Diameter-dependent thermal-oxidative stability of single-walled carbon nanotubes synthesized by a floating catalytic chemical vapor deposition method

In this paper, purified single-walled carbon naotubes (SWCNTs) with three different diameters were synthesized using a floating catalytic chemical vapor deposition method with ethanol as carbon feedstock, ferrocene as catalyst, and thiophene as growth promoter. The thermal-oxidative stability of different-diameter SWCNTs was studied by using thermal analysis (TG, DTA), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) analysis. The results indicate that small diameter SWCNTs (∼1 nm) are less stable and burn at lower temperature (610 °C), however, the larger diameter SWCNTs (∼5 nm) survive after burning at higher temperature (685 °C), the oxidation rate varies inversely with the tube diameter of SWCNTs, which may be concluded that the higher oxidation-resistant temperature of larger diameter SWCNTs can be attributed to the lower curvature-induced strain by rolling the planar graphene sheet for the larger diameter, so small tubes will become thermodynamically unstable.     

TEM investigation on the growth mechanism of carbon nanotubes synthesized by hot-filament chemical vapor deposition

Carbon nanotubes (CNTs) were synthesized using hot-filament chemical vapor deposition on Ni film-coated Si substrate. The CNTs were well-aligned perpendicular to the substrate. The as-grown CNTs were bamboo-like in their morphology, and were investigated using SEM and high-resolution transmission electron microscopy (HRTEM). The SEM and HRTEM studies show that the both ends of a CNT contain metallic catalytic particles, which is different from results previously reported. Our analysis results provide strong evidence that the metallic catalyst remains in a liquid state during nanotube growth. The upward-growth pulling force of the CNT layer elongates the liquid nanoparticles, which are finally broken into two parts. One part remains at the substrate surface (base of the CNTs) and is responsible for the catalytic growth of the CNTs. The other part is enclosed at the tip of the CNTs and is inactive during CNT growth.     

化学气相沉积法制备定向碳纳米管阵列

以二茂铁和二甲苯分别作为催化剂和碳源，采用一种无模板的化学气相沉积法，使用单温炉设备，成功地制备了高度定向的碳纳米管阵列.分别用扫描电子显微镜、透射电子显微镜和电子能量散射谱、拉曼光谱对碳纳米管阵列进行形貌观察和表征, 并研究了不同工艺参数对碳纳米管阵列形貌的影响.结果表明：在生长温度为800℃，催化剂浓度为0.02g/mL，抛光硅片上容易获得高质量的定向碳纳米管阵列，在此优化条件下生长的定向碳纳米管的平均生长速率可达25μm/min.     

Composited BCN/carbon fibers prepared by hot-filament chemical vapor deposition

The combined BCN/carbon fibers with porous configuration have been successfully prepared by hot-filament chemical vapor deposition (HF-CVD). The composited materials consist of carbon fiber inside covered by the cylindrical BCN films. The differences in the surface morphology and the diameter of the composite fibers are related to the different reactant gases. It is demonstrated that the elements of B, C, and N are chemically bonded with atomic-level BCN hybrid in the composite fibers. The resistance of the composite fibers is about 300 Ω which is 10 times higher than that of the isolated carbon fibers (27.5 Ω). When the applying voltage increases up to 8-15 V, the BCN films have been broken down and the resistance of composite fibers decreases to the typical value of the carbon fibers. The composite fibers with porous configuration have the strongly capacity to adsorb oxygen. The findings suggest that the combined BCN/carbon fibers are favorable for achieving high performance nano-optoelectronic and sensor devices.     

Controllable growth of individual, uniform carbon nanotubes by thermal chemical vapor deposition

We report on the controllable growth of individual, uniform carbon nanotubes using thermal chemical vapor deposition (CVD). We performed a detailed study of the various factors influencing the growth of single nanotubes. In particular, we investigated the role played by catalyst layer thickness, catalyst dot size, deposition temperature, and gas source pressure on the growth process of straight, single nanotubes. Straight, individual nanotubes with uniform diameter can be obtained by decomposition of 0.1 mbar of acetylene at a temperature of 800 °C over a 5 nm thick nickel film that is patterned into square dots with dimensions below 500 nm. We compare the performance of thermal CVD and of plasma enhanced CVD for growing individual nanotubes.     

Electrical transport properties of graphene-covered-Cu wires grown by chemical vapor deposition

We investigated the field-effect transistor (FET) characteristics of 15-μm graphene-covered copper wires (G-wires). Unlike the previously reported graphene FET, carries initially showed p-type like FET characteristics in two-terminal transport measurements. Our results indicate that the electrical transport processes in a G-wire FET occur in both the heavily p-doped contact and the p-doped radial graphene channel, as a p-channel. The interfacial potential barrier between the contact electrode and the radial graphene channel is small, but there is a radial potential barrier that limits electrical transport through the copper core in chemical vapor deposition (CVD) grown samples. The p-type FET characteristics appeared clearly after the oxidation of the G-wires.     

