Superior performance of non-activated multi-walled carbon nanotube polymer actuator containing ruthenium oxide over a single-walled carbon nanotube

The electrochemical and electromechanical properties of actuators developed using a non-activated multi-walled carbon nanotube (MWCNT)–ionic liquid (IL) gel electrode containing ruthenium oxide (RuO₂) were compared with only-MWCNT and only-single-walled carbon nanotube (SWCNT) based actuators. The double-layer capacitance of the non-activated MWCNT electrode containing RuO₂ was larger than that of the only-MWCNT electrode. The non-activated MWCNT polymer actuator containing RuO₂ surpassed the performance of the only-MWCNT and only-SWCNT actuators in terms of the strain and maximum generated stress. Both MWCNTs and RuO₂ were required to produce large strain and quick response actuators that surpassed the performance of the only-SWCNT polymer actuator and exhibited characteristics sufficient for practical applications (e.g. tactile display).     

Micropatterning of single-walled carbon nanotube forest

In this work, high-aligned single-walled carbon nanotube (SWCNT) forest have been grown using a high-density plasma chemical vapor deposition technique (at room temperature) and patterned into micro-structures by photolithographic techniques, that are commonly used for silicon integrated circuit fabrication. The SWCNTs were obtained using pure methane plasma and iron as precursor material (seed). For the growth carbon SWCNT forest the process pressure was 15 mTorr, the RF power was 250 W and the total time of the deposition process was 3 h. The micropatterning processes of the SWCNT forest included conventional photolithography and magnetron sputtering for growing an iron layer (precursor material). In this situation, the iron layer is patterned and high-aligned SWCNTs are grown in the where iron is present, and DLC is formed in the regions where the iron precursor is not present. The results can be proven by Scanning Electronic Microscopy and Raman Spectroscopy. Thus, it is possible to fabricate SWCNT forest-based electronic and optoelectronic devices.     

Assembly of cross-linked multi-walled carbon nanotube mats

High content carbon nanotubes mats have been produced to a range of thicknesses and diameters by covalent bonded cross-linking of thiolated multi-walled carbon nanotubes. The Michael addition pathway was used to cross-link benzoquinone to thiol groups attached to the surface of the nanotubes. The mats were characterized by a variety of techniques including X-ray photoelectron spectroscopy, tensile strength as well as qualitative structural analysis by scanning electron microscopy. It was found that the optimum ratio by weight for cross-linking benzoquinone to thiolated carbon nanotubes was ca. 5:1. This work provided a simple route to the production of mats without high pressure processing or irradiation techniques generally used to produce Buckypaper which can require pressure control chambers, argon and hydrogen ion beams and high temperatures. The mat surface can be further functionalized with nanoparticles to form advanced carbon composite materials.     

Characterization of carbon atomistic pathways during single-walled carbon nanotube growth on supported metal nanoparticles

One of the outstanding questions about synthesis of single-walled carbon nanotubes is what is the role and mechanism of carbon diffusion during chemical vapor deposition synthesis. Examination of individual trajectories of all carbon atoms in reactive molecular dynamics simulated growth of single-walled carbon nanotubes on supported nanoparticles identifies carbon atoms involved in surface diffusion, bulk diffusion, and potential carbide formation. We show that transitions between induction, nucleation, and growth are denoted by saturation of the nanoparticle and by changes in the catalytic regime. It is found that nucleation and dissolution may occur simultaneously, with pre-saturation nucleation driven by the low-energy barrier for surface diffusion. It is concluded that for carbon-philic catalysts, induction and nucleation periods are usually governed by bulk diffusion, while the growth period is dominated by surface diffusion. Surface diffusion control during growth is in agreement with successful nanotube growth on metals such as copper and gold, which do not dissolve carbon. In the range studied, C solubility decreases with particle size, and the Ni/C ratios found coincide with stoichiometries of known Ni carbides.     

A multi-walled carbon nanotube/polymer actuator that surpasses the performance of a single-walled carbon nanotube/polymer actuator

Actuators were developed using activated and non-activated multi-walled carbon nanotube (MWCNT)–ionic liquid (IL) gel electrodes and compared to a single-walled carbon nanotube (SWCNT)-based actuator with respect to the electrochemical and electromechanical properties. The activated MWCNT–COOH/polymer actuator surpassed the SWCNT/polymer actuator in terms of the generated strain.     

