Structure comparison of nanotubes produced by different processes

Several methods used for the synthesis of carbon nanotubes have been developed in the last decade. The preparation techniques used, and their associated parameters, have an ultimate effect on the structure of the resulting nanotubes. Consequently, it is of great interest to compare the structure of carbon nanotubes synthesized by different techniques. We investigated a range of nanotubes of different origin by scanning probe microscopy (TM-AFM), and by scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS). Three different types of nanotubes have been investigated: commercial SWNT and MWNT, MWNT (synthesized using a CCVD process) and its SiO₂ coated variant, and nanostructures produced using an electrochemical method. A preparative technique is described and different tube parameters are measured. The quality of coated MWNT-s is investigated and nano-structured rings are revealed in samples obtained by electrolysis of molten salts on graphite electrodes.     

钯金属吸附对半导体性碳纳米管电输运的影响

利用物理蒸发技术,在半导体性的碳纳米管上沉积钯金属,利用导电原子力显微镜检测钯吸附对碳纳米管电输运的影响.结果表明:沉积的钯在碳纳米管上形成纳米颗粒,随着钯颗粒密度的增加,半导体性碳纳米管逐渐向金属性转变.利用第一性原理计算了吸附有钯原子的半导体性单壁碳纳米管的能带结构.研究发现,钯的覆盖率越高,其禁带宽度越窄,直至为零,定性说明了实验结果的合理性. 关键词： 单壁碳纳米管 钯纳米颗粒 导电原子力显微镜 第一性原理计算     

Preparation of Sn films deposited on carbon nanotubes

In this work carbon nanotubes were first grown on copper substrate by chemical vapor deposition method. The Sn deposits were then deposited on the surface of as-grown carbon nanotubes by three different methods: electroplating, electroless plating and displacing methods. The Sn deposits on CNTs surface were characterized by both scanning electron microscope and field emission scanning electron microscope. The compositions of Sn deposits were analyzed by energy dispersive X-ray spectroscope. The results showed that both electroless plating and displacing deposits can but the electroplating deposits cannot cover on the surface of CNTs. Besides C, Sn, Ni and Pd, the electroless deposits also contain element of oxygen and the displacing deposits also contain elements of copper and oxygen.     

Elastic properties of dense nanotube layers

The Young modulus of a thin layer consisting of densely packed carbon nanotubes oriented normally to a substrate is measured using a scanning probe atomic force microscope. It is found that the adhesion of the film and the silicon substrate is not very strong, and, at certain conditions, this may lead to an intense energy dissipation in an oscillatory system loaded by the film.     

Four-point resistance of individual single-wall carbon nanotubes

We have studied the resistance of single-wall carbon nanotubes measured in a four-point configuration with noninvasive voltage electrodes. The voltage drop is detected using multiwalled carbon nanotubes while the current is injected through nanofabricated Au electrodes. The resistance at room temperature is shown to be linear with the length as expected for a classical resistor. This changes at cryogenic temperature; the four-point resistance then depends on the resistance at the Au-tube interfaces and can even become negative due to quantum-interference effects.     

Electric field aligned growth of single-walled carbon nanotubes

Electric field aligned, single-walled carbon nanotubes are grown between electrodes using thermal chemical vapour deposition (CVD) of methane. The growth occurs on a thin film layered catalyst of aluminium, iron and molybdenum patterned on top of electrodes. The nanotubes bridge 10 μm sized electrode gaps and have a typical diameter of less than 2 nm as measured by Raman spectroscopy and atomic force microscopy. We present electrical transport measurements on a directly grown nanotube which shows p-type semiconducting behaviour.     

