Thickness-dependent thermoelectric power factor of polymer-functionalized semiconducting carbon nanotube thin films

The effects of polymer structures on the thermoelectric properties of polymer-wrapped semiconducting carbon nanotubes have yet to be clarified for elucidating intrinsic transport properties. We systematically investigate thickness dependence of thermoelectric transport in thin films containing networks of conjugated polymer-wrapped semiconducting carbon nanotubes. Well-controlled doping experiments suggest that the doping homogeneity and then in-plane electrical conductivity significantly depend on film thickness and polymer species. This understanding leads to achieving thermoelectric power factors as high as 412 μW m^?1 K^?2 in thin carbon nanotube films. This work presents a standard platform for investigating the thermoelectric properties of nanotubes.     

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.     

Doping and phonon renormalization in carbon nanotubes

We show that the Raman frequency associated with the vibrational mode at approximately 1,580 cm(-1) (the G mode) in both metallic and semiconducting carbon nanotubes shifts in response to changes in the charge density induced by an external gate field. These changes in the Raman spectra provide us with a powerful tool for probing local doping in carbon nanotubes in electronic device structures, or charge carrier densities induced by environmental interactions, on a length scale determined by the light diffraction limit. The G mode shifts to higher frequency and narrows in linewidth in metallic carbon nanotubes at large fields. This behaviour is analogous to that observed recently in graphene. In semiconducting carbon nanotubes, on the other hand, induced changes in the charge density only shift the phonon frequency, but do not affect its linewidth. These spectral changes are quantitatively explained by a model that involves the renormalization of the carbon nanotube phonon energy by the electron-phonon interaction as the carrier density in the carbon nanotube is changed.     

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.     

Effect of mixture ratios and nitrogen carrier gas flow rates on the morphology of carbon nanotube structures grown by CVD

We report on the growth of carbon nanotubes (CNTs) by thermal Chemical Vapor Deposition (CVD) and investigate the effects of nitrogen carrier gas flow rates and mixture ratios on the morphology of CNTs on a silicon substrate by vaporizing the camphor/ferrocene mixture at 750 °C in a nitrogen atmosphere. Carbon layers obtained after each CVD growth run of 15 min are characterized by scanning electron microscopy (SEM) and Raman spectroscopy. Growth of CNTs is found to occur on silicon substrates. The SEM micrographs helped better understand the nanotube growth morphology while Raman Spectroscopy was used to detect the presence of nanotubes and also identify their nature vizely semiconducting or metallic, single-walled or multi-walled. Raman Spectra was also useful to estimate the quality of the samples as a ratio of nanotube to non-nanotube content. The length and diameters of the aligned CNTs were found to depend on the pyrolysis temperatures, mixture ratio, and the nitrogen carrier gas flow rates.     

Defects in individual semiconducting single wall carbon nanotubes: Raman spectroscopic and in situ Raman spectroelectrochemical study

Raman spectroscopy and in situ Raman spectroelectrochemistry have been used to study the influence of defects on the Raman spectra of semiconducting individual single-walled carbon nanotubes (SWCNTs). The defects were created intentionally on part of an originally defect-free individual semiconducting nanotube, which allowed us to analyze how defects influence this particular nanotube. The formation of defects was followed by Raman spectroscopy that showed D band intensity coming from the defective part and no D band intensity coming from the original part of the same nanotube. It is shown that the presence of defects also reduces the intensity of the symmetry-allowed Raman features. Furthermore, the changes to the Raman resonance window upon the introduction of defects are analyzed. It is demonstrated that defects lead to both a broadening of the Raman resonance profile and a decrease in the maximum intensity of the resonance profile. The in situ Raman spectroelectrochemical data show a doping dependence of the Raman features taken from the defective part of the tested SWCNT.     

Heat Capacity of Defective Semiconducting Carbon Nanotubes

Using a random tight-binding model within the coherent potential approximation, the effects of boron and nitrogen doping on the temperature dependence of the specific heat of semiconducting zigzag carbon nanotubes are studied. It is shown that the electronic specific heat capacity behaves anomalously when the temperature is lowered. The presence of this anomaly is clarified on the basis of the idea of the so-called Schottky anomaly. More importantly, in the presence of dopants, the position of this anomaly moves towards higher temperatures and its height shifts down as the dopant concentration is increased. Such behavior is attributed to the substantial modifications in the density of states.     

