Nanoscale Charge Percolation Analysis in Polymer‐Sorted (7,5) Single‐Walled Carbon Nanotube Networks

The current percolation in polymer‐sorted semiconducting (7,5) single‐walled carbon nanotube (SWNT) networks, processed from solution, is investigated using a combination of electrical field‐effect measurements, atomic force microscopy (AFM), and conductive AFM (C‐AFM) techniques. From AFM measurements, the nanotube length in the as‐processed (7,5) SWNTs network is found to range from ≈100 to ≈1500 nm, with a SWNT surface density well above the percolation threshold and a maximum surface coverage ≈58%. Analysis of the field‐effect charge transport measurements in the SWNT network using a 2D homogeneous random‐network stick‐percolation model yields an exponent coefficient for the transistors OFF currents of 16.3. This value is indicative of an almost ideal random network containing only a small concentration of metallic SWNTs. Complementary C‐AFM measurements on the other hand enable visualization of current percolation pathways in the xy plane and reveal the isotropic nature of the as‐spun (7,5) SWNT networks. This work demonstrates the tremendous potential of combining advanced scanning probe techniques with field‐effect charge transport measurements for quantification of key network parameters including current percolation, metallic nanotubes content, surface coverage, and degree of SWNT alignment. Most importantly, the proposed approach is general and applicable to other nanoscale networks, including metallic nanowires as well as hybrid nanocomposites.     

Assessment of the electrochemical behavior of two-dimensional networks of single-walled carbon nanotubes

Scanning electrochemical microscopy (SECM) has been employed in the feedback mode to assess the electrochemical behavior of two-dimensional networks of single-walled carbon nanotubes (SWNTs). It is shown that, even though the network comprises both metallic and semiconducting SWNTs, at high density (well above the percolation threshold for metallic SWNTs) and with approximately millimolar concentrations of redox species the network behaves as a thin metallic film, irrespective of the formal potential of the redox couple. This result is particularly striking since the fractional surface coverage of SWNTs is only approximately 1% and SECM delivers high mass transport rates to the network. Finite element simulations demonstrate that under these conditions diffusional overlap between neighboring SWNTs is significant so that planar diffusion prevails in the gap between the SECM tip and the underlying SWNT substrate. The SECM feedback response diminishes at higher concentrations of the redox species. However, wet gate measurements show that at the solution potentials of interest the conductivity is sufficiently high that lateral conductivity is not expected to be limiting. This suggests that reaction kinetics may be a limiting factor, especially since the low surface coverage of the SWNT network results in large fluxes to the SWNTs, which are characterized by a low density of electronic states. For electroanalytical purposes, significantly, two-dimensional SWNT networks can be considered as metallic films for typical millimolar concentrations employed in amperometry and voltammetry. Moreover, SWNT networks can be inexpensively and easily formed over large scales, opening up the possibility of further electroanalytical applications.     

Large third-order optical nonlinearity in directly synthesized single-walled carbon nanotube films

Large third-order optical nonlinearity is observed in single-walled carbon nanotube (SWNT) films that are directly synthesized by CVD method rather than post-deposited from solution. Through z-scan method, the third-order nonlinear susceptibility (chi(3)) is measured, and the |Im chi(3)| is 1.8 x 10(-7) esu at 1064 nm, which is among the highest reported values for optical nonlinear materials. Combined with their transparent morphology and ultrafast carrier relaxation time, our results indicate the promising prospect of directly synthesized SWNT films as saturable absorbers using in mode-lock lasers or ultrafast switching materials in optical telecommunications.     