Electrical properties of boron-doped MWNTs synthesized by hot-filament chemical vapor deposition

We have synthesized a large amount of boron-doped multiwalled carbon nanotubes (MWNTs) by hot-filament chemical vapor deposition. The synthesis was carried out in a flask using a methanol solution of boric acid as a source material. The scanning electron microscopy, transmission electron microscopy, and micro-Raman spectroscopy were performed to evaluate the structural properties of the obtained MWNTs. In order to evaluate the electrical properties, temperature dependence of resistivity was measured in an individual MWNTs with four metal electrodes. The Raman shifts suggest carrier injection into the boron-doped MWNTs, but the resistivity of the MWNTs was high and increased strongly with decreasing temperature. Defects induced by the plasma may cause this enhanced resistivity.     

170keV质子辐照对多壁碳纳米管薄膜微观结构与导电性能的影响

碳纳米管具有优异的导电性, 是未来电子元器件的理想候选材料, 应用前景广阔. 针对碳纳米管在空间电子元器件的应用需求, 本文研究了170 keV质子辐照对多壁碳纳米管薄膜微观结构与导电性能的影响. 采用扫描电子显微镜(SEM)、拉曼光谱仪(Raman)、X射线光电子能谱仪(XPS)及电子顺磁共振谱仪(EPR)对辐照前后碳纳米管试样的表面形貌和微观结构进行分析; 利用四探针测试仪对碳纳米管薄膜进行导电性能分析. SEM分析表明, 170 keV质子辐照条件下, 当辐照注量高于5×10¹⁵ p/cm² (protons/cm²)时, 碳纳米管薄膜表面变得粗糙疏松, 纳米管发生明显弯曲、收缩及相互缠结现象. 目前, 质子辐照纳米管发生的收缩现象被首次发现. 基于Raman和XPS分析表明, 170 keV质子辐照后碳纳米管的有序结构得到改善, 且随辐照注量增加, 碳纳米管的有序结构改善明显. 结构的改善主要是由于170 keV质子辐照碳纳米管所产生的位移效应导致缺陷重组. EPR分析表明, 随着辐照注量的增加, 碳纳米管薄膜内的非局域化电子减少. 利用四探针测试分析表明, 碳纳米管薄膜的导电性能变差, 这是由于170 keV质子辐照导致碳纳米管薄膜中的电子特性及形态发生改变. 本文研究结果有助于利用质子辐照对碳纳米管膜结构和性能进行调整, 从而制备出抗辐射的纳米电子器件.     

Immobilization of redox mediators on functionalized carbon nanotube: A material for chemical sensor fabrication and amperometric determination of hydrogen peroxide

Chemical functionalization of single-walled carbon nanotubes with redox mediators, namely, toluidine blue and thionin have been carried out and the performance of graphite electrode modified with functionalized carbon nanotubes is described. Mechanical immobilization of functionalized single-walled nanotube (SWNT) on graphite electrode was achieved by gently rubbing the electrode surface on carbon nanotubes supported on a glass slide. The electrochemical behaviour of the modified electrodes was investigated by cyclic voltammetry. The SWNT-modified electrodes showed excellent electrocatalytic effect for the reduction of hydrogen peroxide. A decrease in overvoltage was observed as well as an enhanced peak current compared to a bare graphite electrode for the reduction of hydrogen peroxide. The catalytic current was found to be directly proportional to the amount of hydrogen peroxide taken.     

First-principles calculations of contact effect on quantum transport in carbon nanotubes

We report first-principles calculations of conductance of carbon nanotubes between metallic electrodes. The electronic states are calculated using a numerical atomic orbital basis set in the framework of the density functional theory, and the conductance is calculated using the Green's function method. We show transmission spectra of carbon nanotubes connected to electrodes and reveal the contact effect of electrodes on the transport properties of nanotubes.     

