Manipulation and Imaging of Individual Single‐Walled Carbon Nanotubes with an Atomic Force Microscope

The tip of an atomic force microscope is used to create carbon nanotube junctions by changing the position and shape of individual single‐walled carbon nanotubes on a SiO₂ surface. With this manipulation technique, we are able to bend, buckle, cross (see Figure), and break nanotubes, and to unravel a nanotube “crop circle” into a single tube. Tapping‐mode atomic force microscopy measurements of the height of a carbon nanotube on the surface always yield values smaller than the nanotube diameter. Variation of the scan parameters shows that this is due to a tapping deformation by the tip. The tapping deformation of manipulated nanotube crossings and buckles is discussed as well.     

Dissymmetric carbon nanotubes by bipolar electrochemistry

Short carbon nanotubes have been modified selectively on one end with metal using a bulk technique based on bipolar electrochemistry. A stabilized suspension of nanotubes is introduced in a capillary containing an aqueous metal salt solution, and a high electric field is applied to orientate and polarize the individual tubes. During their transport through the capillary under sufficient polarization (30 kV), each nanotube is the site of water oxidation on one end and the site of metal ion reduction on the other end with the size of the formed metal cluster being proportional to the potential drop along the nanotube.     

Charge trapping in carbon nanotube loops demonstrated by electrostatic force microscopy

Electronic devices made from carbon nanotubes (CNTs) can be greatly affected by substrate charges, which, for instance, induce strong hysteresis in CNT field effect transistors. In this work, electrostatic force microscopy (EFM) is employed to investigate single-walled nanotubes grown by chemical vapor deposition on SiO2 substrates. We demonstrate the use of this technique to gain quantitative information on the substrate charges. It is found that charge pools with densities around 10(-8) C/cm2 can be trapped inside nanotube loops for extended periods of time, showing that nanotubes can act as confining barriers for substrate charges. The trapped charges can be removed by scanning probe manipulation.     

Charge transport in a single superconducting tin nanowire encapsulated in a multiwalled carbon nanotube

The charge transport properties of single superconducting tin nanowires encapsulated by multiwalled carbon nanotubes have been investigated by multiprobe measurements. The multiwalled carbon nanotube protects the tin nanowire from oxidation and shape fragmentation and therefore allows us to investigate the electronic properties of stable wires with diameters as small as 25 nm. The transparency of the contact between the Ti/Au electrode and nanowire can be tuned by argon ion etching the multiwalled nanotube. Application of a large electrical current results in local heating at the contact which in turn suppresses superconductivity.     

TiO_2/ZnO纳米管的制备及其光催化性能

采用电化学阳极氧化法制备了高度有序的TiO2纳米管阵列,并利用纳米管的光致超亲水特性,采用斜面毛细组装技术在无定形TiO2表面自组装ZnO溶胶后退火制备了TiO2/ZnO复合纳米管.探讨了阳极氧化各参数对纳米管形貌的影响.利用X射线衍射仪(XRD)、场发射扫描电子显微镜(FE-SEM)等方法对样品的结构和形貌进行了表征.以有机磷农药氯胺磷为光催化降解对象,研究了焙烧温度、管径、管长和TiO2/ZnO复合比例等因素对降解效果的影响.结果表明,焙烧温度、管径以及ZnO复合比例对光催化降解率影响较大.对于管径97 nm、管长315.8nm的TiO2/ZnO纳米管,ZnO最佳复合比例为4.2%(质量分数),5 h后降解率达到78%.     

Mode I and mode II fracture toughness of E-glass non-crimp fabric/carbon nanotube (CNT) modified polymer based composites

In this study, mode I and mode II interlaminar fracture toughness, and interlaminar shear strength of E-glass non-crimp fabric/carbon nanotube modified polymer matrix composites were investigated. The matrix resin containing 0.1 wt.% of amino functionalized multi walled carbon nanotubes were prepared, utilizing the 3-roll milling technique. Composite laminates were manufactured via vacuum assisted resin transfer molding process. Carbon nanotube modified laminates were found to exhibit 8% and 11% higher mode II interlaminar fracture toughness and interlaminar shear strength values, respectively, as compared to the base laminates. However, no significant improvement was observed for mode I interlaminar fracture toughness values. Furthermore, Optical microscopy and scanning electron microscopy were utilized to monitor the distribution of carbon nanotubes within the composite microstructure and to examine the fracture surfaces of the failed specimens, respectively.     

