多壁碳纳米管中的多通道弹道输运特性

借助于扫描电子显微镜中可移动金属探针的测量系统,实现了探针电极与W衬底上生长的单根多壁碳纳米管一端的完美接触.研究了单根多壁碳纳米管室温下的电输运特性,发现多壁碳纳米管具有非常高的电流承载能力.对于直径100nm的碳纳米管,其电阻为34.4Ω,流经碳纳米管的最大电流可达7.27 mA,对应的电导为 460—490G0 .这一实验结果表明,大直径的多壁碳纳米管在室温下可以实现多通道弹道输运,是未来纳电子器件与电路的理想互联导线.     

Interference and Interaction in multi-wall carbon nanotubes

We report equilibrium electric resistance R and tunneling spectroscopy (dI/dV)measurements obtained on single multi-wall nanotubes contacted by four metallic Au fingers from above. At low temperature quantum interference phenomena dominate the magnetoresistance. The phase-coherence (l_φ)and elastic-scattering lengths (l_e)are deduced. Because l_e is of order of the circumference of the nanotubes, transport is quasi-ballistic. This result is supported by a dI/dV spectrum which is in good agreement with the density of states (DOS) due to the one-dimensional subbands expected for a perfect single-wall tube. As a function of temperature T the resistance increases on decreasing T and saturates at ≈1–10 Kfor all measured nanotubes. R(T) cannot be related to the energy-dependent DOS of graphene but is mainly caused by interaction and interference effects. On a relatively small voltage scale of the order ≈10 meV, a pseudogap is observed in dI/dV which agrees with Luttinger-liquid theories for nanotubes. Because we have used quantum diffusion based on Fermi-liquid as well as Luttinger-liquid theory in trying to understand our results, a large fraction of this paper is devoted to a careful discussion of all our results. Received: 17 May 1999 / Accepted: 18 May 1999 / Published online: 4 August 1999     

Synthesis of multi-wall carbon nanotubes by simple pyrolysis

A new pyrolysis technique has been developed for the synthesis of multi-walled carbon nanotubes (MWCNTs). In this simple method diethyl ether and nickelocene is pyrolysized in a reaction quartz tube without using carrier gas. The samples are prepared at pyrolysis temperatures of 650 and 950 ^°C and the effect of temperature on the tube morphology investigated. Purification has been done following the standard oxidation and acid bath treatment. The as-synthesized and purified nanotubes have been characterized by X-ray diffraction (XRD), Scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA) and micro-Raman spectroscopy. The technique has great advantages such as low cost and easy operation for the production of CNTs.     

Aerosol generation and measurement of multi-wall carbon nanotubes

Mass production of some kinds of carbon nanotubes (CNT) is now imminent, but little is known about the risk associated with their exposure. It is important to assess the propensity of the CNT to release particles into air for its risk assessment. In this study, we conducted aerosolization of a multi-walled CNT (MWCNT) to assess several aerosol measuring instruments. A Palas RBG-1000 aerosol generator applied mechanical stress to the MWCNT by a rotating brush at feed rates ranging from 2 to 20 mm/h, which the MWCNT was fed to a two-component fluidized bed. The fluidized bed aerosol generator was used to disperse the MWCNT aerosol once more. We monitored the generated MWCNT aerosol concentrations based on number, area, and mass using a condensation particle counter and nanoparticle surface area monitor. Also we quantified carbon mass in MWCNT aerosol samples by a carbon monitor. The shape of aerosolized MWCNT fibers was observed by a scanning electron microscope (SEM). The MWCNT was well dispersed by our system. We found isolated MWCNT fibers in the aerosols by SEM and the count median lengths of MWCNT fibers were 4–6 μm. The MWCNT was quantified by the carbon monitor with a modified condition based on the NIOSH analytical manual. The MWCNT aerosol concentration (EC mass base) was 4 mg/m³ at 2 mm/h in this study.     

Toxicological effects of multi-wall carbon nanotubes in rats

The aim of this study was to evaluate the lung toxicity of multi-wall carbon nanotubes (MWCNTs). The present work exposed MWCNTs into the rats in intratracheal instillation administration modes. We systematically studied the distribution of nanoparticles in vivo, target organs and time-effects of nanotoxicity, dose-effects of nanotoxicity, etc. These results indicate that under the conditions of this test, pulmonary exposures to MWCNTs in rats by intratracheal instillation produced a series of multiple lesions in a dose-dependent and time-dependent manner, evidence of a foreign tissue body reaction.     

