电场引发的嵌有碳纳米管的黑索金复合材料分解模拟

以电场作为引燃条件对含能材料的分解过程进行了研究。利用黑索金(RDX)单晶结构，构建了镶嵌有碳纳米管(CNT)的黑索金(RDX)复合结构模型，利用反应分子动力学模拟研究了该材料在外电场下的响应。结果表明构建的复合结构在方向沿CNT 的匀强电场下，能够以CNT 为中心形成反应热点；随着热点的成长，形成了自发行进的燃烧层，可以分解掉整个体系。     

界面势垒对碳纳米管场发射特性的影响

以界面势垒对碳纳米管(CNT)场发射的影响为研究目的,在硅衬底上引进很薄的二氧化硅层,以二氧化硅层作为绝缘势垒,然后在二氧化硅界面层上直接生长CNT,来研究二氧化硅绝缘势垒层对CNT场发射的影响。场发射结果为:Fowler-Nordheim(F-N)曲线分为两部分,高电场下偏离F-N曲线并趋于饱和。在双势垒模型的基础上,从电场在两势垒上的分布不同及电子在两势垒上的隧穿几率不同,理论上分析了界面势垒对场发射的影响:低电场下电子在界面势垒的隧穿几率大于在表面势垒的隧穿几率,界面势垒对场发射不起阻碍作用,场发射遵守F-N规律;高电场下电子在界面势垒的隧穿几率小于在表面势垒的隧穿几率,场发射偏离F-N规律。理论对实验结果进行了合理的解释。     

对碳纳米管阵列的场发射电场增强因子以及最佳阵列密度的研究

研究了外电场、碳纳米管自身线度、尤其管的阵列密度对碳纳米管的场发射性能的影响,从理论上深入探索碳纳米管阵列的电场增强因子并提出改善其场发射电子性能的有效途径.研究结果表明,碳纳米管阵列的电场增强因子的数量级一般为102—103,并对任何长径比的碳纳米管阵列,都对应着一个最佳阵列密度,当碳纳米管阵列密度取此最佳密度值时,其电场增强因子明显提高.这里的理论研究对弄清碳纳米管的场发射机理及实验合成高发射性能的碳纳米管阵列有一定的意义 关键词： 碳纳米管阵列 最佳阵列密度 电场增强因子 长径比     

离子轰击控制准直碳纳米管生长的研究

用CH₄,H₂和NH₃作为反应气体，利用等离子体增强热丝化学汽相沉积制备出准直碳纳米管，并用扫描电子显微镜研究了不同负偏压对准直碳纳米管生长的影响. 结果表明，随着负偏压的增大，准直碳纳米管的平均直径减小、平均长度增大. 由于辉光放电的产生，在衬底表面附近形成阴极鞘层，并在阴极鞘层内形成大量的离子和在衬底表面附近形成很强的电场. 离子在电场的作用下对衬底表面的强烈轰击将对准直碳纳米管的生长产生影响. 结合有关理论，分析和讨论了离子的轰击对准 关键词： 准直碳纳米管 离子轰击 负偏压     

一种平行背栅极碳纳米管阵列的场增强因子计算

建立一种平行背栅极碳纳米管阵列阴极,基于电场叠加原理,利用镜像电荷法对其进行计算,给出碳纳米管顶端表面电场增强因子。在此基础上,进一步分析器件各类参数对电场增强因子的影响。分析表明,碳纳米管阵列阴极具有最佳阵列密度,其对应碳纳米管间距大约为碳纳米管高度的两倍,靠阴极阵列边缘部位的碳纳米管发射电子能力比其中心部位的大。除了碳纳米管的长径比之外,栅极宽度、栅极厚度和栅极间距等也对电场增强因子有一定的影响:栅极越宽,场增强因子越大;而栅极厚度、栅极间距越大,场增强因子就越小。     

