Absorption spectroscopy of individual single-walled carbon nanotubes

Current methods for producing single-walled carbon nanotubes (SWNTs) lead to heterogeneous samples containing mixtures of metallic and semiconducting species with a variety of lengths and defects. Optical detection at the single nanotube level should thus offer the possibility to examine these heterogeneities provided that both SWNT species are equally well detected. Here, we used photothermal heterodyne detection to record absorption images and spectra of individual SWNTs. Because this photothermal method relies only on light absorption, it readily detects metallic nanotubes as well as the emissive semiconducting species. The first and second optical transitions in individual semiconducting nanotubes have been probed. Comparison between the emission and absorption spectra of the lowest-lying optical transition reveal mainly small Stokes shifts. Side bands in the near-infrared absorption spectra are observed and assigned to exciton-phonon bound states. No such sidebands are detected around the lowest transition of metallic nanotubes.     

金属型与半导体型碳纳米管的分离方法

根据导电性质的不同,碳纳米管可分为金属型和半导体型.在碳纳米管的合成过程中,不同导电性能的碳纳米管总是混合在一起,很难把它们分离开来.分别从物理、化学和生物的角度介绍了目前分离金属型和半导体型碳纳米管的方法,认为DNA自组装分离碳纳米管的方法优于其它的方法,能够将不同类型的碳纳米管分离出来,并且,在分离的数量上优于所有其它的分离方法.     

Electronic Property Modification of Single‐Walled Carbon Nanotubes by Encapsulation of Sulfur‐Terminated Graphene Nanoribbons

The use of carbon nanotubes (CNTs) as cylindrical reactor vessels has become a viable means for synthesizing graphene nanoribbons (GNRs). While previous studies demonstrated that the size and edge structure of the as‐produced GNRs are strongly dependent on the diameter of the tubes and the nature of the precursor, the atomic interactions between GNRs and surrounding CNTs and their effect on the electronic properties of the overall system are not well understood. Here, it is shown that the functional terminations of the GNR edges can have a strong influence on the electronic structure of the system. Analysis of SWCNTs before and after the insertion of sulfur‐terminated GNRs suggests a metallization of the majority of semiconducting SWCNTs. This is indicated by changes in the radial breathing modes and the D and G band Raman features, as well as UV–vis–NIR absorption spectra. The variation in resonance conditions of the nanotubes following GNR insertion make direct (n,m) assignment by Raman spectroscopy difficult. Thus, density functional theory calculations of representative GNR/SWCNT systems are performed. The results confirm significant changes in the band structure, including the development of a metallic state in the semiconducting SWCNTs due to sulfur/tube interactions. The GNR‐induced metallization of semiconducting SWCNTs may offer a means of controlling the electronic properties of bulk CNT samples and eliminate the need for a physical separation of semiconducting and metallic tubes.     

Purification and separation of single-walled carbon nanotubes (SWCNTs)

Purification or separation of single-walled carbon nanotubes (SWCNTs) is one of the most fundamental steps before they are used for research and technological applications. Based on the difference of their physical and chemical properties, separation of carbon nanotubes (CNTs) can be categorized into three groups: length separation, metallic and semiconducting tubes separation and chirality separation. In this review, we first briefly review the purification of CNTs and then focus on the different methods for the separation of CNTs.     

Label-free imaging of semiconducting and metallic carbon nanotubes in cells and mice using transient absorption microscopy

As interest in the potential biomedical applications of carbon nanotubes increases, there is a need for methods that can image nanotubes in live cells, tissues and animals. Although techniques such as Raman, photoacoustic and near-infrared photoluminescence imaging have been used to visualize nanotubes in biological environments, these techniques are limited because nanotubes provide only weak photoluminescence and low Raman scattering and it remains difficult to image both semiconducting and metallic nanotubes at the same time. Here, we show that transient absorption microscopy offers a label-free method to image both semiconducting and metallic single-walled carbon nanotubes in vitro and in vivo, in real time, with submicrometre resolution. By using appropriate near-infrared excitation wavelengths, we detect strong transient absorption signals with opposite phases from semiconducting and metallic nanotubes. Our method separates background signals generated by red blood cells and this allows us to follow the movement of both types of nanotubes inside cells and in the blood circulation and organs of mice without any significant damaging effects.     

