Synthesis of sea urchin-like carbon nanotubes on nano-diamond powder

Carbon nanotubes (CNTs) have unique atomic structure and properties, such as a high aspect ratio and high mechanical, electrical and thermal properties. On the other hand, the agglomeration and entanglement of CNTs restrict their applications. Sea urchin-like multiwalled carbon nanotubes, which have a small aspect ratio, can minimize the problem of dispersion. The high hardness, thermal conductivity and chemical inertness of the nano-diamond powder make it suitable for a wide range of applications in the mechanical and electronic fields. CNTs were synthesized on nano-diamond powder by thermal CVD to fabricate a filler with suitable mechanical properties and chemical stability. This paper reports the growth of CNTs with a sea urchin-like structure on the surface of the nano-diamond powder. Nano-diamond powders were dispersed in an attritional milling system using zirconia beads in ethanol. After the milling process, 3-aminopropyltrimethoxysilane (APS) was added as a linker. Silanization was performed between the nano-diamond particles and the metal catalyst. Iron chloride was used as a catalyst for the fabrication of the CNTs. After drying, catalyst-attached nano-diamond powders could be achieved. The growth of the carbon nanotubes was carried out by CVD. The CNT morphology was examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The mean diameter and length of the CNTs were 201 nm and 3.25 microm, respectively.     

The influence of Ni catalyst on the growth of carbon nanotubes on Si substrates

This article treats the influence of the treatment of a Ni catalyst upon the growth of carbon nanotubes in alcohol catalytic chemical vapour deposition (AC CVD) equipment. Prior to the growth of diamond, a thin film of Ni was deposited on a silicon substrate by magnetron sputtering. We observed that a combination of annealing of the Ni catalyst in vacuum and NH₃ had a positive effect upon the growth of carbon nanotubes (CNTs). The prepared CNTs were analysed by scanning electron microscopy and Raman spectroscopy.     

催化裂解天然气于碳毡内低成本合成碳纳米管

基于制备碳/碳(C/C)复合材料的等温化学气相渗透(ICVI)技术,在1010～1100℃用Fe催化裂解工业天然气可在碳毡内原位合成出碳纳米管(CNTs).扫描电镜(SEM)观察结果表明,1060℃合成的CNTs具有较好的覆盖形貌和均匀管径(110～120nm)且纯净度高.高分辨率透射电镜(HRTEM)和Raman光谱测试结果进一步表明,该温度下合成的CNTs结晶度高,与碳纤维间结合力强.     

Growth of single-walled carbon nanotube arrays from samarium on substrates

In this letter, it is reported for the first time that samarium is an effective catalyst for single-walled carbon nanotubes(SWNTs) growth via a chemical vapor deposition(CVD) process. Horizontally superlong well-oriented SWNT arrays can be generated under suitable conditions by using ethanol as carbon source. The single-wall structure was characterized by scanning electron microscopy, Raman spectroscopy and atomic force microscopy. The results show that the SWNTs from samarium have better conductivity and better structural uniformity with less defects. This rare earth metal element provides not only an alternative catalyst for SWNTs growth but also a possible way to generate high percentage of superlong semiconducting SWNT arrays for various applications of nanoelectronic device.     

Diameter dependent growth mode of carbon nanotubes on nanoporous SiO2 substrates

Two different growth modes of carbon nanotubes (CNTs) are identified in ethylene chemical vapour deposition (CVD) using SiO₂ as support. With a series of electron microscopy observations, we have found that small-diameter nanotubes favor a root-growth mechanism on nanoporous SiO₂ support, while nanotubes with larger diameters prefer a tip-growth. The dependence of growth mode on tube diameter is explained in terms of the porosity of the support and the size distribution of the catalyst. Our results provide clues to control growth of CNTs and obtain well-organized nanotube structures.     

Carbon nanotube growth on cobalt-sprayed substrates by thermal CVD

We present a very simple spray-coating method for depositing cobalt catalyst over quartz substrates that can be efficiently utilized in the production of carbon nanotubes (CNTs) by thermal chemical vapor deposition (CVD). Very uniform multi-walled carbon nanotubes (MWNTs) have been grown from cobalt catalyst over large surfaces by thermal CVD using mixtures of acetylene and ammonia. The effect of catalyst pretreatments and CNT growth temperature on the CNT diameter has been studied and discussed.     