Processing-structure–property relationships of SWNT–epoxy composites prepared using ionic liquids

Experimentally achieved mechanical properties of nanotube–epoxy composites fail to match theoretical expectations; shortcomings are mainly attributed to poor dispersion. The elastic modulus of a well-dispersed single walled carbon nanotube (SWNT)-ionic liquid-epoxy composite was evaluated in tension and compared to predictions by a micromechanics homogenization model. The model takes into account the mechanical properties of the constituent phases in addition to SWNT aspect ratio, spatial distribution, dispersion, and agglomeration. These parameters were evaluated using information obtained via scanning and transmission electron microscopy. The Young’s modulus of the composite shows excellent agreement with the model at low concentrations, while discrepancies at high SWNT concentrations are possibly due to composite processing limitations. At high concentrations the uncured composite mixture is above the rheological percolation threshold. As the polymer network reaches its maximum capacity for well-dispersed SWNTs, increasing volume fraction does not result in further significant reinforcing effects.     

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.     

Preparation of properties of SWNT/graphene oxide type flexible transparent conductive films

Single walled carbon nanotube (SWNT)/graphene oxide (GO) hybrid films were prepared by a facile bar coating method on a polyethylene terephthalate substrate using a mixed solution of SWCNTs and GO. An acryl type polymer was employed as a dispersion agent to obtain SWCNT and GO suspension in ethyl alcohol. The SWCNT/GO hybrid films were highly transparent and electrically conductive, showing 80% transmittance and 1.8 x 10(3) ohm/sq surface resistance. The surface resistance of the SWCNT/GO film could be further improved to 750 ohm/sq by hydrazine vapor reduction.     

Thermal conductance of an individual single-wall carbon nanotube above room temperature

The thermal properties of a suspended metallic single-wall carbon nanotube (SWNT) are extracted from its high-bias (I-V) electrical characteristics over the 300-800 K temperature range, achieved by Joule self-heating. The thermal conductance is approximately 2.4 nW/K, and the thermal conductivity is nearly 3500 Wm(-1)K(-1) at room temperature for a SWNT of length 2.6 mum and diameter 1.7 nm. A subtle decrease in thermal conductivity steeper than 1/T is observed at the upper end of the temperature range, which is attributed to second-order three-phonon scattering between two acoustic modes and one optical mode. We discuss sources of uncertainty and propose a simple analytical model for the SWNT thermal conductivity including length and temperature dependence.     

Optical anisotropy in single-walled carbon nanotube thin films: implications for transparent and conducting electrodes in organic photovoltaics

Optical anisotropy in single-walled carbon nanotube thin film networks is reported. We obtain the real and imaginary parts of the in-(parallel) and out-of-plane (perpendicular) complex dielectric functions of the single-walled carbon nanotube (SWNT) thin films by combining transmission measurements at several incidence angles with spectroscopic ellipsometry data on different substrates. In sparse networks, the two components of the real part of the complex dielectric constant (epsilon1 parallel and epsilon1 perpendicular) were found to differ by 1.5 at 2.25 eV photon energy. The resulting angular dependence (from 0 to 70 degrees incidence angles) of transmittance is reflected in the conversion efficiency of organic solar cells utilizing SWNT thin films as the hole conducting electrodes. Our results indicate that, in addition to the transparency and sheet resistance, factors such as the optical anisotropy must be considered for optical devices incorporating SWNT networks.     

Double-walled carbon nanotubes under hydrostatic pressure: Raman experiments and simulations

We have used Raman spectroscopy to study the behavior of double-walled carbon nanotubes (DWNT) under hydrostatic pressure. We find that the rate of change of the tangential mode frequency with pressure is higher for the sample with traces of polymer compared to the pristine sample. We have performed classical molecular dynamics simulations to study the collapse of single (SWNT) and double-walled carbon nanotube bundles under hydrostatic pressure. The collapse pressure (pc) was found to vary as 1/R3, where R is the SWNT radius or the DWNT effective radius. The bundles showed approximately 30% hysteresis and the hexagonally close packed lattice was completely restored on decompression. The pc of a DWNT bundle was found to be close to the sum of its values for the inner and the outer tubes considered separately as SWNT bundles, demonstrating that the inner tube supports the outer tube and that the effective bending stiffness of DWNT, D(DWNT) - 2D(SWNT).     