聚合物/碳纳米管复合材料研究进展

聚合物／碳纳米管复合材料近年来引起人们广泛的关注。本文综述了聚合物／碳纳米管复合材料的研究进展，重点介绍了聚合物／碳纳米管复合材料的类型、制备方法及力学、电学和光学性能等。     

Employing Raman spectroscopy to qualitatively evaluate the purity of carbon single-wall nanotube materials

Carbon single-wall nanotubes (SWNTs) have highly unique electronic, mechanical and adsorption properties, making them interesting for a variety of applications. Raman spectroscopy has been demonstrated to be one of the most important methods for characterizing SWNTs. For example, Raman spectroscopy may be employed to differentiate between metallic and semi-conducting nanotubes, and may also be employed to determine SWNT diameters and even the nanotube chirality. Single-wall carbon nanotubes are generated in a variety of ways, including arc-discharge, laser vaporization and various chemical vapor deposition (CVD) techniques. In all of these methods, a metal catalyst must be employed to observe SWNT formation. Also, all of the current synthesis techniques generate various non-nanotube carbon impurities, including amorphous carbon, fullerenes, multi-wall nanotubes (MWNTs) and nano-crystalline graphite, as well as larger micro-sized particles of graphite. For any of the potential nanotube applications to be realized, it is, therefore, necessary that purification techniques resulting in the recovery of predominantly SWNTs at high-yields be developed. It is, of course, equally important that a method for determining nanotube wt.% purity levels be developed and standardized. Moreover, a rapid method for qualitatively measuring nanotube purity could facilitate many laboratory research efforts. This review article discusses the application of Raman spectroscopy to rapidly determine if large quantities of carbon impurities are present in nanotube materials. Raman spectra of crude SWNT materials reveal tangential bands between 1500-1600 cm(-1), as well as a broad band at approximately 1350 cm(-1), attributed to a convolution of the disorder-induced band (D-band) of carbon impurities and the D-band of the SWNTs themselves. Since the full-width-at-half-maximum (FWHM) intensity of the various carbon impurity D-bands is generally much broader than that of the nanotube D-band, an indication of the SWNT purity level may be obtained by simply examining the line-width of the D-band. We also briefly discuss the effect of nanotube bundling on SWNT Raman spectra. Finally, sections on employing Raman spectroscopy, and Raman spectroscopy coupled with additional techniques, to identify the separation and possible isolation of a specific nanotube within purified SWNT materials is provided. Every SWNT can be considered to be a unique molecule, with different physical properties, depending on its (n, m) indices. The production of phase-pure (n, m) SWNTs may be essential for some nanotube applications.     

Direct identification of metallic and semiconducting single-walled carbon nanotubes in scanning electron microscopy

Because of their excellent electrical and optical properties, carbon nanotubes have been regarded as extremely promising candidates for high-performance electronic and optoelectronic applications. However, effective and efficient distinction and separation of metallic and semiconducting single-walled carbon nanotubes are always challenges for their practical applications. Here we show that metallic and semiconducting single-walled carbon nanotubes on SiO(2) can have obviously different contrast in scanning electron microscopy due to their conductivity difference and thus can be effectively and efficiently identified. The correlation between conductivity and contrast difference has been confirmed by using voltage-contrast scanning electron microcopy, peak force tunneling atom force microscopy, and field effect transistor testing. This phenomenon can be understood via a proposed mechanism involving the e-beam-induced surface potential of insulators and the conductivity difference between metallic and semiconducting SWCNTs. This method demonstrates great promise to achieve rapid and large-scale distinguishing between metallic and semiconducting single-walled carbon nanotubes, adding a new function to conventional SEM.     

