Comparison of Structure and Conductivity of Multiwall Carbon Nanotubes Obtained over Ni and Ni/Fe Catalysts

Abstract

Multiwall carbon nanotubes (MWNT) were produced by pyrolysis of acetonitrile (CH₃CN) on metallic particles of Ni and Ni/Fe at 850°C. The special program for statistical treatment of electron micrograph images was developed. Research of diameter distribution of MWNT grown over different catalysts was carried out. Two kinds of carbon nanotubes with different diameter and microstructure are formed on Ni catalyst. The MWNT with smaller diameter and cylindrical packing of layers were found to have the higher conductivity.     

Modeling Electronic Properties of Multiwall Carbon Nanotubes

Reviewing experimental results and based on the physical reasoning, we present a basic circuit model for Multiwall carbon nanotubes (MWCNTs), which can simulate different experimental results. Investigation of different results confirms the severe effects of fabrication process (nanotube and contacts) on electronic properties of the MWCNTs. The circuit model has been developed to show the performance improvements of a CNT interconnect when the single-wall carbon nanotube (SWCNT) is replaced by an MWCNT. To calculate the current-voltage characteristic and the switching delay of MWCNTs, we have simulated their DC and AC properties, respectively, using the developed transmission line models. Based on the physical models, the elements of the circuit model can be changed so that the simulation and the practical measurements for an MWCNT can correspond. Switching Delays of the MWCNTs and SWCNTs are calculated and compared for different cases.     

Fe/Mo/MgO冻凝胶催化剂大规模合成单壁纳米碳管

通过冷冻干燥法制备了高活性的Fe/Mo/MgO冻凝胶催化剂.在1000℃下用该催化剂催化裂解甲烷,大规模合成了高质量的单壁纳米碳管(SWNTs),利用SEM、TEM、HRTEM、TGA和Raman等分析手段对所制备的SWNTs进行了表征.结果表明,冷冻干燥法制备催化剂合成的粗产品中SWNTs含量高达56wt%,管径分布窄,在0.80～0.95 nm之间,形态以束状为主.Fe/Mo/MgO催化剂极易被酸去除,提纯后的SWNTs纯度高达95%以上.     

调变Ni／Mo／MgO催化剂中Ni／Mo比例可控合成薄壁碳纳米管

采用摩尔分数1%Ni及负载少量Mo的Ni/MO/MgO催化剂裂解甲烷合成薄壁碳纳米管.通过SEM、TEM、XRD和Raman光谱表征方法研究了碳纳米管直径和催化剂中Ni/Mo比例关系.实验发现:通过控制Ni/Mo比例可以调变催化剂颗粒大小以及活性相.TEM及XRD表征发现,随着Ni/Mo比例的降低,金属Mo相逐渐从NiMo合金相中析出.NiMo合金相对应的活性组分颗粒很小,容易催化裂解甲烷形成薄壁碳纳米管;而后析出的Mo相则主要形成了大管径厚壁的碳纳米管.当Ni/Mo比例为6时可以高选择性地获得窄分布,内径为1.3nm,外径为3.0nm的溥壁碳纳米管.Raman光谱进一步验证了碳纳米管含有较少的缺陷.薄壁碳纳米管形成的关键因素主要体现为碳在其表而的快速扩散以及小颗粒的碳纳米管催化剂活性相控制.     

Carburization of Fe/Ni Catalyst for Efficient Growth of Single‐Walled Carbon Nanotubes

Scale‐up production of single‐walled carbon nanotubes (SWNTs) with high quality and purity is in pursuit, since the subsequent post purification treatment of residual metal or amorphous carbon is complicated and restricts further applications. Here, a compatible method to efficiently synthesize pure SWNTs on various supporters by using the precarburized Fe/Ni catalysts is reported. The preparation of catalysts is achieved by gas phase deposition together with CO gas at proper temperature, and the carburization of metal particles occurring simultaneously contributes to the size limitation of catalysts. By using micro‐quartz sand as a recyclable supporter, high‐quality SWNTs with a yield of 50 mg h^?1 are prepared with 60% metal precursor utilization, 81% carbon source utilization, and only 0.12% (m/m) metal residues. Taking advantage of carburized Fe/Ni catalysts and appropriate supports makes it possible to balance the quantity, purity, and quality among SWNTs growth. Furthermore, this method provides a straightforward pathway to strongly combine SWNTs and diverse composite materials for further potential applications.     

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。     

钴/碳纳米管催化剂CVD法制备碳纳米管

以乙烯为碳源、多壁碳纳米管为载体负载钴作为催化剂,利用CVD法制备出了高质量的多壁碳纳米管.利用扫描电子显微镜(SEM)对催化剂的形貌进行了表征,利用透射电子显微镜(TEM)、X射线衍射仪(XRD)以及差热-热重(TG-DTA)方法对产物进行了表征.发现在最佳裂解温度770℃下制备的多壁碳纳米管直径分布均匀、曲率小、纯净、产率高,更重要的是不具有难处理的氧化物(如Al2O3)载体,充分体现了碳纳米管作为载体的优越性.     