Influence of substitutional doping on the electronic properties of carbon nanotubes with Stone Wales defects: density functional calculations

Abstract

In this work, we implemented density function theory to investigate the structural and the electronic properties of nitrogen doped single walled carbon nanotube under different orientations of Stone Wales defect. We have found that, the doped defected structures are more stable than the non-doped defected structures. Furthermore, doping defected carbon nanotubes with a nitrogen atom has significantly narrowed the band gap and slightly shifted the Fermi level toward the conduction band. Moreover, nitrogen substitution creates new band levels just above the Fermi level which exemplifies an n-type doping. However, the induced band gap is indirect band gap compared to direct band gap as in pristine carbon nanotubes. Furthermore, the electronic and structural properties of nitrogen doped carbon nanotube with Stone Wales defects is crucially affected by the dopant site as well as the orientations of Stone Wales defects.     

Crystallographic order in multi-walled carbon nanotubes synthesized in the presence of nitrogen

Multi-walled carbon nanotubes were synthesized by chemical vapor deposition from pure toluene and toluene/diazine mixtures using ferrocene as a catalyst precursor at 760 degrees C. As recently announced, characterization of the resulting nanotube films showed that, unlike pure carbon nanotubes, those grown in the presence of nitrogen have an extremely high degree of internal order, both in terms of the uniform chirality in the nanotube walls and of the crystallographic register between them. Here, the structure, defects, and morphology of the nanotubes were analyzed in depth using advanced electron microscopy techniques, and compared with existing models and observations. Nitrogen, which seems to be responsible for the dramatic structural order, was found to segregate preferentially within the core of the nanotubes.     

Photoluminescence imaging of electronic-impurity-induced exciton quenching in single-walled carbon nanotubes

The electronic properties of single-walled carbon nanotubes can be altered by surface adsorption of electronic impurities or dopants. However, fully understanding the influence of these impurities is difficult because of the inherent complexity of the solution-based colloidal chemistry of nanotubes, and because of a lack of techniques for directly imaging dynamic processes involving these impurities. Here, we show that photoluminescence microscopy can be used to image exciton quenching in semiconducting single-walled carbon nanotubes during the early stages of chemical doping with two different species. The addition of AuCl(3) leads to localized exciton-quenching sites, which are attributed to a mid-gap electronic impurity level, and the adsorbed species are also found sometimes to be mobile on the surface of the nanotubes. The addition of H(2)O(2) leads to delocalized exciton-quenching hole states, which are responsible for long-range photoluminescence blinking, and are also mobile.     

On the electron-phonon coupling of individual single-walled carbon nanotubes

We show that the phonon coupling to the electronic system in individual metallic single-walled carbon nanotubes is not due to coupling to low-energy plasmons. The evidence stems from the measured Raman-Stokes G-mode, which for metallic and semiconducting tubes could be fitted well by the superposition of only two Lorentzian lines associated with vibrational modes along the nanotube axis and the nanotube circumference. In the case of metallic tubes the lower-energy G mode is significantly broadened, however maintaining the Lorentzian line shape, in contrast to the theoretically expected asymmetric Breit-Wigner-Fano line shape from phonon-plasmon coupling. The results were obtained by studying 25 individual metallic and semiconducting single-walled carbon nanotubes with atomic force microscopy, electron transport measurements, and resonant Raman spectroscopy.     

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.     

Synthesis and thermoelectric power of nitrogen-doped carbon nanotubes

We have previously shown that high-purity multiwalled carbon nanotubes (pristine MWNTs) can be prepared from a mixture of xylene-ferrocene (99 at% C:1 at% Fe) inside a quartz tube reactor operating at approximately 700 degrees C. In a similar process, approximately 3 g of melamine (C3H6N6) was introduced during the growth of MWNTs to prepare nitrogen-doped nanotubes. The structural and electronic properties of nitrogen-doped MWNTs were determined by scanning electron microscopy, high-resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), and thermopower measurements. The individual nitrogen-doped nanotube exhibits a bamboo-like structure and comprises 6-16 tube walls, as evidenced by HRTEM studies. The EELS measurements yielded an average nitrogen content of approximately 5 at% in the doped tubes. The thermoelectric power data of nitrogen-doped MWNTs remained negative even after exposure to oxygen for an extended period of time, suggesting that nitrogen doping of MWNTs renders them n-type, consistent with scanning tunneling spectroscopic studies on similar nanotubes.     