Templating of self-alignment patterns of anisotropic gold nanoparticles on ordered SWNT macrostructures

We report a simple and versatile technique for oriented assembly of gold nanorods on aligned single-walled carbon nanotube (SWNT) macrostructures, such as thin nanotube films and nanotube fibers. The deposition and assembly is accomplished via drop drying of dilute gold nanorod suspensions on SWNT macrostructures under ambient conditions. Guided by anisotropic interactions, gold nanorods, and polygonal platelets spontaneously align with SWNTs, resulting in macroscopic arrays of locally ordered nanorods supported on aligned SWNT substrates. SEM reveals that the scalar order parameter of rods relative to the local average SWNT alignment is 0.7 for rods on SWNT films and 0.9 for rods on SWNT fibers. This self-alignment is enabled by anisotropic gold nanoparticle-SWNT interactions and is observed for a wide range of nanoparticles, including nanorods with aspect ratios ranging from 2-35, thin gold triangular and other polygonal platelets. The plasmonic properties of aligned gold nanorods together with superior electronic, chemical and mechanical properties of SWNTs make these hybrid nanocomposites valuable for the design of self-assembled multifunctional optoelectronic materials and optical metamaterials.     

Effects of the local environment on CNT-based nanoelectronics: development of a microenvironment probe station

In this study, we report the development of a microenvironment probe station capable of detecting the effect of small changes to the local environment around a carbon nanotube conduction channel. The microenvironment probe station is highly versatile and is used to characterize alterations in carbon nanotube field effect transistor electrical behavior in response to changes in temperature, gas species, infrared and ultraviolet light. All devices were electrically characterized in atmospheric, ultrahigh vacuum and oxygen-rich environments. The results suggest that devices could be changed from n-type at 1 x 10(-8) torr through an intermediate ambipolar state at 1 x 10(-4) torr to p-type at atmosphere solely by increasing the oxygen concentration. The average resistance of these carbon nanotube field effect transistors after annealing was observed to decrease by approximately 54% from their initial value under ultrahigh vacuum to their final value in the presence of pure oxygen while corresponding threshold voltages shifts were also observed. Illumination with infrared light resulted in a approximately 10% increase in drain current with an estimated response time <1 fs due to photon-induced electron-hole pair generation. Illumination with ultraviolet light resulted in approximately 5-15% reduction in drain current due to photon-induced desorption of oxygen adsorbate.     

Dimethyl methylphosphonate detection with a single-walled carbon nanotube capacitive sensor fabricated by airbrush technique

Single-walled carbon nanotube (SWNT) films were prepared on interdigitated electrodes by airbrush technique, and their sensing properties to dimethyl methylphosphonate (DMMP) were studied. The SWNT films were characterized by field-emission scanning electron microscope. The response to different concentrations of DMMP vapors were investigated at room temperature. The results showed that the capacitance of airbrush SWNT sensor decreased rapidly in varying concentrations ranging from 12 to 60 mg/m³ (2.4–12 ppm). The capacitance sensitivity was about 12.5 % when exposed to 12 mg/m³ DMMP vapor. The capacitance sensitivity was higher when the initial capacitance and loss tangent were higher and the SWNT film was denser. It was found that the capacitance sensitivity was nearly 10 times to the resistance sensitivity. The airbrush SWNT sensor exhibited highly and fast capacitance response, good repeatability and selectivity for DMMP vapor.     