化学气相沉积法制备碳纳米管

碳纳米管（CNTs）是一种具有独特理化性能和结构的一维纳米材料,也是当今纳米材料研究的焦点之一．在化学、生物、医药、能源、电子元件等诸多领域具有极高的应用价值．本文以有机溶剂环己烷为碳源．利用化学气相沉积法（CⅥ））在管式电阻炉内,以氩气为栽气,二茂铁为催化剂,一定温度条件下,制备了直径约为50nm,长度达几十微米以上的多壁碳纳米管（MWNTs）．采用拉曼光谱、扫描电镜、透射电镜、X-射线粉末衍射等测试手段,表征了碳纳米管的微观形貌和结构特征．通过对实验结果的分析和讨论,对CVD制备法中碳纳米管的生长机理进行了尝试性探讨。     

The growth of carbon nanotubes on large areas of silicon substrate using commercial iron oxide nanoparticles as a catalyst

A new approach to chemical vapour deposition (CVD) growth of carbon nanotubes (CNTs) using commercial magnetite nanoparticles, avoiding its in situ synthesis, is reported. Commercial magnetite nanoparticles were used as catalyst material to growth multiwalled carbon nanotubes by chemical vapour deposition onto a silicon substrate of several square centimeters in area. It is shown that the application of an alternating electric field during the deposition of catalytical nanoparticles is an effective technique to avoid their agglomeration allowing nanotube growth. Scanning electron microscopy showed that the nanotubes grow perpendicularly to the substrate and formed an aligned nanotubes array. The array density can be controlled by modifying the deposited nanoparticle concentration.     

沉积条件对碳纤维表面碳纳米管生长的影响

采用化学气相沉积(CVD)法在碳纤维(CF)表面原位生长碳纳米管(CNTs)。考察了不同催化剂、沉积温度、氢气流量以及样品距进气口距离等工艺参数对CNTs-CF生长的影响。利用SEM和高分辨透射电子显微镜(HRTEM)对CNTs-CF形貌和微结构进行了表征和分析。结果表明:在CF表面原位生长的CNTs为多壁结构,其中以Ni为催化剂得到的CNTs直径小、分布均匀;在600~750℃温度范围内,随着温度的升高,CNTs直径和长度减小,产量降低;随着氢气流量的增加,CNTs直径和长度均增加;距进气口30cm,在CF表面得到的CNTs覆盖率高、直径小且分布窄,有利于制备高质量CNTs。     

CVD growth of carbon nanotubes on catalyst patterns generated with AFM lithography

We obtain carbon nanotubes (CNTs) by chemical vapor deposition (CVD) using ethanol as carbon source. CNTs are grown on linear and rectangular patterns containing Co–Mo catalysts. These patterns were generated with a combination of dip-pen and ‘scratching’ lithography performed with Atomic Force Microscopy (AFM). In this procedure, a gold thin film deposited on porous alumina substrates is first scratched and subsequently a solution of Co and Mo acetates in ethanol is painted on the scratched area with a syringe mounted on the AFM instrument. CVD growth temperature of CNTs is of about 750°C with an ethanol exposure time of 30 min. In the linear patterns a dense film of CNTs is obtained with average lengths of 1 μm and in the rectangular patterns CNTs grow with diameters of about 50 nm. Sample analysis is performed with scanning electron microscopy (SEM) and AFM.     

Growth of metal-free carbon nanotubes on glass substrate with an amorphous carbon catalyst layer

We have investigated the direct growth of metal-free carbon nanotubes (CNTs) on glass substrates with microwave-plasma enhanced chemical vapor deposition (MPECVD). Amorphous carbon (a-C) films were used as a catalyst layer to grow metal-free CNTs. The a-C films were deposited on Corning glass substrates using RF magnetron sputtering with the use of a carbon target (99.99%) at room temperature. They were pretreated with hydrogen plasma using a microwave PECVD at 600 degrees C. Then, CNTs were prepared using microwave PECVD with a mixture of methane (CH4) and hydrogen (H2) gases. The CNTs were grown at different substrate temperatures (400 degrees C, 500 degrees C, and 600 degrees C) for 30 minutes. Other conditions were fixed. The growth trends of CNTs against substrate temperature were observed by field emission scanning electron microscopy (FE-SEM). The structure of a-C catalyst layer and grown CNTs were measured by Raman spectroscopy. High-resolution transmission electron microscopy (HR-TEM) images showed that the CNTs had bamboo-like multi-walled structures. Energy dispersive spectroscopy (EDS) measurements confirmed that the CNTs consisted of only carbon.     