Nanomechanics of Fiber-like Nanomaterials

Property characterization of nanomaterials is challenged by the small size of the structure because of the difficulties in manipulation. Here we demonstrate a novel approach that allows a direct measurement of the mechanical properties of individual nanotube-like structures by in-situ transmission electron microscopy (TEM). The technique is powerful in a way that it can directly correlate the atomic-scale microstructure of the carbon nanotube with its physical properties, providing a one-to-one correspondence in structure-property characterization. Applications of the technique will be demonstrated on mechanical properties, the electron field emission and the ballistic quantum conductance in individual nanotubes.     

Functionalization of nitrogen-doped carbon nanotubes with gallium to form Ga-CN(x)-multi-wall carbon nanotube hybrid materials

In an effort to combine group III-V semiconductors with carbon nanotubes, a simple solution-based technique for gallium functionalization of nitrogen-doped multi-wall carbon nanotubes has been developed. With an aqueous solution of a gallium salt (GaI(3)), it was possible to form covalent bonds between the Ga(3+) ion and the nitrogen atoms of the doped carbon nanotubes to form a gallium nitride-carbon nanotube hybrid at room temperature. This functionalization was evaluated by x-ray photoelectron spectroscopy, energy dispersive x-ray spectroscopy, Raman spectroscopy, scanning electron microscopy and transmission electron microscopy.     

Synthesis, Structure and Field Emission of Carbon Nanotubes

Multiwall and single-wall nanotubes were produced by carbon arc discharge in helium, and their structures were investigated by electron microscopy. Field emission from (1) as-grown multiwall nanotubes (MWNTs), (2) purified MWNTs and (3) purified single-wall nanotubes (SWNTs) was investigated by field emission microscopy. Of the three kinds of nanotubes studied, purified MWNTs whose tips are open provided the highest current at a fixed voltage. Although purified SWNTs provided the second highest current, SWNTs are not so robust as MWNTs against ion bombardment. As an application of nanotube field emitters, we manufactured cathode ray tube (CRT) lighting-elements by replacing conventional thermionic cathodes with nanotube field emitters. Stable electron emission, adequate luminance, and long life of the emitters were substantiated.     

Adhesion between two radially collapsed single-walled carbon nanotubes

Continuum mechanics analysis and molecular mechanics simulations are performed to study adhesion between two identical, radially collapsed single-walled carbon nanotubes. Not only the inter-adhesion energy between nanotubes but also the inner adhesion energy in a nanotube is considered. A closed-form solution to the adhesion configuration is achieved, which is well consistent with our molecular mechanics simulation. Comparing the potential energy of the adhesion structures formed by two identical single-walled carbon nanotubes, three types of configurations, i.e., circular, deformed, and collapsed shape, will be formed with increasing carbon nanotubes radius and separated by two critical radii of the single-walled carbon nanotube. Furthermore, it is found that the collapsed adhesion structure possesses the highest interfacial adhesion energy. The results demonstrate that, as a potential application in carbon nanotube reinforced composites, arrays formed by collapsed carbon nanotubes will be optimal due to the strong interface strength.     

Fabrication of Schottky barrier carbon nanotube field effect transistors using dielectrophoretic-based manipulation

Nanoscale electronic devices made from carbon nanotubes (CNTs) such as transistors and sensors are much smaller and potentially more versatile than those built using conventional IC technology. In this paper, we present a method that uses dielectrophoretic (DEP) manipulation process for the fabrication of single-channel and multi-channel carbon nanotube field effect transistors (CNT-FETs). For a typical fabrication process, single-walled carbon nanotubes (SWCNTs) are first pre-aligned to micron-precision range between two microelectrodes using DEP technique. The typically applied alternating current (AC) voltage to generate the DEP force for manipulation has a frequency of 1 MHz and amplitude of 10 V. We first demonstrated single-channel or multi-channel structures of CNT-FETs. An AFM is then used to "clean" or "sweep away" unwanted particles or CNTs around the electrodes. Lastly, the fabricated FETs were covered in a polymethylmethacrylate (PMMA) thin film and treated with an annealing process. The PMMA covered devices show improved performances over the non-covered devices.     