Synthesis of multi-wall carbon nanotubes by copper vapor laser

Synthesis of multi-wall carbon nanotubes in a 1473 K furnace using a copper vapor laser (CVL) is reported. The operating parameters of this laser, i.e. a high fluence at the focal point and an extremely high frequency of 10 kHz, distinguished it from common laser sources in the synthesis of CNTs. Therefore, the unexpected experimental findings, the formation of MWNTs instead of the generally reported SWNTs, would be verified by these two notable parameters. Electron microscopy beside Raman spectroscopy illustrates the presence of multi-wall carbon nanotubes in the resulting product.     

Synthesis of single- and multi-wall carbon nanotubes over supported catalysts

The quantities of deposited carbon were measured and the quality of the nanotubes was characterized by means of transmission electron microscopy and scanning tunneling microscopy. The inner and outer diameters of the nanotubes were also measured and the diameter distribution histograms were established. The multi-wall straight and coiled nanotubes were found to be quite regular with an average inner (outer) diameter of 4–7 nm (15–25 nm) and with lengths up to 50 μm. The walls contain concentric cylindrical graphene sheets separated by the graphitic interlayer distance. The single-wall nanotubes were found as bundles of hundreds of aligned straight 1-nm-diameter nanotubes with lengths up to 1-μm. The influence of various parameters such as the method of catalyst preparation, the nature and the pore size of the support, the nature of the metal, the quantity of catalyst active particles, and the reaction conditions on the nanotubes formation were studied. The numbers and dimensions of the catalyst active particles dispersed on the support were found to be of importance in regulating the shape of the produced nanotubes. Following these results, a model of growth mechanism was suggested for the nanotubes obtained by this method. Received: 5 January 1998     

Control of one-dimensional transport in multi-wall carbon nanotubes by wall destruction

We have investigated the damage in multi-wall carbon nanotubes (MWNTs) destroyed by electrical breakdown and focused ion beam bombardment (FIBB). The transport properties of a MWNT destroyed by electrical breakdown have been compared with those of a MWNT destroyed by FIBB. Also the Tomonaga–Luttinger transport (TLT) model has been applied to each type of destroyed MWNT. The MWNT destroyed by FIBB showed TLT behavior because of the weak destruction of the remaining walls. However, in the case of MWNTs destroyed by electrical breakdown, three-dimensional variable-range hopping (VRH) was observed in the low temperature transport. This suggests that the local damage has been caused by strong breakdown. There exists a clear difference between the effects of electrical breakdown and FIBB. Wall destruction by FIBB could be applied to control the one-dimensional transport of MWNTs.     

Formula for the absorption coefficient for multi-wall nanotubes

We present a formalism for calculating the absorption coefficient of a pair of coaxial tubules. A spatially nonlocal, dynamical self-consistent field theory is obtained by calculating the electrostatic potential produced by the charge density fluctuations as well as the external electric field. There are peaks in the absorption spectrum arising from plasma excitations corresponding either to plasmon or particle-hole modes. In this Letter, we numerically calculate the plasmon contribution to the absorption spectrum when an external electric field is applied. The number of peaks depends on the radius of the inner as well as outer tubule. The height of each peak is determined by the plasmon wavelength and energy. For a chosen wave number, the most energetic plasmon has the highest peak corresponding to the largest oscillator strength of the excited modes. Some of the low-frequency plasmon modes have such weak coupling to an external electric field that they are not seen on the same scale as the modes with larger energy of excitation. We plot the peak positions of the plasmon excitations for a pair of coaxial tubules. The coupled modes on the two tubules are split by the Coulomb interaction. The energies of the two highest plasmon branches increase with the radius of the outer tubule. On the contrary, the lowest modes decrease in energy as this radius is increased. No effects due to inter-tubule hopping are included in these calculations.     

Sonocatalytic epoxidation of alkenes by vanadium-containing polyphosphomolybdate immobilized on multi-wall carbon nanotubes

A Keggin type polyoxometalate (POM) has been immobilized in the unique network structure of multi-wall carbon nanotubes (CNTs). The vanadium-containing polyphosphomolybdate (PVMo) supported on CNTs, which was prepared by a one-step solid-state reaction, was characterized by FT-IR, XRD, SEM and elemental analyses. These uniform nanoparticles have an average size 20–30 nm. Furthermore, due to the chemical interaction between PVMo and carboxylic acid groups, PVMo nanoparticles were successfully immobilized on the CNTs. Moreover, the obtained composite was found as an efficient catalyst for oxidation of hydrocarbons under reflux and ultrasonic irradiation (US) conditions.     