一种平行背栅极碳纳米管阵列的场增强因子计算

建立一种平行背栅极碳纳米管阵列阴极,基于电场叠加原理,利用镜像电荷法对其进行计算,给出碳纳米管顶端表面电场增强因子。在此基础上,进一步分析器件各类参数对电场增强因子的影响。分析表明,碳纳米管阵列阴极具有最佳阵列密度,其对应碳纳米管间距大约为碳纳米管高度的两倍,靠阴极阵列边缘部位的碳纳米管发射电子能力比其中心部位的大。除了碳纳米管的长径比之外,栅极宽度、栅极厚度和栅极间距等也对电场增强因子有一定的影响:栅极越宽,场增强因子越大;而栅极厚度、栅极间距越大,场增强因子就越小。     

阵列碳纳米管的石墨化程度

采用化学气相沉积法制备了阵列碳纳米管薄膜,对阵列碳纳米管的石墨化程度进行了系统研究。利用扫描电子显微镜(SEM)、拉曼光谱(Raman)对样品形貌以及结构进行了表征。探讨了不同实验参数对阵列碳纳米管石墨化程度影响的机理。结果发现,在一定催化剂浓度范围内,催化剂浓度过低时,阵列碳纳米管的石墨化程度较差,而随着催化剂浓度的增加,阵列碳纳米管的石墨化程度逐渐变好;生长石墨化程度较好的阵列碳纳米管需要合适的进液速度,进液速度过低或过高都会使得碳纳米管的石墨化程度变差;此外,生长石墨化程度较好的阵列碳纳米管也需要合适的生长温度,生长温度过低或过高都会使得碳纳米管的石墨化程度变差。     

快速生长超长定向碳纳米管阵列的制备及机理

 采用一种无模板的化学气相沉积法裂解金属有机物,以二茂铁为催化剂,二甲苯为碳源,利用单温炉加热装置在100 min内成功制备了2.7 mm超长定向碳纳米管阵列,生长速率高达27 μm·min^-1。运用扫描电子显微镜、透射电子显微镜、拉曼光谱对定向碳纳米管阵列进行形貌观察和表征,结果表明:制得的碳纳米管阵列具有优越的定向性和管结构,并且石墨化程度高。给出了快速生长超长定向碳纳米管阵列的优化制备条件,结合表征结果讨论了碳纳米管阵列的生长机制,认为超长碳纳米管阵列采用的是一种催化剂固定不动的开口生长方式,碳源和催化剂的连续供应保证了超长碳纳米管阵列的快速生长。     

电场调控的碳纳米管非线性光学开关及其管径效应

本文借助密度泛函理论方法获得了五个不同管径碳纳米管在外电场作用下的最优几何结构和相应的性质,研究了外电场对碳纳米管的结构和性质的调控作用.结果表明外电场导致了碳纳米管内部的电荷转移,引起了碳纳米管第一超极化率(β₀)的急剧增大.例如CNT(6, 3),当电场从0增大到工作电场F_w=80×10^-4 au时,碳纳米管的β₀值从0 au可增大到最大83695 au,导致了极大的β₀对比,因此碳纳米管成为新型的非线性光学(NLO)开关.新型NLO开关的管径效应表明,较大管径的碳纳米管具有更优的NLO开关性质.除此之外,电子吸收光谱表明这些碳纳米管具有小于300 nm和大于2500 nm的光学工作区,因此碳纳米管可成为一类新的灵敏、快速、可逆的紫外兼红外的NLO开关.     