超临界干燥法制备催化剂合成单壁纳米碳管及表征

采用超临界干燥法制备了活性高、比表面大的Fe/Mo/Al₂O₃催化剂.通过超临界干燥,催化剂的比表面由294m²/g提高到401m²/g.在1000℃下用该催化剂催化裂解甲烷, 合成了大产量、高质量的单壁纳米碳管(SWNTs).利用SEM、TEM、HRTEM、TGA 和Raman等手段对所制备的SWNTs进行了表征.结果表明:超临界法制备催化剂合成的粗产品中SWNTs含量在30%以上,大大高于同一配方催化剂采用常规干燥法的产率(约2%); SWNTs的管径分布在0.8-1.0nm之间,其形态以束状为主.     

Fe/Fe_3C填充的碳纳米管复合材料的制备与微波吸收性质

利用化学气相沉积法,以乙醇为碳源,二茂铁为催化剂前驱物,对二氯苯为添加剂,制备了Fe/Fe3C纳米线填充的碳纳米管复合材料,并通过SEM、XRD、HRTEM等分析方法对产物的形貌和微结构进行了研究。实验结果表明对二氯苯对碳纳米管的填充起决定作用,产物中Fe/Fe3C纳米线填充率可达33%;使用该复合材料制备的吸波涂层在厚度为2mm、频率为4.5GHz时有强吸收峰,厚度增加时吸收峰往低频方向移动,表明此材料有望在低频段实现对电磁波的有效吸收。     

Synthesis of binary and triple carbon nanotubes over Ni/Cu/Al2O3 catalyst by chemical vapor deposition

Novel binary and triple carbon nanotubes (CNTs) with one common catalytic particle encapsulated have been synthesized using Ni/Cu/Al₂O₃ catalyst, which was produced by a sol-gel method. But when using Ni/Al₂O₃ as catalyst, a mass of common CNTs, that is, one CNT with one catalytic particle encapsulated, was obtained. The results showed that copper-element doping to the Ni/Al₂O₃ catalyst played a key role in the synthesis of CNTs, signifying a novel approach to modify the Ni/Al₂O₃ catalyst. Based on the transmission electron microscopy observations, a simple growth mechanism was developed to describe the growth of the binary or triple CNTs, which could be well explained by a diffusion segregation process.     

碳纳米管和镓掺杂碳纳米管场发射性能研究

采用催化热解方法分别 制备出碳纳米管和镓掺杂碳纳米管, 并利用丝网印刷工艺将其制备成纳米管薄膜. 对此薄膜进行低场致电子发射测试表明, 碳纳米管和镓掺杂纳米管开启电场分别为2.22和1.0V/μm, 当外加电场为2.4V/μm, 碳纳米管发射电流密度为400μA/cm², 镓掺杂纳米管发射电流密度为4000μA/cm². 可见镓掺杂碳纳米管的场发射性能优于同样条件下未掺杂时的碳纳米管. 对镓掺杂纳米管场发射机理进行了探讨.     

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.     

单壁碳纳米管的制备及生长特性研究

采用Fe/MgO作为催化剂 ,催化裂解CH4制备了较纯的单壁碳纳米管 ,用TEM和Raman对碳纳米管进行了表征 ,对不同生长温度下制备的碳纳米管Raman径向呼吸振动峰 (RBM)进行了分析 ,研究了生长温度对单壁碳纳米管生长特性和结构特性的影响     

Carbon Nanotubes Grown by RF Heating and Their Morphological and Structural Properties

Multiwall and single-wall carbon nanotubes were synthesized on Fe-Co/CaCO₃ and a Fe-Co/MgO catalyst system, respectively, by using two different catalytic chemical vapor deposition methods, external furnace (EF) heating and radio frequency (RF) excitation. The carbon nanotubes synthesized with radio frequency excitation have a smaller outer diameter, fewer layers (smaller outer/inner diameter ratio), and better crystalline properties than the nanotubes grown with external furnace heating. The radio frequency process was found to be responsible for a faster growth rate of the carbon nanotubes over longer periods of time due to a higher localized heating. These findings can be explained by the skin currents induced in the metallic catalytic clusters, which keep the catalysts active for longer periods of time and diminish the amount of noncrystalline carbon formed in the synthesis process.     

