对PECVD制备碳纳米管的研究和探讨

高纯度和高产率的制备碳纳米管是碳纳米管研究的一个重点。目前制备碳纳米管的方法有电弧法、激光蒸发法、化学气相沉积法(又称CVD法)和模板法等。本文主要介绍采用PECVD化学气相沉积法制备碳纳米管,并对该种方法制备碳纳米管进行了系统的研究和探讨。     

多孔氧化铝模板催化制备定向碳纳米管阵列

在不加过渡金属做催化剂的前提下,利用化学气相沉积法在二次阳极氧化法制得的多孔氧化铝模板中制备沉积了定取向碳纳米管阵列。考察了不同沉积温度以及退火处理对沉积结果的影响。温度达到600℃以上时,能得到开口的、定取向的多壁碳纳米管阵列；当沉积温度降至550℃左右时,沉积结果中存在碳纳米管、纳米纤维以及类似于弯曲的竹节状的结构；温度继续降低至500℃以下时,不能得到碳纳米管或碳纳米纤维；从实验结果中可以得出,在氧化铝模板中沉积碳纳米管过程中氧化铝起到了催化乙炔裂解以及催化沉积的碳石墨化成碳纳米管两种作用。另外,退火处理虽然能够提高沉积的碳纳米管的石墨化程度,但是也可能会引入新的缺陷。     

石墨基底上垂直生长碳纳米管为芯的碳锥结构

采用一种改进的化学气相沉积方法，成功地在石墨基底上自组装生长出以碳锥为支撑的、碳纳米管为芯的新型功能材料.该结构的材料可以用作扫描电子显微镜探针和场发射电子显微镜的针尖.利用电子显微镜研究了不同合成条件对该碳纳米管与碳锥结构生长的影响，给出了最优生长条件，并讨论了生长机制. 关键词： 碳锥 碳纳米管 化学气相沉积 场发射     

多壁碳纳米管膜湿敏特性的研究

研究了多壁碳纳米管(MWNTs)薄膜的湿敏特性，实验所用的多壁碳纳米管是用热灯丝化学气相沉积法(CVD)合成的.分别对未修饰和修饰的多壁碳纳米管膜温度和湿度特性进行研究后发现，修饰的多壁碳纳米管对温度和湿度非常敏感，且对湿度的响应时间和恢复时间短，重复性好.而未修饰的多壁碳纳米管对温度和湿度不太敏感.对修饰多壁碳纳米管的湿敏特性进行了理论分析，给出了其理论表示式. 关键词： 多壁碳纳米管 化学修饰 湿敏特性 物理吸附     

非晶空心碳球的制备及生长机制

采用射频等离子体增强化学气相沉积技术,在CH4/H2的气氛中合成了非晶空心碳球.利用SEM,TEM,拉曼光谱对样品的形貌、成分和结构进行了表征.非晶空心碳球的直径在100～800nm之间,分布在弯曲的碳纳米管丛中.非晶空心碳球的生长机制可能为膨胀生长.     

LPCVD法制备碳纳米管薄膜及其场发射性能的研究

采用低压化学气相沉积法(LPCVD)在镍片上直接制备碳纳米管(CNTs)薄膜,系统地研究了生长温度(500~800℃)对碳纳米管薄膜形貌、结构及场发射性能的影响,并对此方法的生长机理进行了分析。当温度从500℃升高到650℃时,碳纳米管的生长速率随着温度升高而增大,而温度继续上升,速率则明显减小。利用扫描电镜(SEM)和拉曼光谱仪表征和检测了碳纳米管薄膜的形貌和结构。碳纳米管的管径、长度、一致性和晶化程度随温度都有明显的变化。同时还对碳纳米管薄膜的场发射特性进行了测试,对其场发射机理进行了深入地探讨,表明温度对碳纳米管的性能有很大影响,并存在最优化的温度条件。实验结果表明碳纳米管薄膜的形貌、结构及其场发射性能可通过生长温度进行一定范围的控制。     

生长参数对碳纳米管阵列制备的影响

利用化学气相沉积法在沉积铁纳米颗粒的硅衬底上制备了垂直方向高度有序的碳纳米管阵列．扫描电子显微镜的观测发现，碳纳米管阵列的形貌受到若干生长参数的影响，包括催化剂颗粒大小、反应温度和反应气体的分压等．研究发现，当反应温度升高，或反应气体中碳源气体含量增加时，碳纳米管变粗、变短．当催化剂薄膜的厚度减小时，碳纳米管的直径随之减小而纳米管阵列的高度则先增后减，有一个最大值．这些结果表明，碳纳米管的直径和阵列的高度可通过选择合适的反应温度、匀胶机转速和反应气比率来调节．     