Measurement of metal/carbon nanotube contact resistance by adjusting contact length using laser ablation

A technique of measuring contact resistance between an individual nanotube and a deposited metallic film is described. Using laser ablation to sequentially shorten the contact length between a nanotube and the evaporated metallic film, the linear resistivity of the nanotube as well as the specific contact resistivity between the nanotube and metallic film can be determined. This technique can be generally used to measure the specific contact resistance that develops between a metallic film and a variety of different nanowires and nanotubes.     

Plumbing carbon nanotubes

Since their discovery, the possibility of connecting carbon nanotubes together like water pipes has been an intriguing prospect for these hollow nanostructures. The serial joining of carbon nanotubes in a controlled manner offers a promising approach for the bottom-up engineering of nanotube structures--from simply increasing their aspect ratio to making integrated carbon nanotube devices. To date, however, there have been few reports of the joining of two different carbon nanotubes. Here we demonstrate that a Joule heating process, and associated electro-migration effects, can be used to connect two carbon nanotubes that have the same (or similar) diameters. More generally, with the assistance of a tungsten metal particle, this technique can be used to seamlessly join any two carbon nanotubes--regardless of their diameters--to form new nanotube structures.     

Contactless Stimulation and Control of Biomimetic Nanotubes by Calcium Ion Gradients

Membrane tubular structures are important communication pathways between cells and cellular compartments. Studying these structures in their native environment is challenging, due to the complexity of membranes and varying chemical conditions within and outside of the cells. This work demonstrates that a calcium ion gradient, applied to a synthetic lipid nanotube, triggers lipid flow directed toward the application site, resulting in the formation of a bulge aggregate. This bulge can be translated in a contactless manner by moving a calcium ion source along the lipid nanotube. Furthermore, entrapment of polystyrene nanobeads within the bulge does not tamper the bulge movement and allows transporting of the nanoparticle cargo along the lipid nanotube. In addition to the synthetic lipid nanotubes, the response of cell plasma membrane tethers to local calcium ion stimulation is investigated. The directed membrane transport in these tethers is observed, but with slower kinetics in comparison to the synthetic lipid nanotubes. The findings of this work demonstrate a novel and contactless mode of transport in lipid nanotubes, guided by local exposure to calcium ions. The observed lipid nanotube behavior can advance the current understanding of the cell membrane tubular structures, which are constantly reshaped during dynamic cellular processes.     

The structure and function of ribonuclease A upon interacting with carbon nanotubes

Ribonucleic acid (RNA) is an important genetic material whose lifetime is most often determined by the rate of its enzymatic degradation. Our studies showed that multi-walled carbon nanotubes and single-walled carbon nanotubes functionalized with carboxylic groups interacted with ribonuclease A (RNase A) and caused the reduction of its activity by changing its conformation, thus protecting RNA from enzymatic cleavage. The results showed that RNase A was less active on the carbon nanotube surface than in free solution, and the activity was decreased further on larger carbon nanotubes, suggesting that carbon nanotubes with various surface modifications may be useful in RNA extraction, purification, and manipulation.     

The influence of the stacking orientation of C and BN stripes in the structure, energetics, and electronic properties of BC2N nanotubes

Carbon and boron nitride nanotubes present significant differences in their electronics. However, they have isoelectronic bonds and very similar geometrical structures that allow BCN nanotubes to be synthesized. These BCN nanotubes present properties that can vary according to their relative number of B, C, and N atoms, and their atomic distribution on the nanotube surface. Here we employ first-principles density functional theory to study BCN nanotubes with BC(2)N stoichiometry. These nanotubes are composed of pure BN and C stripes which are stacked (i) in parallel, (ii) perpendicularly, and (iii) forming helicoidal patterns along the nanotube axes. We found that the different strain energies of the curved C and BN arcs in the nanotubes with parallelly aligned stripes can lead to geometries that deviate significantly from the usual circular shape. A sinusoidal shape was predicted for a BC(2)N nanotube with a helicoidal arrangement of the C and BN stripes due to differences in the C-B and C-N bonds parallel to the tube axis. It was shown that the phase segregation is energetically favoured. Such structural preference and the relative stability of the BC(2)N nanotubes can be explained in terms of the ratio between the total number of bonds and the number of C-B and C-N bonds in the nanotubes. Finally, we found that one type of BC(2)N nanotube with helicoidal C and BN stripes, although having a zigzag structure, exhibits a metallic character.     