Catalysts effect on single-walled carbon nanotube branching

The catalytic effect on the Y-shaped single-walled carbon nanotubes (Y-SWNTs) branching is investigated. The formation of Y-shaped branches is found to be dependent on the catalysts composition, which can be correlated to the Gibbs free energy of metal carbide formation. Easier carbide formers, like Mo or Zr, have a strong tendency to attach to the sidewall of SWNTs, enhancing the degree of carbon nanotube branching. The electrical conductance of the Y-SWNTs demonstrated rectification characteristics at room temperature, which is attributed to the Schottky barrier formed at the junction position. The Y-SWNTs can be used as a building block for future nanoelectronic, sensor and composite.     

Evaluation of metallic and semiconducting single-walled carbon nanotube characteristics

The nature of the mixed electronic type metallic (M-) and semiconducting (S-) single-walled carbon nanotubes (SWNTs) synthesized by current methods has posed a key challenge for the development of high performance SWNT-based electronic devices. The precise measurements of M- to S-SWNT ratio in as-grown or separated samples are of paramount importance for the controlled synthesis, separation and the realization of various applications. The objective of this review is to provide comprehensive overview of the progress achieved so far for measuring the M/S ratio both on individual and collective levels of SWNT states. We begin with a brief introduction of SWNT structures/properties and discussion of the problems and difficulties associated with precise measurement of the M/S ratio, and then introduce the principles for obtaining distinguished signals from M-and S-SWNTs. These techniques are classified into different groups based either on the single/ensemble detection of SWNT samples or on the principles of techniques themselves. We then present the M/S ratio evaluation results of these methods, with emphasis on scanning probe microscopy (SPM)-based detection techniques. Finally, the prospects of precise and large-scale measurement of M/S ratio in achieving controlled synthesis and understanding growth mechanism of SWNTs are discussed.     

Surfactant-free assembling of functionalized single-walled carbon nanotube buckypapers

The electrical and textural properties of single-walled carbon nanotube buckypapers were tunned through chemical functionalization processes. Single-walled carbon nanotubes (SWCNTs) were covalently functionalized with three different chemical groups: Carboxylic acids (-COOH), benzylamine (-Ph-CH₂-NH₂), and perfluorooctylaniline (-Ph-(CF₂)₇-CF₃). Functionalized SWCNTs were dispersed in water or dimethylformamide (DMF) by sonication treatments without the addition of surfactants or polymers. Carbon nanotube sheets (buckypapers) were prepared by vacuum filtration of the functionalized SWCNT dispersions. The electrical conductivity, textural properties, and processability of the functionalized buckypapers were studied in terms of SWCNT purity, functionalization, and assembling conditions. Carboxylated buckypapers demonstrated very low specific surface areas (< 1 m²/g) and roughness factor (R_a = 14 nm), while aminated and fluorinated buckypapers exhibited roughness factors of around 70 nm and specific surface areas of 160-180 m²/g. Electrical conductivity for carboxylated buckypapers was higher than for as-grown SWCNTs, but for aminated and fluorinated SWCNTs it was lower than for as-grown SWCNTs. This could be interpreted as a chemical inhibition of metallic SWCNTs due to the specificity of the diazonium salts reaction used to prepare the aminated and fluorinated SWCNTs. The utilization of high purity as-grown SWCNTs positively influenced the mechanical characteristics and the electrical conductivity of functionalized buckypapers.     

Correlation between catalyst particle and single-walled carbon nanotube diameters

Single-walled carbon nanotubes (CNTs) were synthesised at different conditions by a novel aerosol method based on the introduction of pre-formed iron catalyst particles into conditions leading to CNT formation. The results of statistical measurements of individual CNT dimensions based on high-resolution TEM images showed the effects of the residence time and temperature in the reactor. The ratio between catalyst particle and CNT diameters was close to 1.6 and independent of the experimental conditions, thus revealing an astonishing “universality” in the growth process. A proposed geometric model of heptagon defect formation, which initiates and maintains the CNT growth, allowed us to theoretically explain the phenomenon.     

Millimeter-tall single-walled carbon nanotube forests grown from ethanol

Millimeter-tall vertically-aligned carbon nanotubes (VA-CNTs) were grown from ethanol under ambient pressure by Co-catalyzed chemical vapor deposition (CVD), with systematic optimization of the CVD temperature and catalytic conditions using combinatorial catalyst libraries. We investigated the use of both aluminum oxide and silicon oxide as underlayers for the Co catalyst and found that VA-CNTs grew to millimeter heights in 15-30 min when the pyrolysis of ethanol was carried out at high temperatures (?850 °C) and long residence times (?10 s). Thick Co catalytic layers (?1.3 nm) produced (sub)millimeter-tall multi-walled VA-CNTs on both the aluminum oxide and silicon oxide underlayers. However, thin Co catalytic layers (0.62-1.0 nm) produced (sub)millimeter-tall VA-CNTs, which consisted mainly of single-walled CNTs, only on the aluminum oxide underlayers. Stripe patterns were found in the VA-CNTs near the substrate on both aluminum oxide and silicon oxide, indicating some instability prior to growth termination. The possible roles of aluminum oxide in growing millimeter-tall single-walled VA-CNTs were discussed.     

