTs are especially important since fundamental physics studies and many important applications will not be possible without alignment. Even though there have been significant endeavors on growing CNTs in an aligned configuration since their discovery, little success had been realized before our first report on growing individually aligned CNTs on various substrates by plasma-enhanced chemical vapor deposition (PECVD) [Science 282 (1998) 1105–1108]. Our report spearheaded a new field on growth, characterization, physics, and applications of aligned CNTs. Up to now, there have been thousands of scientific publications on synthesizing, studying, and utilizing aligned CNTs in various aspects. In this communication, we review the current status of aligned CNTs, the physics for their alignment, their applications in field emission, optical antennas, subwavelength light transmission in CNT-based nanocoax structures, nanocoax arrays for novel solar cell structures, etc.

The focus of this review is to examine various aligned CNT systems, either as an individual or as an array, either the orientation is vertical, parallel, or at other angles to the substrate horizon, either the CNT core structures are mostly hollow channels or are composed of complex compartments. Major fabrication methods are illustrated in detail, particularly the most widely used PECVD growth technique on which various device integration schemes are based, followed by applications whereas current limitations and challenges will also be discussed to lay down the foundation for future developments.     

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．     

沉积工艺参数对碳纳米管薄膜场发射性能的影响

利用微波等离子体化学气相沉积(MWPCVD)方法,在不锈钢衬底上直接沉积碳纳米管膜。通过SEM、拉曼光谱和XRD表征,讨论了制备温度和甲烷浓度对碳纳米管膜场发射的影响。结果表明:不同条件下制备的碳纳米管膜的场发射性能有很大差异,保持氢气的流量(100sccm)、生长时间(10min)、反应室压力不变,当甲烷流量为8sccm、温度为700~800℃时,场发射性能最好,开启场强仅为0.8V/μm,发射点分布密集、均匀。     

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     

The evolution of catalyst layer morphology and sub-surface growth of CNTs over the hot filament grown Fe-Cr thin films

In this study a hot filament chemical vapour deposition (HFCVD) technique was used to prepare Fe-Cr films on Si substrate as catalysts for thermal CVD (TCVD) growing of carbon nanotubes (CNTs) from liquid petroleum gas (LPG) at 800 °C. To characterize the catalysts or CNTs, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy were used. The XPS spectra obtained at different stages of Ar⁺ sputtering revealed that in the depth of catalyst layers, the relative Fe-Cr concentrations are higher than the top-surface. SEM images of samples after TCVD indicate a significant CNT growing at the backside of catalyst layer compared with its top which is accompanied with morphological changes on catalyst layer such as formation of cone-shape structures, rippling, cracking and rolling of the layer. These observations were attributed to the more catalytic activity of the sub-surface beside the poor activity of the top-surface as well as the presence of individual active islands over the surface of the catalyst thin film.     

金镍复合膜上碳纳米管的定向生长及生长过程中金的作用

以金镍复合膜作催化剂，在96%的高氢气浓度下实现了碳纳米管的定向生长，并对其生长过 程进行了深入探讨.结果表明，高氢气浓度下碳纳米管生长的实现与本实验所选用的催化剂 ——金镍复合膜有密切关系.催化剂中金的参与，促进了碳在催化剂中的扩散，提高了碳在 催化剂中的活度.与催化剂中没有金的情况相比较，金的参与有利于镍吸收气氛中的碳，从 而使镍更容易达到碳饱和，有利于在高的氢气浓度下实现碳纳米管的定向生长. 关键词： 金镍复合膜 高氢气浓度 原子氢 碳活度     

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 process and mechanism of a multi-walled carbon nanotube nest deposited on a silicon nanoporous pillar array

A large scale nest array of multi-walled carbon nanotubes (NACNTs) was grown on silicon nanoporous pillar array (Si-NPA) by thermal chemical vapor deposition. Through observing its macro/micromorphology and structure, ascertaining the catalyst component and its locations at different growth time by hiring field emission scanning electron microscopy, transmission electron microscopy (TEM), high-resolution TEM, and selected area electron diffraction, the growth process was deduced. Its thermal properties were also investigated by using a thermogravimetric analyzer. Our experiments demonstrated that the CNTs growth by means of root-growth mechanism at the initial growth stage, then a continuous growth process with its tip open is suggested, finally, a schematic growth model of NACNT/Si-NPA was presented.     

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.     

Study on structure change of carbon nanotubes depending on different reaction gases

Aligned carbon nanotubes were grown by plasma-enhanced hot filament chemical vapor deposition using different reaction gases and they were investigated by scanning electron microscopy and transmission electron microscopy. It is found that the hollow carbon nanotubes were formed using methane and hydrogen as the reaction gases, but the bamboo-structured carbon nanotubes were grown when ammonia was added into the reaction gases, indicating that the structure of the aligned carbon nanotubes was changed depending on different reaction gases. On setting of diffusion of carbon, the effects of the nitrogenous gas on the structure change of carbon nanotubes are studied.     

Selective alignment of carbon nanotubes on sapphire surfaces: bond formation between nanotubes and substrates

We present our first-principles total-energy calculations performed for carbon nanotubes (CNTs) on sapphire substrates. We find that the formation of covalent and partly ionic bonds between Al and C atoms on the Al-rich surfaces causes the selective alignment of CNTs, this being the principal reason for the CNT growth along particular crystallographic directions. We also find that the van der Waals interaction which is important on the stoichiometric surfaces produces no directional preference. The characteristic features in the electron states of the CNT on the substrate are clarified.     

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.