真空热处理碳纳米管的储氢性能研究

研究了真空热处理对多壁碳纳米管(MWNTs)电化学储氢性能的影响.采用化学气相沉积法(CVD)制备碳纳米管，碳纳米管与LaNi₅储氢合金按质量比1∶10混合，制作成CNTs-LaNi₅电极.电解池采用三电极体系，6mol/L KOH为电解液，Ni(OH)₂为正极，Hg/HgO为参比电极.实验结果表明，在相同的充放电条件下，850℃时CNTs-LaNi₅电极的储氢性能最好，克容量最大为503.6mAh/g，相应的平台电压高达1.18V.从500—850℃随着温度升高，放电量有较大幅度的增加，但到950℃时放电量反而下降.由此可见，碳纳米管的热处理温度对碳纳米管的电化学储氢性能有着较大的影响. 关键词： 碳纳米管(CNTs) 储氢性能 5合金')" href="#">LaNi₅合金 化学气相沉积法(CVD法)     

气体滞留时间对高速沉积的微晶硅薄膜性能的影响分析

实现高速沉积对于薄膜微晶硅太阳电池产业化降低成本是一个重要手段.采用超高频等离子体增强化学气相沉积(VHF-PECVD)技术，实现了微晶硅硅薄膜的高速沉积，并通过改变气体总流量改变气体滞留时间，考察了气体滞留时间在化学气相沉积(CVD)过程中对薄膜的生长速率以及光电特性和结构特性的影响.采用沉积速率达到12?/s的高速微晶硅工艺制备微晶硅电池，电池效率达到了5.3％. 关键词： 气体滞留时间 高速沉积 微晶硅 超高频等离子体增强化学气相沉积     

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.     

氢气与氮气对硼碳氮纳米管生长的影响

在对不同温度和不同催化剂对硼碳氮(BCN)生长影响研究的基础上，进一步研究了氮气与氢气对高温热解法制备BCN纳米管结构、产量等的影响.实验中发现氮气在制备过程中只对BCN纳米管的产量有微小影响，对所生成的纳米管的结构有一定影响，气流量太小时，乙二胺的转化率低，气流量太大时，会在所生成的BCN纳米管管壁上出现断裂生长现象.与氮气不同的是氢气不仅对所生成的纳米管的结构有很大影响，还对产量有明显影响，当制备过程中没有氢气时，所生成的BCN纳米管有明显的弯曲，甚至出现了急剧的弯折，大部分管壁附着无定形碳，还伴随中 关键词： BCN纳米管 热解 氢气 氮气     

Electron microscope vualization of muliphase fluids contained in closed carbon nanotubes

Aqueous multiphase fluids trapped in closed multiwall carbon nanotubes are visualized with high resolution using transmission electron microscopy (TEM). The hydrothermally synthesized nanotubes have inner diameter of 70 nm and wall thickness 20 nm, on average. The nanotubes are hydrophilic due to oxygen groups attached on their wall surfaces. Segregated liquid inclusions contained in the nanotubes under high pressure can be mobilized by heating. A resistive heating stage is utilized to heat a thin membrane inside a nanotube, causing the membrane to evaporate slowly and eventually pinch off. Focused electron beam heating is employed as a second means of thermal stimulation, which results in localized heating. With the latter method, gas/liquid interface motion is observed inside the thin channel of a carbon nanotube. Experiments like the ones presented herein may help understand the dynamics of fluids contained in nanoscale channels.     

阳极氧化法制备Y型TiO2纳米管

在含有质量分数为0.5%的NH₄F和体积分数为5% 的H₂O的乙二醇混合溶液中,采用三步阳极氧化法制备了表面形貌高度有序的Y型TiO₂纳米管阵列。讨论了钛片预处理过程对优化TiO₂纳米管阵列表面形貌的影响以及采用升温法制备Y型TiO₂纳米管的内在机理,并在较宽的温度范围内(20~60 ℃)对钛片进行阳极氧化。实验结果表明当阳极氧化第三步的电解液温度设置在40 ℃以上时,Y型TiO₂纳米管阵列的顶端将出现环状纳米线、管壁破裂以及管长减小等现象,不利于保证Y型TiO₂纳米管阵列的整体质量。因此,30~40 ℃是选取阳极氧化第三步温度的理想范围。     

Investigation of metal-containing carbon nanostructures prepared from functional polymers

Metal-containing carbon nanostructures are prepared by heating poly(vinyl alcohol) in mineral media with a lamellar structure at a temperature below 300°C. It is demonstrated that three possible types of nanostructures can be formed, namely, multilayer carbon nanotubes, spherical carbon nanoparticles, and finely crystalline carbon structures. According to the data of transmission electron microscopy, the nanotube size falls in the range from 50 to 300 nm and the nanotubes themselves have a stranded structure.     

Atomic structure of boron nitride nanotubes with an armchair-type structure studied by HREM

Hexagonal networks of boron nitride (BN) nanotubes were investigated by high-resolution electron microscopy (HREM) and image simulation. From HREM images, lattice planes of {002} and hexagonal rings of a BN nanotube were confirmed. Asymmetrical layer arrangements were found, and a structure model for double-walled BN nanotube with an armchair-type structure has been proposed.     