Charge transfer in single-walled carbon nanotubes filled with cadmium halogenides

In this work the internal channels of the single-walled carbon nanotubes (SWCNTs) were filled with cadmium chloride, cadmium bromide, and cadmium iodide by a capillary method using melts of these salts. The influence of incorporated chemical compounds on the electronic properties of the carbon nanotubes was investigated by optical absorption spectroscopy, Raman spectroscopy, near edge X-ray absorption fine structure spectroscopy, and X-ray photoelectron spectroscopy. It was found that there is the chemical bonding between carbon atoms of nanotube walls and metal atoms of encapsulated CdX₂ nanocrystals. The obtained data testify acceptor doping effect of cadmium halogenides incorporated into the SWCNT channels, which is accompanied by the charge transfer from nanotube walls to introduced substances.     

Structural dependence of excitonic optical transitions and band-gap energies in carbon nanotubes

The optical transitions of semiconducting carbon nanotubes have been ascribed to excitons. Here we use two-photon excitation spectroscopy to measure exciton binding energies, as well as band-gap energies, in a range of individual species of semiconducting SWNTs. Exciton binding energies are large and vary inversely with nanotube diameter, as predicted by theory. Band-gap energies are significantly blue-shifted from values predicted by tight-binding calculations.     

Frequency dependence of the dielectrophoretic separation of single-walled carbon nanotubes

Dielectrophoresis on single-walled carbon nanotubes in surfactant suspensions has been demonstrated to separate metallic from semiconducting tubes by their different electric field-induced polarisabilities. Here we report that the interaction between SWNTs and the surfactant induces a nanotube surface conductance which gives rise to a unique electric field frequency dependence of the dielectrophoretic force acting on semiconducting SWNTs. We observe a surfactant concentration dependent crossover frequency enabling separation of metallic from semiconducting SWNTs at high frequency and deposition of metallic and semiconducting SWNTs at low frequency. Proof for the effectiveness of separation is given by a comparative Raman spectroscopy study on dielectrophoretically deposited tubes excited with two different wavelengths.     

Understanding the Impact of Inductance in Carbon Nanotube Bundles for VLSI Interconnect Using Scalable Modeling Techniques

In this paper, we develop accurate and scalable models for the magnetic inductance in bundles of single-walled carbon nanotubes, which have been proposed as a means to alleviate the increasingly critical resistance problems associated with traditional copper interconnect in very large scale integration (VLSI) applications. The models consider the density and statistical distribution of both metallic and semiconducting nanotubes within the bundle. We evaluate the speed, accuracy, and scalability of our magnetic inductance modeling techniques and previously proposed inductance models. The inductance model with the best performance evaluates the magnetic inductance of nanotube bundles with excellent accuracy when compared to modeling each nanotube individually and provides orders of magnitude improvement in CPU time as the bundle size increases. Leveraging the magnetic inductance modeling techniques, we determine the relative impact of magnetic and kinetic inductance. Based on our results, the relative value of magnetic and kinetic inductance on single-walled carbon nanotube (SWCNT) bundles is highly dependent on the bundle geometry and the per unit length kinetic inductance     

Electronic properties of magnetically doped nanotubes

Effect of doping of carbon nanotubes by magnetic transition metal atoms has been considered in this paper. In the case of semiconducting tubes, it was found that the system has zero magnetization, whereas in metallic tubes the valence electrons of the tube screen the magnetization of the dopants: the coupling to the tube is usually antiferromagnetic (except for Cr).     

Influence of structural and dielectric anisotropy on the dielectrophoresis of single-walled carbon nanotubes

We report on a carbon nanotube network which is composed of aligned metallic and randomly oriented semiconducting single-walled carbon nanotubes. The material is formed by using a novel radio frequency dielectrophoresis setup, which generates very large dielectrophoretic force fields and allows dielectrophoretic assembling of nanotube films up to 100 nm thickness. Polarization dependent absorption measurements provide experimental evidence for the electronic type specific alignment behavior. We explain the experimental data with an advanced model for nanotube dielectrophoresis, which explicitly takes into account both the longitudinal and transversal polarizability. On the basis of this model, we calculate the dielectrophoretic force fields and show that semiconducting nanotubes deposit under very large fields due to their transversal polarizability even for high field frequencies.