多壁碳纳米管在循环相变过程中结构变化初探

对由离子束辐照多壁碳纳米管（MWCNTs）产生的无定形碳纳米线（ACNWs）进行了高温退火（2400℃）处理，通过透射电子显微镜(TEM)观察发现，ACNWs体部转变成与原来MWCNTs相似 的管状石墨结构，而其封端区域的石墨晶体结构形态却与原来的MWCNTs完全不同，且变化多 端.基于实验结果，对其相变过程机理提出了一个概念性的模型. 关键词： 无定形碳纳米线 高温退火 相变 透射电子显微镜     

Improvement in performance of organic light-emitting devices by inclusion of multi-wall carbon nanotubes

Poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) was modified by different concentrations of multi-wall carbon nanotubes (MWNTs), and the nanocomposites of PEDOT:PSS and MWNTs were firstly used as hole-injection layer in fabrication of organic light-emitting devices (OLEDs) by using a double-layer structure with hole-injection layer of doped PEDOT:PSS and emitting/electron transport layer of tris(8-hydroxyquinolinato) aluminum (Alq₃). PEDOT:PSS solution doped with MWNTs was spin-coated on clean polyethylene terephthalate (PET) substrate with indium tin oxide (ITO). It was found that the electroluminescence (EL) intensity of the OLEDs were greatly improved by using PEDOT:PSS doped with MWNTs as hole-injection layer which might have resulted from the hole-injection ability improvement of the nanocomposites. Higher luminescence intensity and lower turn-on voltage were obtained by these devices and the luminance intensity obtained from the device with the hole-injection layer of PEDOT:PSS doped by 0.4 wt.% MWNTs was almost threefolds of that without doping.     

Surface modification of indium tin oxide films by amino ion implantation for the attachment of multi-wall carbon nanotubes

Amino ion implantation was carried out at the energy of 80 keV with fluence of 5 × 10¹⁵ ions cm⁻² for indium tin oxide film (ITO) coated glass, and the existence of amino group on the ITO surface was verified by X-ray photoelectron spectroscopy analysis and Fourier transform infrared spectra. Scanning electron microscopy images show that multi-wall carbon nanotubes (MWCNTs) directly attached to the amino ion implanted ITO (NH₂/ITO) surface homogeneously and stably. The resulting MWCNTs-attached NH₂/ITO (MWCNTs/NH₂/ITO) substrate can be used as electrode material. Cyclic voltammetry results indicate that the MWCNTs/NH₂/ITO electrode shows excellent electrochemical properties and obvious electrocatalytic activity towards uric acid, thus this material is expected to have potential in electrochemical analysis and biosensors.     

Sensitive voltammetric determination of cysteamine using promazine hydrochloride as a mediator and modified multi-wall carbon nanotubes carbon paste electrodes

This paper presents a sensitive electrochemical method for the determination of cysteamine (CA) using promazine hydrochloride-modified multi-wall carbon nanotubes carbon paste electrode (PrH/MWCNTs CPE). Because of the good electrochemical activity of MWCNTs and the acceptable performance of promazine hydrochloride (PrH) as an electrocatalytic mediator, the modified electrode significantly enhanced the sensitivity for the detection of CA in comparison to the bare carbon paste electrode (CPE). All chemical parameters such as pH of solution, concentration of PrH and kinetic parameters of the system were investigated. Linear sweep voltammetric (LSV) method was used to follow the electrocatalytic effect of CA on the current–potential response of PrH. Under optimum conditions, the obtained net peak current ?I _p(I _sample???I _blank) was linear with CA concentrations in two dynamic ranges of 2.0–346.5 μmol l^?1 (?I _p?=?(0.0195?±?0.0043)C _CA?+?(0.7648?±?0.0397) (r ²?=?0.9948)) and 346.5–1,912.5 μmol l^?1 (?I _p?=?(0.0100?±?0.0026)C _CA?+?(3.8981?±?0.0828) (r ²?=?0.9911)) with a detection limit of 0.8 μmol l^?1. Finally, the PrH/MWCNTs CPE was successfully applied for the determination of CA in urine and drug samples with satisfactory results.     

