衬底温度对碳纳米管生长和结构的影响

用CH4、NH3和H2为反应气体,利用等离子体增强热丝化学气相沉积在沉积有Ta缓冲层和Ni催化剂层的Si衬底上制备了准直碳纳米管,并用扫描电子显微镜和透射电子显微镜研究了它们的生长和结构随温度的变化.结果表明生长的准直碳纳米管是竹节型结构,其直径随衬底温度的降低而减小,生长速率随衬底温度的升高有一极值.从催化剂在衬底温度作用下的变化开始,分析了衬底温度对碳纳米管生长和结构的影响.     

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.     

沉积条件对CVD碳纤维生长的影响

用CH4、H2或包含NH3的混合气体为反应气体,利用负偏压增强热丝化学气相沉积方法在沉积有过渡层(Ta或Ti)和催化剂层(NiFe)的Si衬底上制备碳纤维,并用扫描电子显微镜研究了它们的生长和结构,结果发现不同的沉积条件对碳纤维的生长和结构有很大的影响。在无辉光放电的条件下,衬底温度较低时碳纳米管或纤维生长困难;提高衬底温度,能够弯曲生长;在辉光放电的条件下,则呈现定向生长的特点。     

辅助气体对RF-PECVD制备碳纳米管薄膜形貌的影响

采用射频等离子体增强化学气相沉积(RF-PECVD)技术,以Ni为催化剂,经600℃裂解C2H2在Si基底上制备出定向碳纳米管薄膜。采用扫描电子显微镜(SEM)表征了刻蚀后Ni颗粒与沉积的碳纳米管薄膜的形貌。研究了辅助气体对等离子体预处理催化剂与碳纳米管生长的影响。结果表明:辅助气体(H2与N2)流量比对催化剂颗粒尺寸、分布以及碳纳米管生长有显著影响;合适的气体流量比有利于减少碳纳米管薄膜的杂质颗粒,促进其定向生长。预处理过程中气体流量比H2:N2=20:5时,预处理后催化剂Ni颗粒分布密度大、粒径小且分布范围窄,适合碳纳米管均匀着床;沉积生长碳纳米管薄膜时,H2:N2=20:15可得到纯度高、定向性好的碳纳米管。     

理论分析辉光放电对碳纳米管生长速率的影响

利用负偏压增强热丝化学气相沉积 ,在沉积过渡层Ta和催化剂NiFe层的Si衬底上制备了碳纳米管 ,并用扫描电子显微镜研究了它们的形貌。发现辉光放电后 ,碳纳米管的平均长度比无辉光放电时大 ,并且随着负偏压的增大而增大 ,即辉光放电增大了它们的生长速率。结合辉光放电和扩散理论分析了辉光放电对碳纳米管生长速率的影响 ,结果表明在生长碳纳米管的过程中 ,由于辉光放电的产生 ,碳在催化剂中的活度得到增强 ,从而增大了碳纳米管的生长速率。     

非定向多壁碳纳米管制备过程中引入水对其生长的影响

用催化化学气相沉积法制备非定向多壁碳纳米管时,利用气体携带水进入反应区域,考察了水对碳纳米管生长的影响,并用透射电子显微镜对其形貌进行表征.结果显示,带入适量的水后,碳纳米管的产率可以得到较大提高,同时对碳纳米管形貌基本不产生影响.但水量太多或太少都会影响所得碳纳米管的产率,尤其当水过多时,还会对碳纳米管的产率产生较大影响.     

大面积取向生长碳纳米管的ECR-CVD方法制备与表征

本文采用电子回旋共振微波等离子体化学气相沉积方法(ECR-CVD),以CH4和H2为气源、Fe3O4 纳米粒子为催化剂,未加电场,在多孔硅基底上制备出大面积取向生长碳纳米管.使用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、X射线能量色散分析(EDX)对样品形貌和结构进行表征.结果显示:合成的碳纳米管为多壁碳管;碳纳米管直径60 nm～90 nm,长度约8 μm;碳纳米管展现出中空管状和链状两种结构;碳纳米管的生长采取催化剂底端生长模式.     

理论分析辉光放电对碳纳米管生长速率的影响

利用负偏压增强热丝化学气相沉积，在沉积过渡层Ta和催化剂NiFe层的Si衬底上制备了碳纳米管，并用扫描电子显微镜研究了它们的形貌。发现辉光放电后，碳纳米管的平均长度比无辉光放电时大，并且随着负偏压的增大而增大，即辉光放电增大了它们的生长速率。结合辉光放电和扩散理论分析了辉光放电对碳纳米管生长速率的影响，结果表明在生长碳纳米管的过程中，由于辉光放电的产生，碳在催化剂中的活度得到增强，从而增大了碳纳米管的生长速率。     

辉光放电和压强对准直碳纳米管生长的影响

利用负偏压增强热丝化学气相沉积系统在沉积有过渡层Ta和催化剂层NiFe的Si村底上制备出准直碳纳米管，并用扫描电子显微镜研完了它们的生长和结构，结果表明辉光放电和压强对其生长和结构有极大的影响。若无辉光放电产生，碳纳米管是弯曲的，有辉光放电时，碳纳米管是准直的。当压强较大时，准直碳纳米管较容易生长，并且随着压强的减小，其平均直径减小和平均长度增大。但压强为5Pa时，准直碳纳米管却不能够生长。最后，分析和讨论了辉光放电和压强对准直碳纳米管生长和结构的影响。     

化学气相沉积法低温合成螺旋碳纳米管

以水溶性氯化钠负载Fe做催化剂,直接通过化学气相沉积法在没有掺杂任何含硫气体噻吩的条件下催化裂解乙炔在450℃下进行反应制备纳米碳材料。产物通过扫描电子显微镜和高分辨透射电子显微镜进行了表征。结果表明:在该条件下制备了选择性较高的螺旋碳纳米管,其直径在25~200nm之间,绝大部分碳纳米管都有着非常规整的螺旋性并且其螺距很短。所制备螺旋碳纳米管晶格没有好的连续性,中间有断痕出现,并且排列也很不规则,为一种有缺陷的石墨结构。     

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 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.     