Well-dispersed single-walled carbon nanotube/polyaniline composite films

Single-walled carbon nanotube (SWNT)/polyaniline (PANI) composite films with good uniformity and dispersion were prepared by electrochemical polymerization of aniline containing well-dissolved SWNTs. The results of atomic force microscopy (AFM) and UV-Vis adsorption spectroscopy show that aniline can be used to solubilize SWNTs via formation of donor-acceptor complexes. The electrochemical deposition of SWNT-aniline solutions have been investigated by cyclic voltammetry. The results show that SWNT-based aniline solutions exhibit a drastic increase in peak current within the potential scanning region. The doping effect of SWNTs on PANI films was investigated by electrochemistry and FTIR spectroscopy. The results indicate that the enhanced electroactivity and conductivity of the SWNT/PANI composite films may be due to the strong interaction between SWNTs and PANI, which facilitates the effective degree of electron delocalization.     

Towards high purity graphene/single-walled carbon nanotube hybrids with improved electrochemical capacitive performance

CoMgAl layered double hydroxides were prepared as catalysts for the in situ synchronous growth of graphene and single-walled carbon nanotubes (SWCNTs) from methane by chemical vapor deposition. The as-calcined CoMgAl layered double oxide (LDO) flakes served as the template for the deposition of graphene, and Co nanoparticles (NPs) embedded on the LDOs catalyzed the growth of SWCNTs. After the removal of CoMgAl LDO flakes, graphene (G)/SWCNT/Co₃O₄ hybrids with SWCNTs directly grown on the surface of graphene and 27.3 wt.% Co₃O₄ NPs encapsulated in graphene layers were available. Further removal of the Co₃O₄ NPs by a CO₂-oxidation assistant purification method induced the formation of G/SWCNT hybrids with a high carbon purity of 98.4 wt.% and a high specific surface area of 807.0 m²/g. The G/SWCNT/Co₃O₄ hybrids exhibited good electrochemical performance for pseudo-capacitors due to their high Co₃O₄ concentration and the high electrical conductivity of SWCNTs and graphene. In another aspect, the G/SWCNT hybrids can be used as excellent electrode materials for double-layer capacitors. A high capacity of 98.5 F/g_electrode was obtained at a scan rate of 10 mV/s, 78.2% of which was retained even when the scan rate increased to 500 mV/s.     

Anisotropic electrical conduction of vertically-aligned single-walled carbon nanotube films

Anisotropic electrical conduction measurements have been carried out for thin films of vertically-aligned single-walled carbon nanotubes (VA-SWCNTs) grown by an alcohol catalytic CVD process. Combined with controlled synthesis and structure characterization by optical spectroscopy, the influence of the aligned structure on the electrical conduction has been identified. The out-of-plane conductivity of the films was measured to be about 0.56 S/mm, independently of the film thickness. On the other hand, the in-plane conductivity was found to be more than an order of magnitude smaller, which gives rise to highly anisotropic electrical conduction, reflecting the high degree of alignment in the VA-SWCNT films. The in-plane conductivity decreases with increasing film thickness, in contrast to the film of random SWCNT networks, which exhibit thickness-independent in-plane resistance. The thickness-dependent in-plane conductivity can be expounded by a growth model of vertically aligned SWCNT films in which a thin layer of nanotube networks form on top of films at the initial stage of the growth. Such electrical anisotropy of VA-SWCNT films can be useful in miniaturized sensing devices.     

The influence of single-walled carbon nanotube functionalization on the electronic properties of their polyaniline composites

The “in situ” preparation and characterization of composites of polyaniline (PANI) and single-walled carbon nanotubes (SWCNTs) are reported. To improve the dispersion and compatibility with the polymer matrix the raw SWCNTs were modified following different routes. SWCNTs oxidized by chemical or thermal treatments (nitric acid and air oxidation, respectively) were subjected to covalent functionalization with octadecylamine (ODA). SWCNT/PANI composites were prepared either from just oxidized SWCNTs, or from ODA functionalized SWCNTs. Temperature-programmed desorption, elemental analyses, ultraviolet-visible (UV-vis), UV-vis with near infrared and Raman spectroscopy, X-ray diffraction, scanning and transmission electron microscopy and conductivity measurements were used to characterize the functionalized SWCNT materials, dispersions and composites. The PANI composite prepared from air oxidized SWCNTs showed the best electrical conductivity indicating a better interaction with polyaniline than ODA functionalised SWCNTs. The improvement of conductivity is attributed to the doping effect or charge transfer of quinoide rings from PANI to SWCNTs.     