The geometrical effect of single walled carbon nanotube network transistors on low frequency noise characteristics

The noise characteristics of randomly networked single walled carbon nanotubes grown directly by plasma enhanced chemical vapor deposition with field effect transistor. Geometrical complexity due to the large number of tube-tube junctions in the nanotube network is expected to be one of the key factors for the noise power of 1/f dependence. We investigated low frequency noise as a function of channel length (2-10 microm) and found that increased with longer channel length. Percolational behaviors of nanotube network that differs from ordinary semiconducting and metallic materials can be characterized by a geometrical picture with electrical homo- and hetero-junctions. Fixed nanotube density provides a test conditions to evaluate the contributions of junctions as a noise center. Hooge's empirical law is applied to investigate the low frequency noise characteristics of single walled carbon nanotube random network transistors. The noise power shows the dependence of the transistor channel length. It is understood that nanotube/nanotube junctions act as a noise center. However, the differences induced by channel length in the noise power are observed as not so significant. We conclude that tolerance of low frequency noise is important property for SWNT networks as an electronic device application.     

Multimodal biomedical imaging with asymmetric single-walled carbon nanotube/iron oxide nanoparticle complexes

Magnetic iron oxide nanoparticles and near-infrared (NIR) fluorescent single-walled carbon nanotubes (SWNT) form heterostructured complexes that can be utilized as multimodal bioimaging agents. Fe catalyst-grown SWNT were individually dispersed in aqueous solution via encapsulation by oligonucleotides with the sequence d(GT)15, and enriched using a 0.5 T magnetic array. The resulting nanotube complexes show distinct NIR fluorescence, Raman scattering, and visible/NIR absorbance features, corresponding to the various nanotube species. AFM and cryo-TEM images show DNA-encapsulated complexes composed of a approximately 3 nm particle attached to a carbon nanotube on one end. X-ray diffraction (XRD) and superconducting quantum interference device (SQUID) measurements reveal that the nanoparticles are primarily Fe2O3 and superparamagnetic. The Fe2O3 particle-enriched nanotube solution has a magnetic particle content of approximately 35 wt %, a magnetization saturation of approximately 56 emu/g, and a magnetic relaxation time scale ratio (T1/T2) of approximately 12. These complexes have a longer spin-spin relaxation time (T2 approximately 164 ms) than typical ferromagnetic particles due to the smaller size of their magnetic component while still retaining SWNT optical signatures. Macrophage cells that engulf the DNA-wrapped complexes were imaged using magnetic resonance imaging (MRI) and NIR mapping, demonstrating that these multifunctional nanostructures could potentially be useful in multimodal biomedical imaging.     

Microwave‐Assisted Regeneration of Single‐Walled Carbon Nanotubes from Carbon Fragments

Direct growth of chirality‐controlled single‐walled carbon nanotubes (SWNTs) with metal catalyst free strategy, like cloning or epitaxial growth, has suffered from the low efficiency. The underlying problem is the activation of seed edge. Here an unexpectedly efficient microwave‐assisted pathway to regenerate SWNTs from carbon fragments on SiO₂/Si substrate is demonstrated via Raman spectroscopy and atomic force microscope (AFM) characterization. In this attempt, microwave irradiation provides fast heating to remove polar groups bonded to carbon nanotubes and reduce the spontaneous closure of tubes’ open ends. The survived SWNT and carbon fragments connected to it after plasma treatment are simply microwaved and then they serve as the template for regeneration. Scanning electron microscope and AFM characterizations indicate that the efficiency of the regeneration can reach 100%. And the regenerated SWNT has been proved without any change in chirality compared to the original SWNT. Electrical measurements on regenerated carbon nanotube films indicate 1 and 2 times increase in on/off ratio and on‐state current respectively than original carbon nanotube films obtained from solution‐phase separation, confirming the improvement of SWNT's quality. The microwave‐assisted regeneration is found to be highly effective and would be applied to improve the cloning efficiency of carbon nanotubes potentially.     