Ultrasound-assisted synthesis of unzipped multiwalled carbon nanotubes/titanium dioxide nanocomposite as a promising next-generation energy storage material

Carbon-based systems have been discussed as prospective alternatives for conventional metal-based catalysts over the past decade. These studies were motivated by the abundance, low cost, lightweight and diversity of structural allotropes of carbon. We reported here the synthesis of a new type of unzipped multiwalled carbon nanotubes/titanium dioxide (UzMWCNT/TiO₂) nanocomposite by the two-stage procedure. By the modified Hummers method, multiwalled carbon nanotubes (MWCNTs) were converted to oxidized multi-walled carbon nanotubes (O-MWCNT). Then, through a facile ultrasound-assisted route prepared UzMWCNT/TiO₂ nanocomposite. For this, the oxidized multiwalled carbon nanotubes are treated with TiCl₄ under an ultrasonic probe for 3 h to generate UzMWCNT/TiO₂ and then explored its environmental friendliness and energy applications as a supercapacitor. This novel UzMWCNT/TiO₂ nanocomposite was characterized using XRD, TGA, FT-IR, Raman, TEM and EDX analysis. The electrochemical performance can be evaluated by using cyclic voltammetry (CV) and galvanostatic charging-discharging (GCD) study. Finally, the electrodes prepared using UzMWCNT/TiO₂ nanocomposite have been analyzed through electrochemical impedance spectroscopy (EIS) to probe the charge transfer characteristics and the results are consistent with other electrochemical measurements.     

Measurement of the elastic moduli of dense layers of oriented carbon nanotubes by a scanning force microscope

A technique is developed for measuring the modulus of elasticity of a material with a Nanoscan scanning force microscope on the basis of measuring the dependence of probe vibration frequency on the penetration depth of the needle into the specimen. This technique makes it possible to study materials with elastic moduli from 50 to 1000 GPa. The Young moduli of dense films of carbon nanotubes oriented at angles of 45° and 90° to the quartz substrate are measured. From their ratio, the Young modulus in the direction perpendicular to the tubes and the anisotropy of the elastic moduli are determined. A comparison of these values with the corresponding values obtained for a nanotube film deposited on a silicon substrate is carried out. On the basis of this comparison, a conclusion is made concerning the interaction between single-layer nanotubes and between nanotubes in a mixture of single-layer and multilayer ones.     

Single-wall carbon nanotube chemical attachment at platinum electrodes

Self-assembled monolayer (SAM) techniques were used to adsorb 4-aminothiophenol (4-ATP) on platinum electrodes in order to obtain an amino-terminated SAM as the base for the chemical attachment of single-wall carbon nanotubes (SWCNTs). A physico-chemical, morphological and electrochemical characterizations of SWCNTs attached onto the modified Pt electrodes was done by using reflection-absorption infrared spectroscopy (RAIR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and cyclic voltammetry (CV) techniques. The SWNTs/4-ATP/Pt surface had regions of small, medium, and large thickness of carbon nanotubes with heights of 100-200 nm, 700 nm to 1.5 μm, and 1.0-3.0 μm, respectively. Cyclic voltammetries (CVs) in sulfuric acid demonstrated that attachment of SWNTs on 4-ATP/Pt is markedly stable, even after 30 potential cycles. CV in ruthenium hexamine was similar to bare Pt electrodes, suggesting that SWNTs assembly is similar to a closely packed microelectrode array.     

Investigation of the radial compression of carbon nanotubes with a scanning probe microscope

Efforts have been made to characterize the mechanical properties of carbon nanotubes. Previous work has concentrated on the tubes' longitudinal properties, and studies of their radial properties have lagged behind. We have used a scanning probe microscope with an indentation/scratch function to investigate the radial compression of multiwalled carbon nanotubes under an asymmetric stress. In particular, we have determined the radial compressive elastic modulus at different compression levels and have estimated the compressive strength to be well beyond 5.3 GPa.     