Progress towards monodisperse single-walled carbon nanotubes

The defining characteristic of a nanomaterial is that its properties vary as a function of its size. This size dependence can be clearly observed in single-walled carbon nanotubes, where changes in structure at the atomic scale can modify the electronic and optical properties of these materials in a discontinuous manner (for example, changing metallic nanotubes to semiconducting nanotubes and vice versa). However, as most practical technologies require predictable and uniform performance, researchers have been aggressively seeking strategies for preparing samples of single-walled carbon nanotubes with well-defined diameters, lengths, chiralities and electronic properties (that is, uniformly metallic or uniformly semiconducting). This review highlights post-synthetic approaches for sorting single-walled carbon nanotubes - including selective chemistry, electrical breakdown, dielectrophoresis, chromatography and ultracentrifugation - and progress towards selective growth of monodisperse samples.     

碳纳米管的组装

碳纳米管具有很多奇异的物理、化学性能．组装后的碳纳米管在光、磁、电、催化、机械等方面都展现出更加优异的特性，具有广泛的应用前景。本文对碳纳米管组装技术的现状和最新研究进展情况进行了综述，也讨论了组装机理．并对碳纳米管组装的未来进行了展望。     

Transition of single-walled carbon nanotubes from metallic to semiconducting in field-effect transistors by hydrogen plasma treatment

We report hydrogen plasma treatment results on converting the metallic single-walled carbon nanotubes to semiconducting single-walled carbon nanotubes. We found that the as-grown single-walled carbon nanotubes (SWNTs) can be sorted as three groups which behave as metallic, as-metallic, and semiconducting SWNTs. These three groups have different changes under hydrogen plasma treatment and successive annealing process. The SWNTs can be easily hydrogenated in the hydrogen plasma environment and the as-metallic SWNTs can be transformed to semiconducting SWNTs. The successive annealing process can break the C-H bond, so the conversion is reversible.     

Synthesis of Inorganic Nanotubes

Nanotubes constitute an exciting class of one‐dimensional nanomaterials of which carbon nanotubes are recognized widely as materials of importance. The possibility of having inorganic nanotubes was recognized early in the 1990s, accompanied by the report of nanotubes of MoS₂ and WS₂. Since then, nanotubes of several inorganic materials have been prepared and characterized. While nanotubes of metal chalcogenides and oxides form a high proportion of the inorganic nanotubes investigated hither to, nanotubes of many other materials have also been prepared and characterized. Several synthetic strategies including both physical and chemical methods have been employed, of which the use of templates, precursors, and hydro‐ or solvothermal methods are prominent. In this article, we shall present a brief account of the present status of the synthesis of nanotubes of elemental materials as well as binary and complex metal oxides, chalcogenides, pnictides and carbides.     

Mechanical alloying synthesis of carbon nanotubes in the presence of AlFe small clusters

Carbon nanotubes and small metallic particles (1-3 nm) have been obtained using mechanical alloying techniques. High resolution electron microscope (HREM) techniques have been employed for the structural characterization of the small metallic particles and for the carbon multiwalled nanotubes. Theoretical simulations based on molecular dynamics and quantum mechanic calculations have been used to get insights on the experimental structural results.     

Highly selective sorting of semiconducting single wall carbon nanotubes exhibiting light emission at telecom wavelengths

Single wall carbon nanotubes (SWNTs) are known for their exceptional electronic properties.However,most of the synthesis methods lead to the production of a mixture of carbon nanotubes having different chiralities associated with metallic (m-SWNTs) and semiconducting (s-SWNTs) characteristics.For application purposes,effective methods for separating these species are highly desired.Here,we report a protocol for achieving a highly selective separation of s-SWNTs that exhibit a fundamental optical transition centered at 1,550 nm.We employ a polymer assisted sorting approach,and the influence of preparation methods on the optical and transport performances of the separated nanotubes is analyzed.As even traces of m-SWNTs can critically affect performances,we aim to produce samples that do not contain any detectable fraction of residual m-SWNTs.     