氮掺杂及水分子吸附碳纳米管电子场发射第一性原理研究

对闭口碳纳米管(CNT)顶端分层掺氮及吸附不同数目水分子体系,运用第一性原理研究了有电场存在时的电子场发射性能.结果表明：掺氮并吸附水分子的CNT结构稳定;外电场愈强、水分子数愈多,体系态密度(DOS)向低能端移动幅度愈大且最高分子占据轨道(HOMO)/最低分子空轨道(LUMO)能隙愈小.吸附能,DOS/LDOS,HOMO/LUMO及其能隙分析一致表明,第三层氮掺杂CNT吸附不同数目水分子体系的场发射性能最佳. 关键词： 氮掺杂 水吸附 密度泛函理论 电子场发射     

Coupled process of plastics pyrolysis and chemical vapor deposition for controllable synthesis of vertically aligned carbon nanotube arrays

Efficient conversion of waste plastics into advanced materials is of conspicuous environmental, social and economic benefits. A coupled process of plastic pyrolysis and chemical vapor deposition for vertically aligned carbon nanotube (CNT) array growth was proposed. Various kinds of plastics, such as polypropylene, polyethylene, and polyvinyl chloride, were used as carbon sources for the controllable growth of CNT arrays. The relationship between the length of CNT arrays and the growth time was investigated. It was found that the length of aligned CNTs increased with prolonged growth time. CNT arrays with a length of 500 μm were obtained for a 40-min growth and the average growth rate was estimated to be 12 μm/min. The diameter of CNTs in the arrays can be modulated by controlling the growth temperature and the feeding rate of ferrocene. In addition, substrates with larger specific surface area such as ceramic spheres, quartz fibers, and quartz particles, were adopted to support the growth of CNT arrays. Those results provide strong evidence for the feasibility of conversion from waste plastics into CNT arrays via this reported sustainable materials processing.     

Nanofabrication by electrochemical routes of Ni-coated ordered arrays of carbon nanotubes

Ordered arrays of carbon nanotubes (CNT) have been coated by Ni nanoparticles and Ni thin films by using the chronoamperometry technique for nickel reduction. Two different kinds of nanotube arrays have been used: aligned bundles of CNT grown on Si substrates by chemical vapour deposition (CVD) and networks of CNT bundles positioned via a dielectrophoretic post-synthesis process between the electrodes of a multifinger device. The morphology and structure of the Ni-coated CNT bundles have been characterized by field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD). By changing the parameters of the electrochemical process, it is possible to modulate the morphological characteristics of the Ni deposits, which can be obtained in form of nanoparticles uniformly distributed along the whole length of the CNT bundles or of Ni thin films. A qualitative study of the nucleation and growth mechanism of Ni onto CNT has been performed using the theoretical model for diffusion-controlled electrocrystallization, and a correlation between growth mechanism and samples morphology is presented and discussed. The possibility to maintain the architecture of the pristine nanotube deposits after the Ni coating process opens new perspectives for integration of CNT/Ni systems in magnetic and spintronics devices.     

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)     

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.     

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)     

The effects of catalyst treatment on fast growth of millimeter-long multi-walled carbon nanotube arrays

An optimized strategy was developed for fast growth of millimeter-long CNT arrays using chemical vapor deposition (CVD). Growth temperature of 800 °C was firstly determined, and catalyst heat treatment conditions were then optimized to probe the full potential of growth rate. 1.5 mm long CNT arrays were obtained in 10 min under optimized growth and catalyst heat treatment conditions. The growth rate of CNT arrays strongly depends on the growth temperature and catalyst heat treatment. Insufficient reduction could not reduce iron oxide into metallic state or/and crack down catalyst film into particles, but excessive treatment may result in large particles due to Ostwald ripening process. This method would offer more freedoms in designing the fast growth of high-purity, long CNT arrays.     

Aligned Ni nanoparticle arrays encapsulated in carbon nanotubes

Using the carbon nanotube (CNT) arrays embedded in anodic aluminum oxide (AAO) template as an electrode, large amounts of Ni nanoparticles have been encapsulated into the CNTs by an alternating current (AC) electrodepostion technique. As deposited Ni nanoparticles with a typical size of 50–60 nm randomly nucleated on the CNT walls, thus inhomogeneously distributed in the CNTs. After annealing at 600 ^°C, the nanoparticles transformed into quasi-spherical structures with the diameter increasing to 60–80 nm. The quasi-spherical nanoparticles were aligned in orderly rows along the axis of the CNT channels. Magnetic hysteresis measured at 5 K showed that the coercivity was 450 Oe for the as-deposited sample and 385 Oe for annealed sample, with the applied magnetic field parallel with the CNT’s axis. The structures and magnetic properties were discussed for both as-deposited and annealed samples.     