Carbon nanotube based bolometer

The contacts of single carbon nanotubes and bundles of carbon nanotubes with superconducting and metallic electrodes are investigated in order to create bolometers and electron coolers. Tunneling contacts of the carbon nanotubes with aluminum electrodes are obtained. The current-voltage characteristics of junctions are analyzed for temperatures from room temperature to 300 mK. The resistance of individual nanotubes is primarily determined by defects and is too large for applications. The use of the bundles of carbon nanotubes makes it possible to considerably reduce the resistance of the bolometer, which is determined by a small number of conducting tubes with good tunneling contacts with the electrodes. The energy gap is equal to hundreds and tens of millivolt in the former and latter cases, respectively. Structures containing bundles of carbon nanotubes can be described in a model with a Schottky barrier. The samples with bundles of carbon nanotubes exhibit the bolometric response to external high-frequency radiation at a frequency of 110 GHz with an amplitude up to 100 μV and a temperature voltage response to 0.4 mV/K.     

Superconducting properties of carbon nanotubes

Metallic single wall carbon nanotubes have attracted much interest as 1D quantum wires combining a low carrier density and a high mobility. It was believed for a long time that low temperature transport was exclusively dominated by the existence of unscreened Coulomb interactions leading to an insulating behavior at low temperature. However experiments have also shown evidence of superconductivity in carbon nanotubes. We distinguish two fundamentally different physical situations. When carbon nanotubes are connected to superconducting electrodes, they exhibit proximity induced superconductivity with supercurrents which strongly depend on the transmission of the electrodes. On the other hand intrinsic superconductivity was also observed in suspended ropes of carbon nanotubes and recently in doped individual tubes. These experiments indicate the presence of attractive interactions in carbon nanotubes which overcome Coulomb repulsion at low temperature, and enables investigation of superconductivity in a 1D limit never explored before. To cite this article: M. Ferrier et al., C. R. Physique 10 (2009).     

Towards molecular-scale electronics and biomolecular self-assembly

This paper provides an overview of recent research developments in the field of nanoelectronics with organic materials such as carbon nanotubes and DNA-templated nanowires. Carbon nanotubes and gold electrodes are chemically functionalized in order to contact carbon nanotubes by self-assembly. The transport properties of these nanotubes are dominated by charging effects and display clear Coulomb blockade behaviour. A different approach towards nanoscale electronics is based on the molecular recognition properties of biomolecules such as DNA. As an example, DNA is stretched between electrodes using a molecular combing technique. A two-step metallization procedure leads to the formation of highly conductive gold nanowires.     

Conductance of bulk samples of multiwall carbon nanotubes-metal junctions

Conductance as a function of voltage and temperature was measured in junctions made of bulk samples of multiwall carbon nanotubes and metal electrodes. A clear zero bias anomaly was observed at low temperatures. The experimental results were analyzed within existing models based on Luttinger liquid and disorder theories. We find that our results are well explained using the quasi-one-dimensional disordered model.     

Mesoscopic thermal and thermoelectric measurements of individual carbon nanotubes

We discuss the mesoscopic experimental measurements of electron energy dissipation, phonon thermal transport, and thermoelectric phenomena in individual carbon nanotubes. The temperature distributions in electrically heated individual multiwalled carbon nanotubes have been measured with a scanning thermal microscope. The temperature profiles along the tube axis in nanotubes indicate the bulk dissipation of electronic energy to phonons. In addition, thermal conductivity of an individual multiwalled nanotube has been measured using a microfabricated suspended device. The observed thermal conductivity is two orders of magnitude higher than the estimation from previous experiments that used macroscopic mat samples. Finally, we present thermoelectric power (TEP) of individual single walled carbon nanotubes using a novel mesoscopic device. A strong modulation of TEP as a function of the gate electrode was observed.     

Study on structure change of carbon nanotubes depending on different reaction gases

Aligned carbon nanotubes were grown by plasma-enhanced hot filament chemical vapor deposition using different reaction gases and they were investigated by scanning electron microscopy and transmission electron microscopy. It is found that the hollow carbon nanotubes were formed using methane and hydrogen as the reaction gases, but the bamboo-structured carbon nanotubes were grown when ammonia was added into the reaction gases, indicating that the structure of the aligned carbon nanotubes was changed depending on different reaction gases. On setting of diffusion of carbon, the effects of the nitrogenous gas on the structure change of carbon nanotubes are studied.