Unexpected hole transfer leads to high efficiency single-walled carbon nanotube hybrid photovoltaic

We report surprisingly efficient photocurrent generation at individual single-walled carbon nanotube (SWNT) /poly(3-hexylthiophene-2,5-diyl) (P3HT) junctions. Contrary to previous prediction, both semiconducting SWNTs (s-SWNTs) and metallic SWNTs (m-SWNTs) function as efficient hole acceptors. By active tuning of SWNTs' Fermi level, we confirm that P3HT p-dopes both s-SWNT and m-SWNT, and the work function difference between the nanotube and P3HT leads to a built-in voltage driving the efficient exciton dissociation and hole transfer. We further demonstrate square millimeter scale SWNT/P3HT bilayer photovoltaics using horizontally aligned SWNT arrays. Importantly, the devices exhibit greater than 90% effective external quantum efficiency. These key findings will not only enhance our knowledge of photocurrent generation at nanoscale interfaces, but also make selective omission of m-SWNT redundant, promising carbon nanomaterial-based, low-cost, high-efficiency hybrid photovoltaics.     

Voltage-induced dependence of Raman-active modes in single-wall carbon nanotube thin films

We report on electrical Raman measurements in transparent and conducting single-wall carbon nanotube (SWNT) thin films. Application of external voltage results in downshifts of the D and G modes and in reduction of their intensity. The intensities of the radial breathing modes increase with external electric field related to the application of the external voltage in metallic SWNTs, while decreasing in semiconducting SWNTs. A model explaining the phenomenon in terms of both direct and indirect (Joule heating) effects of the field is proposed. Our work rules out the elimination of large amounts of metallic SWNTs in thin film transistors using high field pulses. Our results support the existence of Kohn anomalies in the Raman-active optical branches of metallic graphitic materials.     

非掺杂金属型碳纳米管的电导特性

依据介观物理学的基本概念、半经典电子输运理论和碳纳米管的电子结构,对非掺杂直状金属型单层碳纳米管（ＳＷＮＴｓ）的电导特性进行理论研究,计算表明;ＳＷＮＴｓ的电导是量子化的．     

Transparent boron-doped carbon nanotube films

We report results of studies on the sheet resistance and optical transmission of thin films of boron-doped single-walled carbon nanotubes (SWNTs). Boron doping was carried out by exposure of SWNTs to B 2O 3 and NH 3 at 900 degrees C and 1-3 atom % boron was found in the SWNT bundles via electron energy loss spectroscopy (EELS). Boron doping was found to downshift the positions of the optical absorption bands associated with the van Hove singularities (E 11 (s) E 22 (s) and E 11 (m)) by approximately 30 meV relative to their positions in acid-treated and annealed SWNTs. Raman spectroscopy, EELS, and optical data are consistent with the picture that a few atom % boron has been substituted for carbon in the sp (2) framework of SWNTs. Finally, our results show that boron doping does not significantly affect the optical transmittance in the visible region. However, boron doping lowers the sheet resistance by approximately 30% relative to pristine SWNT films from the same batch. Boron-doped SWNT may provide a better approach to touch-screen technology.     

Analysing one isolated single walled carbon nanotube in the near-field domain with selective nanovolume Raman spectroscopy

In this paper, we describe a new method to the selective nanovolume analysing of one isolated single walled carbon nanotube (SWNT). This concept is based on actually available imaging micro-spectrometry systems for working in near-field domain combined with a stigmatic solid immersion lens. This combination of different analytical methods, and modified and configured equipment entitles us to expand the functionality toward a three-dimensional (3D) nanovolume Raman mapping and photoluminescence intensity with a possible discrimination in polarization, as well as photoluminescence decaytime constant mapping with their unique combination. Subsequently, selective spectra can be acquired from the same location on the samples. By spectrally selecting a SWNT, we registered the spatial distribution of the emitted photons in x, y, z vectors to determine the position of a SWNT in the near-field domain. For the SWNTs that are localized with an accuracy better than 18 nm in the x, y and <1 nm in the z directions, we demonstrate an analytical sensitivity close to a single nanotube with unity throughput. This near-field capability is applied to resolve local variations unambiguously in the Raman spectrum along one single SWNT. Finally, in this paper, we report what we believe to be the first evidence of Raman mapping and 3D real optical imaging of carbon nanotubes with near-field resolution.