Outer-specific surface area as a gauge for absolute purity of single-walled carbon nanotube forests

We present a simple approach to estimate the absolute purity of carbon nanotube (CNT) forests based on outer-specific surface area (SSA). The outer-SSA and absolute purity for diverse forms of CNT forests to increased levels of carbonaceous impurities showed similar behavior and revealed a method to distinguish between CNTs and carbonaceous impurities. Furthermore, these experiments showed a direct proportionality between the outer-SSA and absolute purity which led to a simple analytical model to use outer-SSA as a gauge for absolute purity analysis.     

Neutralized fluorine radical detection using single-walled carbon nanotube network

It is known that single-walled carbon nanotubes (SWCNTs) can be functionalized by fluorine gas. Here, we report neutralized fluorine radical detection using a matted sheet of SWCNTs, prepared by alternating current dielectrophoresis. Upon exposure to neutralized radicals containing fluorine atoms in a plasma, as model analytes, the conductance of the SWCNT matt showed fast modulation. The transduction mechanism was investigated by electrical transport measurements, X-ray photoelectron spectroscopy and Raman spectroscopy. Metallic nanotubes were shown to react covalently to the near exclusion of semiconducting species. The selectivity was promoted by the curvature-induced strain of the nanotubes. The results open new opportunities for the detection of fluorine radicals at specific locations inside the reaction zone using a simple, miniaturized carbon nanotube network.     

Reinforcing randomly oriented transparent freestanding single-walled carbon nanotube films

We report an improvement of the mechanical properties of transparent randomly oriented freestanding single-walled carbon nanotube (SWCNT) films by deposition of polymers using a drop casting method and aluminum oxide utilizing an atomic layer deposition (ALD) technique. Due to the thickness increase, the polymer coating resulted in an increase in toughness, however, simultaneously decreasing the ultimate tensile strength. The 100 nm thick SWCNT films ALD-coated with Al₂O₃ layer revealed significant increase in the ultimate tensile strength from 46 ± 5 to 213 ± 17 and 80 ± 4 to 318 ± 16 MPa depending on the network density, preserving the high level of porosity of the structure.     

Molecular electronic devices based on single-walled carbon nanotube electrodes

As the top-down fabrication techniques for silicon-based electronic materials have reached the scale of molecular lengths, researchers have been investigating nanostructured materials to build electronics from individual molecules. Researchers have directed extensive experimental and theoretical efforts toward building functional optoelectronic devices using individual organic molecules and fabricating metal-molecule junctions. Although this method has many advantages, its limitations lead to large disagreement between experimental and theoretical results. This Account describes a new method to create molecular electronic devices, covalently bridging a gap in a single-walled carbon nanotube (SWNT) with an electrically functional molecule. First, we introduce a molecular-scale gap into a nanotube by precise oxidative cutting through a lithographic mask. Now functionalized with carboxylic acids, the ends of the cleaved carbon nanotubes are reconnected with conjugated diamines to give robust diamides. The molecular electronic devices prepared in this fashion can withstand and respond to large environmental changes based on the functional groups in the molecules. For example, with oligoanilines as the molecular bridge, the conductance of the device is sensitive to pH. Similarly, using diarylethylenes as the bridge provides devices that can reversibly switch between conjugated and nonconjugated states. The molecular bridge can perform the dual task of carrying electrical current and sensing/recognition through biological events such as protein/substrate binding and DNA hybridization. The devices based on DNA can measure the difference in electrical properties of complementary and mismatched strands. A well-matched duplex DNA 15-mer in the gap exhibits a 300-fold lower resistance than a duplex with a GT or CA mismatch. This system provides an ultrasensitive way to detect single-nucleotide polymorphisms at the individual molecule level. Restriction enzymes can cleave certain cDNA strands assembled between the SWNT electrodes; therefore, these strands maintain their native conformation when bridging the ends of the SWNTs. This methodology for creating novel molecular circuits forges both literal and figurative connections between chemistry, physics, materials science, and biology and promises a new generation of integrated multifunctional sensors and devices.