用ECR-CVD方法制备定向碳纳米管

以FeaO4纳米粒子为催化剂,CH4和H2为气源,采用电子回旋共振微波等离子体化学气相沉积技术(ECR-CVD)在多孔硅基底上制备出定向生长的碳纳米管.研究了气氛组成、气压、温度和反应时间对碳纳米管生长特性的影响.使用扫描电子显微镜(SEM)、透射电子显微镜(TEM)和拉曼光谱(Raman spectrum)表征了样品的形貌和结构.结果表明:气氛组成和气压影响了反应腔内离解碳的浓度,从而影响碳纳米管的成核、生长速度及定向生长;温度的变化改变催化剂的尺寸从而改变碳纳米管的直径,在过低的温度下碳纳米管不能实现定向生长;碳纳米管随着反应时间的延长而不断增长,但超过一定时间后催化剂颗粒被碳包覆而失去催化作用,生长停止.     

Synthesis of carbon nanotubes on metal mesh in inverse diffusion biofuel flames

In this study, renewable biofuels (ethanol and n-butanol) were utilized to synthesize carbon nanotubes on substrate of inexpensive metal mesh (copper alloy and nickel) using inverse diffusion flame. The effects of metal mesh, synthesis time and flame temperature on growth of carbon nanotubes (CNTs) were investigated in details. The morphology and structure of CNTs were characterized by scanning electron microscopy (SEM), high resolution transmission electron microscope (HRTEM) and Raman spectroscopy. The results showed that there were no CNTs formed on nickel mesh. When the substrate was copper alloy mesh, the yield of CNTs increased from 2?min and reached maximum at about 15?min as the synthesis time increased. Under the condition of 15?min, CNTs synthesized in ethanol flame of 1023?K and in n-butanol flame of 1273?K had higher degree of graphitic structure. In addition, multi-walled carbon nanotubes (MWCNTs) with straight tube wall were synthesized in ethanol flame of 1023?K and 1273?K when the synthesis time was 15?min. For these experiments, CNTs with excellent quality could be synthesized effectively in ethanol flame with temperatures of 1023?K and 1273?K when the synthesis time was 15?min and the substrate was copper alloy mesh.     

High-rate low-temperature growth of vertically aligned carbon nanotubes

We report the low-temperature growth of vertically aligned carbon nanotubes (CNTs) at high growth rates by a photo-thermal chemical vapour deposition (PTCVD) technique using a Ti/Fe bilayer film as the catalyst. The bulk growth temperature of the substrate is as low as 370?°C and the growth rate is up to 1.3 μm min(-1), at least eight times faster than the values reported by traditional thermal CVD methods. Transmission electron microscopy observations reveal that as-grown CNTs are uniformly made of highly crystalline 5-6 graphene shells with an approximately 10 nm outer diameter and a 5-6 nm inner diameter. The low-temperature rapid growth of CNTs is strongly related to the unique top-down heating mode of PTCVD and the use of a Ti/Fe bimetallic solid solution catalyst. The present study will advance the development of CNTs as interconnects in nanoelectronics, through a CMOS-compatible low-temperature deposition method suitable for back-end-of-line processes.     

Synthesis and characterization of Ni-Si mixed oxide nanocomposite as a catalyst for carbon nanotubes formation

Ni-Si mixed oxide nanocomposite was prepared by co-precipitation method with Ni(NO₃)₂ · 6H₂O and tetraethylorthosilicate (TEOS) at pH = 10.5 under reflux condition for 6 days. It was then used as a catalyst for the formation of carbon nanotubes (CNTs) by CVD procedure. Characterization of the catalyst and the CNTs was carried out using X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The results showed that Ni-Si mixed oxides nanorods with the average diameter of 3 to 4 nm play a key role in CNTs formation.     