Selective tuning of the electronic properties of coaxial nanocables through exohedral doping

The electronic properties of exohedrally doped double-walled carbon nanotubes (DWNTs) have been investigated using density functional theory and resonance Raman spectroscopy (RRS) measurements. First-principles calculations elucidate the effects of exohedral doping on the M@S and S@M systems, where a metallic (M) tube is either inside or outside a semiconducting (S) one. The results demonstrate that metallic nanotubes are extremely sensitive to doping even when they are inner tubes, in sharp contrast to semiconducting nanotubes, which are not affected by doping when the outer shell is a metallic nanotube (screening effects). The theoretical predictions are in agreement with RRS data on Br2- and H2SO4-doped DWNTs. These results pave the way to novel nanoscale electronics via exohedral doping.     

Carbon Nanotubes Grown by RF Heating and Their Morphological and Structural Properties

Multiwall and single-wall carbon nanotubes were synthesized on Fe-Co/CaCO₃ and a Fe-Co/MgO catalyst system, respectively, by using two different catalytic chemical vapor deposition methods, external furnace (EF) heating and radio frequency (RF) excitation. The carbon nanotubes synthesized with radio frequency excitation have a smaller outer diameter, fewer layers (smaller outer/inner diameter ratio), and better crystalline properties than the nanotubes grown with external furnace heating. The radio frequency process was found to be responsible for a faster growth rate of the carbon nanotubes over longer periods of time due to a higher localized heating. These findings can be explained by the skin currents induced in the metallic catalytic clusters, which keep the catalysts active for longer periods of time and diminish the amount of noncrystalline carbon formed in the synthesis process.     

Carbon nanotube reinforced polymer composites—A state of the art

Because of their high mechanical strength, carbon nanotubes (CNTs) are being considered as nanoscale fibres to enhance the performance of polymer composite materials. Novel CNT-based composites have been fabricated using different methods, expecting that the resulting composites would possess enhanced or completely new set of physical properties due to the addition of CNTs. However, the physics of interactions between CNT and its surrounding matrix material in such nano-composites has yet to be elucidated and methods for determining the parameters controlling interfacial characteristics such as interfacial shear stress, is still challenging. An improvement of the physical properties of polymer nanocomposites, based on carbon nanotubes (CNTs), is addicted to a good dispersion and strong interactions between the matrix and the filler.     

General theories for the electrical transport properties of carbon nanotubes

We have shown that the general theories of metals and semiconductors can be employed to understand the diameter and voltage dependency of current through metallic and semiconducting carbon nanotubes, respectively. The current through a semiconducting multiwalled carbon nanotube (MWCNT) is associated with the energy gap that is different for different shells. The contribution of the outermost shell is larger as compared to the inner shells. The general theories can also explain the diameter dependency of maximum current through nanotubes. We have also compared the current carrying ability of a MWCNT and an array of the same diameter of single wall carbon nanotubes (SWCNTs) and found that MWCNTs are better suited and deserve further investigation for possible applications as interconnects.     

碳纳米管纯化处理的研究进展

目前制备碳纳米管的方法有很多,但这些方法制备的碳纳米管样品中大部分含有无定形碳、碳纳米颗粒和催化剂等杂质,这些杂质的存在直接影响其性能并限制其应用,因此碳纳米管的纯化研究很有必要。结合该领域的研究前沿概述了碳纳米管纯化处理的研究现状,简单介绍了物理纯化方法和化学纯化方法的特点,详细介绍了物理纯化法、化学纯化法和综合纯化法,并展望了纯化方法的趋势。     

Logic circuits based on individual semiconducting and metallic carbon-nanotube devices

Nanoscale transistors employing an individual semiconducting carbon nanotube as the channel hold great potential for logic circuits with large integration densities that can be manufactured on glass or plastic substrates. Carbon nanotubes are usually produced as a mixture of semiconducting and metallic nanotubes. Since only semiconducting nanotubes yield transistors, the metallic nanotubes are typically not utilized. However, integrated circuits often require not only transistors, but also resistive load devices. Here we show that many of the metallic carbon nanotubes that are deposited on the substrate along with the semiconducting nanotubes can be conveniently utilized as load resistors with favorable characteristics for the design of integrated circuits. We also demonstrate the fabrication of arrays of transistors and resistors, each based on an individual semiconducting or metallic carbon nanotube, and their integration on glass substrates into logic circuits with switching frequencies of up to 500 kHz using a custom-designed metal interconnect layer.