The feasibility of producing MWCNT paper and strong MWCNT film from VACNT array

This study sought to produce carbon nanotube (CNT) pulp out of extremely long, vertically aligned CNT arrays as raw materials. After high-speed shearing and mixing nitric acid and sulfuric acid, which served as the treatment, the researchers produced the desired pulp, which was further transformed into CNT paper by a common filtration process. The paper’s tensile strength, Young’s modulus and electrical conductivity were 7.5 MPa, 785 MPa and 1.0×10⁴ S/m, respectively, when the temperature of the acid treatment was at 110°C. Apart from this, the researchers also improved the mechanical property of CNT paper by polymers. The CNT paper was soaked in polyethylene oxide, polyvinyl pyrrolidone, and polyvinyl alcohol (PVA) solution, eventually making the CNT/PVA film show its mechanical properties, which increased, while its electrical conductivity decreased. To diffuse the polymer into the CNT paper thoroughly, the researchers used vacuum filtration to fabricate a CNT/PVA film by penetrating PVA into the CNT paper. After a ten-hour filtration, the tensile strength and Young’s modulus of CNT/PVA film were 96.1 MPa and 6.23 GPa, respectively, which show an increase by factors of 12 and 7, respectively, although the material’s electrical conductivity was lowered to 0.16×10⁴ S/m.     

Acetic acid effects on enhancement of growth rate and reduction of amorphous carbon deposition on CNT arrays along a growth window in a floating catalyst reactor

The mm-long carbon nanotube (CNT) arrays were grown in a floating catalyst reactor, using xylene-ferrocene and a small amount of acetic acid as the feed. The CNT arrays deposited on a quartz substrate at several positions along the reactor were extensively characterized using Raman spectroscopy, scanning electron microscopy, X-ray diffraction, high-resolution transmission electron microscopy, and optical microscopy. Various characterization methods consistently reveal that the acetic acid additive to the feed alleviates deposition of amorphous carbon layer, which gradually thickens CNTs along the reactor. The acetic acid also resulted in a higher growth rate along the so-called growth window, where CNT arrays are deposited on the quartz substrate. High-performance liquid chromatography of extracted byproducts (PAHs) confirmed the presence of some polycyclic aromatic hydrocarbons. The solid weight of PAHs decreased upon addition of ferrocene as the catalyst precursor, as well as of acetic acid to xylene feed. The results suggest that primary light products of xylene pyrolysis can be competitive reactants for both catalytic and subsequent pyrolytic reactions. They may also be more efficient feeds for CNT growth than xylene itself.     

Structural and morphological dependence of carbon nanotube arrays on catalyst aggregation

Catalyst aggregation affects the growth of carbon nanotube (CNT) arrays in terms of tubular structures, waviness, entanglement, lengths, and growth density etc., which are important issues for application developments. We present a systematic correlation between the aggregation of catalyst on the SiO₂/Si substrate and the structure and morphology of CNT arrays. The thickness of the catalyst film has a direct effect on the areal density of the catalytic particles and then the alignment of the CNT array. Introducing alumina as buffer layer and annealing the catalyst film at low pressure are two effective approaches to downsize the catalyst particles and then the diameter, wall number of the CNTs. Both the size and areal density of the catalyst also change with the CNT growth in accordance with Ostwald ripening process, with the bottom of the CNT array varying from well-aligned to disordered and adhesion between catalyst particles and the substrate getting enhanced. Strategies including tuning the thickness of the catalyst film, changing buffer layer, controlling on the growth time and the system pressure were used to regulate the aggregation of the catalyst. CNT arrays from disordered to well-aligned, from multi-walled to few-walled and further to single-walled were reproducibly synthesized by chemical vapor deposition of acetylene.