Systematic study on synthesis and purification of double-walled carbon nanotubes synthesized via CVD

Carbon nanotubes have unique properties, such as thermal and electrical conductance, which could be useful in the fields of aerospace, microelectronics and biotechnology. However, these properties may vary widely depending on the dimensions, uniformity and purity of the nanotube. Nanotube samples typically contain a significant percentage of more allotropes forms of carbon as well as metal particles left over from catalysts used in manufacturing. Purity characterization of double-walled carbon nanotubes (DWCNTs) is an increasingly popular topic in the field of carbon nanotechnology. In this study, DWCNTs were synthesized in a catalytic reaction, using Fe:MgO as catalyst and methane or methane/ethanol as carbon feedstock for chemical vapor deposition (CVD). The addition of ethanol as carbon feedstock allowed to investigate the influence of oxygen on the sample quality. The purification of the as-produced material from the metallic particles and the catalyst support was performed by sonication in an acid solution. The influence of the duration of the acid treatment using ultrasound on the sample purity was investigated, and the optimal value of this parameter was found. Transmission electron microscopy (TEM) images confirmed the removal of impurities and served to elucidate the morphology of the samples. The purity of carbon nanotubes was analyzed using thermal gravimetric analysis (TGA). The Raman spectra of the samples, as a measure of the concentration of defects, were also reported.     

Direct synthesis of Y-junction carbon nanotubes by microwave-assisted pyrolysis of methane

Both Y-junction carbon nanotubes and individual carbon nanotubes were synthesized without any additive catalyst by microwave decomposition of methane. Detailed microstructures of as-synthesized products have been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman spectroscopy. The results show that these Y-junction CNTs possess an internal bamboo-shaped structure, and some three dimensional multi-terminal junctions are also observed on CNTs. As gas flow rate decreased to 15 sccm, only individual nanotubes could be obtained. A possible mechanism is proposed for the synthesis of the Y-junction carbon nanotubes on these observations. This technique may also have great potential in making other nano-structured carbon materials on a large scale and at low cost.     

碳纳米管/羟基磷灰石复合材料的制备及表征

以含钴介孔分子筛为催化剂、乙醇为碳源, 采用CVD法制备碳纳米管(CNTs)。通过原位合成法制备一系列不同碳纳米管含量的碳纳米管/羟基磷灰石(CNTs/HA)复合材料。分别采用XRD、FTIR、TEM、N₂吸附-脱附和Raman光谱等分析手段, 对所合成CNTs/HA复合材料的晶相、结构、形貌和比表面积等进行了表征。同时研究了碳纳米管的添加量对所合成CNTs/HA复合材料形貌的影响。XRD与Raman结果表明, 所得CNTs/HA复合粉体中仅有CNTs与HA两种物相, 纯度较高, 结晶度较好; TEM结果显示, CNTs/HA复合材料中CNTs表面均匀包裹着一层纳米级的针状HA晶粒, 两者形成了较强的界面结合, 且当CNTs与HA的质量比为3:17时, CNTs与HA形成最佳结合状态; N₂吸附-脱附表征结果表明, 与HA的比表面积相比, CNTs/HA复合材料具有较高比表面积。     

Carbon dioxide as a carbon source for synthesis of carbon nanotubes by chemical vapor deposition

Carbon dioxide was successfully used as carbon source in the synthesis of carbon nanotubes (CNTs) by chemical vapor deposition (CVD) over Fe/CaO catalyst. The product was evaluated using both transmission electron microscopy (TEM) and Raman spectroscopy. Crooked and branching structures of multi-walled carbon nanotubes (MCNTs) with diameters of around 50 nm were observed on the TEM micrographs. Raman spectrum results show that the nanotubes have small defects, which is in agreement with the results of TEM. The influence of reaction variable such as furnace temperature and types of support media was also studied and the reaction mechanism was then discussed in this paper.     

Efficient strategy to Cu/Si catalyst into vertically aligned carbon nanotubes with bamboo shape by CVD technique

Bamboo-shaped vertically aligned carbon nanotubes (bs-VACNTs) were fabricated on Cu/Si catalyst by chemical vapour deposition (CVD) technique under the atmospheric pressure. The catalytic material (Cu/Si) played a vital role in attaining bs-VACNTs, which is synthesized by drop cast method in a cost-effective manner. Using this catalytic support, we have achieved the tip growth bs-VACNTs at low temperature with well graphitization. The as-grown carbon material was then characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX) analyzer, high-resolution transmission electron microscope (HRTEM) and Raman spectroscopy. XRD technique confirms the formation of hexagonal graphitic carbon planes of carbon nanotubes (CNTs). The surface morphology of the material was characterized by SEM, which clearly infer vertically aligned CNTs. The nature, diameter and crystallinity were noticed by HRTEM and Raman spectroscopy, respectively. Further, we have also studied the electrochemical properties of the bs-VACNTs and it seems to be proved as highly electroconductive when compared to multi-walled carbon nanotubes (MWCNTs).