Synthesis,Structure and Field Emission of Carbon Nanotubes

Abstract

Multiwall and single-wall nanotubes were produced by carbon arc discharge in helium, and their structures were investigated by electron microscopy. Field emission from (1) as-grown multiwall nanotubes (MWNTs), (2) purified MWNTs and (3) purified single-wall nanotubes (SWNTs) was investigated by field emission microscopy. Of the three kinds of nanotubes studied, purified MWNTs whose tips are open provided the highest current at a fixed voltage. Although purified SWNTs provided the second highest current, SWNTs are not so robust as MWNTs against ion bombardment. As an application of nanotube field emitters, we manufactured cathode ray tube (CRT) lighting-elements by replacing conventional thermionic cathodes with nanotube field emitters. Stable electron emission, adequate luminance, and long life of the emitters were substantiated.     

Electrophoretic transport in surfactant nanotube networks wired on microfabricated substrates

Nanofluidic devices are rapidly emerging as tools uniquely suited to transport and interrogate single molecules. We present a simple method to rapidly obtain compact surfactant nanotube networks of controlled geometry and length. The nanotubes, 100-300 nm in diameter, are pulled from lipid vesicles using a micropipet technique, with multilamellar vesicles serving as reservoirs of surfactant material. In a second step, the nanotubes are wired around microfabricated SU-8 pillars. In contrast to unrestrained surfactant networks that minimize their surface free energy by minimizing nanotube path length, the technique presented here can produce nanotube networks of arbitrary geometries. For example, nanotubes can be mounted directly on support pillars, and long stretches of nanotubes can be arranged in zigzag patterns with turn angles of 180 degrees. The system is demonstrated to support electrophoretic transport of colloidal particles contained in the nanotubes down to the limit of single particles. We show that electrophoretic migration velocity is linearly dependent on the applied field strength and that a local narrowing of the nanotube diameter results from adhesion and bending around SU-8 pillars. The method presented here can aid in the fabrication of fully integrated and multiplexed nanofluidic devices that can operate with single molecules.     

Ion channel mimetic micropore and nanotube membrane sensors

This paper describes synthetic micropore and nanotube membranes that mimic the function of a ligand-gated ion channel; that is, these membranes can be switched from an "off" state (no or low ion current through the membrane) to an "on" state (higher ion current) in response to the presence of a chemical stimulus. Ion channel mimics based on both microporous alumina and Au nanotube membranes were investigated. The off state was obtained by making the membranes hydrophobic by chemisorbing either a C18 silane (alumina membrane) or a C18 thiol (Au nanotube membrane). Water and electrolyte are forbidden from entering these very hydrophobic pores/nanotubes. The transition to the on state was induced by the partitioning of a hydrophobic ionic species (e.g., a drug or a surfactant) into the membrane. The membrane switches to the on state because at a sufficiently high concentration of this ionic analyte species, the pores/nanotubes flood with water and electrolyte. A pH-responsive membrane was also prepared by attaching a hydrophobic alkyl carboxylic acid silane to the alumina membrane.     

A possible role of the dipole moment of the catalyst droplet in nanotube growth, alignment, chirality, and characteristics

Why vapor species land on the surface of the nanoparticle seed for nanotube synthesis is a vital question. An investigation has been carried out to find an answer to it. For this, a model of the dipole moment has been developed. A bimetallic alloy (non-alloy, solid solution) exhibiting the shape of a cap has been assumed to function as the nanoparticle seed. Various features of the dipole moment have been examined. The influence of the dipole moment on nanotube synthesis, alignment, chirality, and characteristics has also been studied. Available experiments on the synthesis of carbon nanotubes employing bimetallic catalysts have been compared with the results from calculations. Close correspondence between the two demonstrates that the catalysts may exhibit a dipole moment and have a crucial role in nanotube synthesis and characteristics. The dipole moment has also been employed to determine why some nanotubes grow vertically, while others are bent. Calculated results appear to explain the basic causes for this. These results suggest that the electric field resulting from the dipole moment of catalysts may be important for the vertical alignment of nanotubes. They may attest to the validity of the model and to the existence of a dipole moment in seeds. Although considered for nanotube syntheses, the results may be applicable to other nanomaterials (nanotubes, nanowires, nanodots).