特定手性单壁碳纳米管的可控生长

单壁碳纳米管具有优异的电学、光学、热学、力学等性能,可能成为未来纳米器件的支撑材料之一。实现碳纳米管的结构可控生长制备依然面临着严峻的挑战。其中手性控制是单壁碳纳米管可控制备的最大挑战,它的实现标志着直径、壁数、手性角及导电属性等的可控制备。以特定手性单壁碳纳米管的可控生长为中心,分别综述了利用化学气相沉积法在粉体生长与表面生长两方面实现手性可控生长的研究进展,并在此基础上总结出基本思路,为实现单一手性碳纳米管的可控制备奠定基础。     

The Intramolecular Junctions of Carbon Nanotubes

For the miniaturization of microelectronics, carbon nanotubes (CNTs) are regarded as ideal candidates for the next generation of nanoelectronics because of their excellent properties. To realize CNT‐based electronics, intramolecular junctions are required components, which can not only connect different CNTs for integration, but can also act as functional building blocks in the circuit, such as rectifiers, field‐effect transistors, switches, amplifiers, photoelectrical devices, etc. Therefore, intense attention has been focused on this topic and many advances have been achieved, especially in recent years. On the other hand, some challenges also exist. To provide researchers with a comprehensive overview of this field, this review discusses the synthesis, properties, and applications of intramolecular junctions of CNTs in detail. Among them, the applications of CNT integration are discussed specially. Furthermore, a brief summary and an outlook of future work are provided.

     

Carbon nanotube synthesis over glow discharge-treated Ni/AAO membrane

Glow discharge plasma has been widely used in metal supported catalyst preparation. In this paper, this non-thermal plasma was applied for the fabrication of Ni/AAO membrane. This process, including incipient wetness impregnation, drying, plasma treatment and calcinations, is similar with the preparation of supported catalyst. XPS analysis of Ni/AAO membrane indicated the enrichment of nickel element in membrane nanopores during plasma treatment. As-prepared AAO membrane was used in the synthesis of carbon nanotube arrays by corona discharge enhanced chemical vapor deposition. They were much different in morphology with that from conventional Ni/AAO membrane without glow discharge treatment. In addition, the NiO nanoparticles were highly dispersed in nanotube walls.     

The Pattern Growth of Carbon Nanotubes by Self-assembled Monolayers Techniques

The well controllable selective growth of carbon nanotubes (CNTs)on the desired area is an important issue for their future applications. In this study, a novel method for selective growth of CNTs was proposed by using the technology of self-assembly monolayers (SAMs) and the Fe-assisted CNTs growth. The Si wafers with the a: Si/Si3N4 layer patterns were first prepared by low pressure chemical vapor deposition (LPCVD)and lithography techniques to act as the substrates for selective deposition of SAMs. The selectivity of SAMs from APTMS solution (N-(2-aminoethyl)-3-aminopropyltrimethoxsilane) is based on its greater reactivity of head group on a-Si than Si3N4 films. The areas of pattern with SAMs will first chelate the Fe3 ions by their diamine-terminated group. The Fe3 ions were then consolidated to become Fe-hydroxides in sodium boron hydride solution to form the Fe-hydroxides pattern. Finally, the Fe-hydroxides pattern was pretreated in H plasma to become a well-distributed Fe nano-particles on the surface, and followed by CNTs deposition using Fe as catalyst in a microwave plasma-chemical vapor deposition (MP-CVD) system to become the CNTs pattern. The products in each processing step, including microstructures and lattice images of CNTs, were characterized by contact angle measurements, scanning electron microscopy(SEM), XPS, Auger spectroscopy, transmission electron microscopy (TEM) and high resolution TEM (HRTEM)deposition. The results show that the main process parameters include the surface activation process and its atmosphere, consolidation time and temperature, H plasma pretreatment. The function of each processing step will be discussed.     

The Pattern Growth of Carbon Nanotubes by Self-assembled Monolayers Techniques

The well controllable selective growth of carbon nanotubes (CNTs)on the desired area is an important issue for their future applications. In this study, a novel method for selective growth of CNTs was proposed by using the technology of self-assembly monolayers (SAMs) and the Fe-assisted CNTs growth. The Si wafers with the a ： Si/Si3N4 layer patterns were first prepared by low pressure chemical vapor deposition (LPCVD)and lithography techniques to act as the substrates for selective deposition of SAMs. The selectivity of SAMs from APTMS solution (N-(2-aminoethyl)-3-aminopropyltrimethoxsilane) is based on its greater reactivity of head group on a-Si than Si3N4 films. The areas of pattern with SAMs will first chelate the Fe3 ions by their diamine-terminated group. The Fe^3 ions were then consolidated to become Fe-hydroxides in sodium boron hydride solution to form the Fe-hydroxides pattern. Finally, the Fe-hydroxides pattern was pretreated in H plasma to become a well-distributed Fe nano-particles on the surface, and followed by CNTs deposition using Fe as catalyst in a microwave plasma-chemical vapor deposition (MP-CVD) system to become the CNTs pattern. The products in each processing step, including microstructures and lattice images of CNTs, were characterized by contact angle measurements, scanning electron microscopy (SEM), XPS, Auger spectroscopy, transmission electron microscopy (TEM) and high resolution TEM (HRTEM) deposition. The results show that the main process parameters include the surface activation process and its atmosphere, consolidation time and temperature, H plasma pretreatment. The function of each processing step will be discussed.