Rapid nucleation of diamond films by pulsed laser chemical vapor deposition

The nucleation of diamond films could be greatly enhanced on mirror-polished Si substrate by a pulsed Nd:YAG laser beam without any thermal- and plasma-assisted processes during a very short time. The nucleation density increased with decreasing laser power density from 1.38×10¹⁰ to 1.17×10⁹ W/cm² and deposition pressure from 1013 to 4 mbar. The pulsed laser beam made no contribution to enhance nucleation at substrate temperature as low as 650°C. X-ray diffraction measurements showed the (1 1 1) diffraction peak of diamond for the samples obtained using only pulsed laser during 40 min. The enhanced nucleation and growth of diamond crystallites were attributed to effective excitation of reactive gases and etching of non-diamond carbon phases by the pulsed laser beam.     

激光轴向偏焦法平整化CVD金刚石膜

利用Nd:YAG型金刚石精密激光切割机,采用激光轴向偏焦法对化学气相沉积（CVD）法制备的金刚石膜表面进行扫描式平整化处理,利用扫描电子显微镜（SEM）、粗糙度仪和金相显微镜对平整化后的金刚石表面进行表征,研究了激光充电电压和焦点位置对扫描凹槽宽度和深度的影响,以及扫描间距对平整化效果的影响。研究结果表明:扫描凹槽宽度随激光充电电压的升高而增大;凹槽深度随激光充电电压的升高而增大,随偏焦量的增大而增大。激光轴向偏焦法对CVD金刚石膜进行平整化处理后,其粗糙度显著减小,利用氢等离子体对其表面进行刻蚀处理,能够有效去除表层石墨,从而达到理想的平整化效果。     

场致发射阴极碳纳米管的热化学气相沉积法低温生长

结合丝网印刷和过滤阴极真空电弧法、离子束溅射方法，在普通玻璃衬底上制备催化剂图案，采用低温热化学气相沉积法(CVD)生长碳纳米管/纤维(CNTs)薄膜.研究了不同种类催化剂对CNTs薄膜生长及其场发射的影响.结果表明，在a-C:Co,Ni-Cu和Cu三种催化剂上没有获得明显的CNTs，在外加电场小于4.4V/μm时没有观察到场发射；而在Ni-Fe及Ni-Cr两种催化剂上获得了大量的CNTs，并且表现出良好的场发射性能，开启电场为2.5V/μm，这种热CVD有简单、低温等优点，在CNTs场发射显示器的阴极制备中有潜在的应用价值.     

激光轴向偏焦法平整化CVD金刚石膜

利用Nd：YAG型金刚石精密激光切割机,采用激光轴向偏焦法对化学气相沉积（CVD）法制备的金刚石膜表面进行扫描式平整化处理,利用扫描电子显微镜（SEM）、粗糙度仪和金相显微镜对平整化后的金刚石表面进行表征,研究了激光充电电压和焦点位置对扫描凹槽宽度和深度的影响,以及扫描间距对平整化效果的影响。研究结果表明：扫描凹槽宽度随激光充电电压的升高而增大;凹槽深度随激光充电电压的升高而增大,随偏焦量的增大而增大。激光轴向偏焦法对CVD金刚石膜进行平整化处理后,其粗糙度显著减小,利用氢等离子体对其表面进行刻蚀处理,能够有效去除表层石墨,从而达到理想的平整化效果。     

Substrate preparation techniques for direct investigation by TEM of single wall carbon nanotubes grown by chemical vapor deposition

We have investigated and evaluated different TEM sample preparation techniques for studying carbon single-walled nanotube (C-SWNT) nucleation and growth, issued from CVD processes when the catalyst is supported on a substrate. This kind of study requires means to observe individual and isolated tubes. It implies using synthesis conditions able to produce only a low density of tubes and to thin the substrate to electron transparency, to observe the nanotubes and the catalytic particles from which they have grown in their native state. We have tested two approaches, depending if the substrate is thinned after or before the synthesis. The low tube density requirement led us to exclude all the techniques where the substrate is thinned to electron transparency after the synthesis. We have shown, that, with this last approach, all TEM preparation techniques dramatically suffer from a lack of control of thin areas with respect to the location of the tubes, which is unknown. However we have demonstrated that the suitable approach is to perform synthesis directly on transparent substrates presenting several holes. We have tested the capabilities and the potentialities of these supports for studying the size distribution and composition of the catalytic particles, the nucleation mode, the diameter and helicity of the tubes. These results are very promising and represent an important step for performing specific nanoscale TEM analyses necessary for the study of the growth mechanism of nanotubes on substrates.     