Catalytic synthesis of carbon nanofibers and nanotubes by the pyrolysis of acetylene with iron nanoparticles prepared using a hydrogen-arc plasma method

Carbon nanofibers (CNFs) and carbon nanotubes (CNTs) were synthesized at different temperatures by the catalytic pyrolysis of acetylene with iron nanoparticles prepared using a hydrogen-arc plasma method. The obtained carbon nanomaterials were characterized by transmission electron microscopy and field-emission scanning electron microscopy. An iron nanoparticle was always located at the tip of CNFs or CNTs, whose diameter was approximately identical with the diameter of the iron nanoparticle. The structures of the products were closely related to the reaction temperature, and could be changed from fibers to tubes by simply increasing the temperature. CNFs were obtained at the reaction temperature of 550-650 °C. When the reaction temperature was increased to 710-800 °C, CNTs were obtained.     

Effect of ferrocene catalyst particle size on structural and morphological characteristics of carbon nanotubes grown by microwave oven

The influence of catalyst particle size on the formation and diameter of carbon nanotubes (CNTs) is investigated. Ferrocene catalyst with an average diameter of 19.7, 21.4, 23.6 and 27.0 µm is used for the growth of CNTs by a cost-effective and facile method using microwave oven. Morphological observations by transmission electron microscopy and field emission scanning electron microscopy reveal consistently that smaller catalyst diameter generates CNTs with smaller diameter. Raman spectroscopy indicates that the full width at half maximum of G-, D- and 2D-bands decreases gradually with increasing CNTs diameter; meanwhile, G-band/D-band intensity ratio is found to be sensitive to crystal defects, showing a drop for CNTs diameter in the range 25–40 nm then followed by a slight increase for higher diameters. This may be associated with CNTs curvature and strain which developed along tube walls. X-ray diffraction analysis demonstrates an increase in d ₍₀₀₂₎ interlayer spacing with decreasing CNTs diameter. Furthermore, CNTs diameter is found to be inversely proportional to (002) linewidth. Finally, the energy band gap estimated from UV–NIR–Vis measurements increases slightly with CNTs diameter, 5.69–5.84 eV.     

Investigation of the effective parameters in the growth of carbon nanotubes by thermal chemical vapour deposition method

Synthesis and growth of carbon nanotubes (CNTs) from C₂H₂ by thermal chemical vapour deposition (TCVD) using a mixture of different gases were investigated. A thin film of nickel was coated as catalyst on silicon substrates by ion beam sputtering technique. Various parameters such as thickness of oxide layer and time, as well as reduction temperature were investigated in view of obtaining the best conditions for CNTs growth. C₂H₂ was very effective as carbon feedstock and NH₃ pretreatments were crucial steps towards obtaining a high density of nucleation sites for CNTs growth by inhibiting amorphous carbon generation in the initial stage of the synthesis. The substrate oxide layer was analysed by secondary ion mass spectrometry. The prepared CNTs were confirmed by Raman spectroscopy and were further characterised using scanning electron microscopy and transmission electron microscopy.     

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.     

Root growth of multi-wall carbon nanotubes by MPCVD

This work examines the relationships among the growth and interlayer reactions of carbon nanotubes (CNTs) to develop an effective process for controlling the nanostructure, orientation and characteristics of CNTs. Vertically oriented CNTs were successfully synthesized by microwave plasma chemical vapor deposition (MPCVD) with CH₄/H₂ as source gases. Additionally, the Ti and SiO₂ barrier layers and the Co catalyst were used in an experiment on the growth of CNTs on the Si wafer. Then, the SiO₂ barrier layer was deposited by low-pressure chemical vapor deposition (LPCVD). The Ti barrier layer and Co catalyst films were deposited on the Si wafer by physical vapor deposition (PVD). The deposited nanostructures were characterized by scanning and transmission electron microscopy, the results of which reveal that the deposited MWCNTs were grown under the influence of a catalyst on Si substrates with or without a barrier layer, by MPCVD. Vertically grown, dense MWCNTs attached to a catalytic film demonstrate that various MWCNTs penetrated the root particles. The diameter of the root particles, of approximately in the order of 100 nm, is larger than those of the tube, 10–15 nm. The well-known model of the growth of CNTs includes base- and tip-root growth. The interaction between the catalytic film and the supporting barrier layer is suggested to determine whether the catalytic particles are driven up or pinned down on the substrate during the growth.     

Synthesis and characterization of large area well-aligned carbon nanotubes by ECR-CVD without substrate bias

Large area, well-aligned carbon nanotubes (CNTs) were synthesized on porous silicon by electron cyclotron resonance chemical vapor deposition (ECR-CVD). No bias was applied on the substrate in this experiment. CH₄ and H₂ were used as source gases and Fe₃O₄ nanoparticles as the catalyst. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction spectroscopy (XRD), and Raman spectrum were used to evaluate the structure and composition. The results show that these CNTs have varying outer diameters from 10 to 90 nm and uniform length over 10 μm. They display hollow tubular and chain structures. The possible formation mechanism of aligned CNTs is discussed.