Effect of Ni, Pd and Ni-Pd nano-islands on morphology and structure of multi-wall carbon nanotubes

In this research, the effect of Ni, Pd and Ni-Pd catalysts have studied on morphology and structure of synthesized multi-wall carbon nanotubes (MWCNTs). Initially, thin films of Ni (with two thicknesses of 10 and 20 nm), Pd/Ni (5/10 nm) and Pd (10 nm) were deposited as catalysts on SiO₂ (60 nm)/Si(1 0 0) substrates, using dc magnetron sputtering technique. The deposited films were annealed at 900 °C in ammonia environment for 45 min, in order to obtain nano-structured catalyst on the surface. Using scanning electron microscopy (SEM), the average size of Ni nano-islands (synthesized by the 10 and 20 nm Ni films), Pd and Ni-Pd nano-islands were measured about 55, 110, 45 and 50 nm, respectively. According to X-ray photoelectron spectroscopy analysis (XPS), the ratio of Ni/Pd on the surface was about 3 for the bilayer sample. The CNTs were synthesized on the nano-island catalysts at 940 °C in CH₄ ambient using a thermal chemical vapor deposition method. The results revealed that average diameter of the CNTs were about 70, 110, 120 nm for Ni, Ni-Pd and Pd catalysts, respectively. Raman spectra of the MWCNTs showed that intensity ratio of two main peaks located in the range of 1550-1600 and 1250-1450 cm⁻¹ (as a quality factor for the CNTs) for Ni, Pd and Ni-Pd catalysts were 1.42, 0.91 and 0.85, respectively. Therefore, based on our data analysis, although addition of Pd to Ni catalyst caused a considerable reduction in the quality of the grown MWCNTs as compared to the pure Ni catalyst, but it resulted in an enhancement in the methane decomposition rate. For the pure Pd catalyst samples, both a slow methane decomposition rate as compared with Ni-Pd catalyst samples and a poor quality of CNTs were observed as compared with the Ni catalyst, under similar experimental conditions.     

A one-dimensional continuous model for carbon nanotubes

The two-dimensional (2D) continuous elastic energy model for isotropic tubes is reduced to a one-dimensional (1D) curvature elastic energy model strictly. This 1D model is in accordance with the Kirchhoff elastic rod theory. Neglecting the in-plane strain energy in this model, it is suitable to investigate the nature features of carbon nanotubes (CNTs) with large deformations and can also reduce to the string model in [Z.C. Ou-Yang et al., Phys. Rev. Lett. 76, 4055 (1997)] when the deformation is small enough. For straight chiral shapes, this general model indicates that the difference of the chiral angle between two equilibrium states is about π/6, which is consistent with the lattice model. It also reveals that the helical shape has lower energy for per atom than the straight shape has in the same condition. By solving the corresponding equilibrium shape equations, the helical tube solution is in good agreement with the experimental result, and super helical shapes are obtained and we hope they can be found in future experiments.     

多壁碳纳米管外壁高温蒸发的分子动力学模拟

采用经典分子动力学（MD）方法,使用EDIP（environment-dependent interatomic potential)势描述C纳米管内C原子之间相互作用,对多壁C纳米管由于Stone-Wales缺陷引起外层管高温剥落蒸发现象进行了计算模拟.研究结果表明,高温下多壁C纳米管外层管Stone-Wales缺陷处C原子剧烈振动导致C—C键断裂形成悬键,并逐渐向四周扩散导致外层管剥落蒸发.利用Lindemann指数作为判据,得出多壁C纳米管外层管出现剥落蒸发的温度为2290 K左右,与Huang Jianyu等实验中观测到多壁C纳米管外层管剥落蒸发现象产生的温度2000 ℃基本一致.     

多壁碳纳米管外壁高温蒸发的分子动力学模拟

采用经典分子动力学（MD）方法,使用EDIP（environment-dependent interatomic potential)势描述C纳米管内C原子之间相互作用,对多壁C纳米管由于Stone-Wales缺陷引起外层管高温剥落蒸发现象进行了计算模拟.研究结果表明,高温下多壁C纳米管外层管Stone-Wales缺陷处C原子剧烈振动导致C—C键断裂形成悬键,并逐渐向四周扩散导致外层管剥落蒸发.利用Lindemann指数作为判据,得出多壁C纳米管外层管出现剥落蒸发的温度为2290 K左右,与Huang Jianyu等实验中观测到多壁C纳米管外层管剥落蒸发现象产生的温度2000 ℃基本一致. 关键词： 多壁C纳米管 分子动力学 Stone-Wales缺陷 剥落蒸发