Synthesis and field-emission of aligned SnO2 nanotubes arrays

Aligned tin dioxide (SnO₂) nanotubes have been synthesized by high-frequency inductive heating. Nanotubes with high yield were grown on silicon substrates in less than 5 min, using SnO₂ and graphite as the source powder. Scanning electron microscopy and transmission electron microscopy showed nanotube with diameters from 50 to 100 nm and lengths up to tens of mircrometers. The SnO₂ nanotubes synthesized under the optimum condition have better field-emission characteristics. The turn-on field needed to produce a current density of 10 μA/cm² is found to be 1.64 V/μm. The samples show good field-emission properties with a fairly stable emission current. This type of SnO₂ nanotubes can be applied as field emitters in displays as well as vacuum electric devices.     

催化裂解CH4制备碳纳米管的影响因素

以柠檬酸法制备的Fe MgO、Co MgO和Ni MgO为催化剂 ,CH4 为碳源气 ,H2 为还原气 ,在 873、973和 10 73K制备出碳纳米管 ,通过TEM和拉曼光谱表征 ,讨论了催化剂、制备温度、反应时间等因素对碳纳米管形貌、产率和内部结构的影响 .结果表明 :不同的催化剂在相同的温度下制备的碳纳米管的形态和内部结构有很大的差异 .其中Fe MgO催化剂制备的碳纳米管管径粗 ,且大小不均匀 ,而Ni MgO催化剂制备的碳纳米管管径较细、较均匀 .碳纳米管的产率随着裂解温度的变化而改变 .Fe MgO催化剂制备碳纳米管的产率随制备温度的升高而提高 ,而Ni MgO催化剂制备碳纳米管的产率随制备温度的升高而降低 .Fe MgO催化剂制备碳纳米管 ,在10 73K甚至更高的制备温度才能达到其最高产率 .Co MgO催化剂制备碳纳米管的产率在 973K左右产率较高 ,而用Ni MgO催化剂制备碳纳米管 ,则在 873K甚至更低的制备温度就能达到最高产率 .反应时间与碳纳米管的产率不成正比 ,有一最佳反应时间 ,如Ni MgO催化剂的最佳反应时间为 2h .     

Catalytic activity of Fe, Co and Fe-Co-MCM-41 for the growth of carbon nanotubes by chemical vapour deposition method

Iron, cobalt and a mixture of iron and cobalt incorporated mesoporous MCM-41 molecular sieves were synthesised by hydrothermal method and used to investigate the rules governing their nanotube producing activity. The catalysts were characterised by XRD and N₂ sorption studies. The effect of the catalysts has been investigated for the production of carbon nanotubes at an optimised temperature 750 °C with flow rate of N₂ and C₂H₂ is 140 and 60 ml/min, respectively for a reaction time 10 min. Fe-Co-MCM-41 catalyst was selective for carbon nanotubes with low amount of amorphous carbon with increase in single-walled carbon nanotubes (SWNTs) yield at 750 °C. Formation of nanotubes was studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. Transmission electron microscope and Raman spectrum was used to follow the quality and nature of carbon nanotubes formed and the graphitic layers and disordered band, which shows the clear evidence for the formation of SWNTs, respectively. The result propose that the diameter of the nanotubes in the range of 0.78-1.35 nm. Using our optimised conditions for this system, Fe-Co-MCM-41 showed the best results for selective SWNTs with high yield when compared with Fe-MCM-41 and Co-MCM-41.     

Magnetic field dependence of the hexagonal to isotropic transition temperature of a single-walled carbon nanotubes dispersed lyotropic liquid crystal

We have carried out electrical conductivity studies on a single-walled carbon nanotubes dispersed lyotropic liquid crystal consisting of 50 wt.% TX-100 in water as a function of magnetic field and temperature. This system exhibits hexagonal and isotropic phases on heating. For all the applied magnetic fields, the temperature dependence of electrical conductivity of the carbon nanotubes dispersed lyotropic liquid crystal system exhibits a discontinuous change at the hexagonal to isotropic transition temperature. We find that the magnetic field dependence of the hexagonal to isotropic transition temperature is similar to that of the viscosity of the system. Using photo images of the sample, we find that the carbon nanotubes in the lyotropic liquid crystal form magnetic field dependent aggregates. We find spherical, rod and hook-like nanotube aggregates for low and high applied magnetic fields respectively. These nanotube aggregates alter the viscosity of our system which in turn alters the transition temperatures.     

Laser heating method for estimation of carbon nanotube purity

A new method of a carbon nanotube purity estimation has been developed on the basis of Raman spectroscopy. The spectra of carbon soot containing different amounts of nanotubes were registered under heating from a probing laser beam with a step-by-step increased power density. The material temperature in the laser spot was estimated from a position of the tangential Raman mode demonstrating a linear thermal shift (-0.012 cm^-1/K) from the position 1592 cm^-1 (at room temperature). The rate of the material temperature rise versus the laser power density (determining the slope of a corresponding graph) appeared to correlate strongly with the nanotube content in the soot. The influence of the experimental conditions on the slope value has been excluded via a simultaneous measurement of a reference sample with a high nanotube content (95 vol. %). After the calibration (done by a comparison of the Raman and the transmission electron microscopy data for the nanotube percentage in the same samples) the Raman-based method is able to provide a quantitative purity estimation for any nanotube-containing material. Received: 11 December 2001 / Accepted: 12 December 2001 / Published online: 4 March 2002