Effect of alcohol sources on synthesis of single-walled carbon nanotubes

The effect of oxidant species forming an alcohol molecule for hot-filament chemical vapor deposition (HFCVD) on single-walled carbon nanotubes (SWCNTs) growth has been investigated. To use a graphite rod as a filament for HFCVD to decompose alcohol sources, contamination-free sample surface can be obtained and SWCNTs are successively and densely grown at a lower temperature than those by conventional thermal CVD. It is found that the higher the molecule number of alcohol among CH₃OH, C₂H₅OH, and 2-C₃H₇OH is, the lower the initial growth rate of SWCNTs is. As for CH₃OH, diameter distribution of SWCNTs is dynamically changed with the growth time passed, and a negative growth rate is observed at the later stage of growth. The growth kinetics depending on the alcohol sources is discussed on the basis of a capability of the oxidant species to burn away SWCNTs and deactivation of Co catalysts used for the growth.     

Synthesis of flower-like WS2 by chemical vapor deposition

Flower-like tungsten disulfide (WS₂) with a diameter of 5-10 μm is prepared by chemical vapor deposition (CVD). Scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), Raman spectroscopy, and ultraviolet-visible (UV-vis) spectroscopy are used to characterize its morphological and optical properties, and its growth mechanism is discussed. The key factors for the formation of flower-like WS₂ are determined. Firstly, the cooling process causes the generation of nucleation dislocations, and then the "leaf" growth of flower-like WS₂ is achieved by increasing the temperature.     

化学气相沉积法制备Zn2GeO4纳米线及其发光性质的研究

利用化学气相沉积法（CVD）,气-液-固（VLS）生长法则在表面溅有金属Au催化剂层的1 cm×1 cm的Si片上制备三元Zn₂GeO₄纳米线。X射线衍射仪（XRD）测试结果表明,锌源与锗源质量比为8：1时可成功制备出Zn₂GeO₄纳米结构;扫描电子显微镜（SEM）测试结果表明,Zn₂GeO₄纳米线直径为100 nm,长度为10~11 μm;光致发光（PL）测试结果表明,Zn₂GeO₄纳米线在432和480 nm处具有两个发光峰,最后对其生长机理进行了分析。     

热丝化学气相沉积技术低温制备多晶硅薄膜的结构与光电特性

以金属W和Ta为热丝，采用热丝化学气相沉积 ，在250℃玻璃衬底上沉积多晶硅薄膜.研究了热丝温度、沉积气压、热丝与衬底间距等沉积参数对硅薄膜结构和光电特性的影响，在优化条件下获得晶态比X_c＞90%，暗电导率σ_d=10^-7—10-6Ω ^-1cm^-1，激活能E_a=0.5eV，光能隙E_opt≤1.3 eV的多晶硅薄膜. 关键词： 多晶硅薄膜 热丝化学气相沉积 光电特性     

高质量大面积石墨烯的化学气相沉积制备方法研究

石墨烯因其奇特的能带结构和优异的物理性能而成为近年来大家研究的热点, 但是目前单层石墨烯的质量与尺寸制约了其实际应用的发展. 本文采用常压化学气相沉积(CVD)方法, 基于铜箔衬底, 利用甲烷作为碳源制备了高质量大面积的单层与多层石墨烯. 研究发现: 高温度、稀薄的甲烷浓度、较短的生长时间以及合适的气体流速是制备高质量、大面积石墨烯的关键. Raman光谱, 扫描电子显微镜、透射电子显微镜等表征结果表明: 制备的石墨烯主要为单层, 仅铜箔晶界处有少量多层石墨烯. 电学测试表明CVD制备的石墨烯在低温时呈现出较明显的类半导体特性; 薄膜电阻随外界磁场的增大而减小.     

Kinetics of chemical vapor deposition of SiC from methyltrichlorosilane and hydrogen

In this study, the dependence of the deposition rate on processing parameters, such as temperature, and partial pressure is studied by chemical vapor deposition from mixture of methyltrichlorosilane (CH₃SiCl₃, MTS) and hydrogen. The kinetics investigation is carried out in a tubular, hot-wall reactor coupled to a sensitive magnetic suspension microbalance. The results show that the active energy limited by surface reactions is 188 kJ/mol. In the case, the deposition rate is linear to the partial pressure of MTS and the square of partial pressure of hydrogen. SiCl₂ and CH₃ are proposed as the effective precursor for SiC. A reaction model was proposed concluding gas phase reactions and surface reactions. The theoretical relation between deposition rate and partial pressures of MTS and H₂ was in a good accordance with experimental results.     

Structure and magnetic properties of FeCo nanoparticles encapsulated in carbon nanotubes grown by microwave plasma enhanced chemical vapor deposition

Plasma enhanced chemical vapor deposition is a simple technique for preparing magnetic nanoparticles encapsulated in carbon nanotubes. We employed alloy catalysts when growing carbon nanotubes to control the composition and magnetic properties of encapsulated nanoparticles. Single-crystal nanoparticles were successfully encapsulated in carbon nanotubes, and their crystal structure varied depending on the composition of the alloy catalysts. The coercive force of nanoparticles also varied according to the composition of the catalysts.