Controlled oxidative cutting of single-walled carbon nanotubes

The oxidation reaction of piranha solutions with purified HiPco carbon nanotubes was measured as a function of temperature. At high temperatures, piranha is capable of attacking existing damage sites, generating vacancies in the graphene sidewall, and consuming the oxidized vacancies to yield short, cut nanotubes. Increased reaction time results in increasingly shorter nanotubes. However, significant sidewall damage occurs as well as selective etching of the smaller diameter nanotubes. On the other hand, room-temperature piranha treatments show the capability of cutting existing damage sites with minimal carbon loss, slow etch rates, and little sidewall damage. Combined with a method of introducing controlled amounts of damage sites, these room-temperature piranha solutions have the potential to yield an efficient means of creating short, cut nanotubes.     

Highly efficient metal-free growth of nitrogen-doped single-walled carbon nanotubes on plasma-etched substrates for oxygen reduction

We have for the first time developed a simple plasma-etching technology to effectively generate metal-free particle catalysts for efficient metal-free growth of undoped and/or nitrogen-doped single-walled carbon nanotubes (CNTs). Compared with undoped CNTs, the newly produced metal-free nitrogen-containing CNTs were demonstrated to show relatively good electrocatalytic activity and long-term stability toward oxygen reduction reaction (ORR) in an acidic medium. Owing to the highly generic nature of the plasma etching technique, the methodology developed in this study can be applied to many other substrates for efficient growth of metal-free CNTs for various applications, ranging from energy related to electronic and to biomedical systems.     

Growth of millimeter-long and horizontally aligned single-walled carbon nanotubes on flat substrates

Millimeter-long and well-aligned single-walled carbon nanotubes (SWNTs) have been produced on silica/silicon surfaces using the carbon monoxide chemical vapor deposition (CO-CVD) method. The orientation of the nanotube arrays can be well-controlled by the gas flow during the growth. The majority of the orientated SWNTs are straight and individual. The length of the nanotubes can be >2 mm for a 10 min growth. Furthermore, multidimensional crossed-networks of SWNT can be easily generated by multistep processes. These results present a great opportunity in the controllable production of organized SWNT arrays for large-scale carbon nanotube-based nanodevice fabrication.     

Growth of high-density parallel arrays of long single-walled carbon nanotubes on quartz substrates

Herein we report a CVD approach to prepare high-density and perfectly aligned arrays of long SWNTs on stable temperature (ST)-cut quartz substrates using copper as catalyst and ethanol as carbon source. Compared with earlier reports, we have demonstrated that the aligned nanotube arrays can be grown on ST quartz substrate without the need of thermal annealing. The density can reach >50 nanotubes per micron and the length can be a few millimeters. Additionally, we have obtained direct proof on the "tip-growth" mechanism for the aligned nanotubes and important evidence that explained the termination of the growth.     

Diameter control and growth mechanism of single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) have been synthesized using the alcohol chemical vapor deposition technique. On comparing the SWNTs synthesized using different catalyst compositions, an obvious fact has been clarified – the diameter of SWNTs is strongly dependent on the sizes of the catalyst particles and metal species. Iron atoms exhibit a strong interaction with carbon atoms and keep their diameters narrow. Cobalt atoms exhibit a poorer interaction than the iron atoms, but work to decompose ethanol. As a result, narrow SWNTs are generated on the iron-rich catalyst. In this Letter, we propose the most probable growth mechanism of the SWNTs.     

Vertical array growth of small diameter single-walled carbon nanotubes

A hot filament chemical vapor deposition method has been developed to grow vertical array single-walled carbon nanotubes (SWNTs). In this study, a hot filament (temperature greater than 2000 degrees C) was used to activate gas mixtures of hydrogen and carbon containing species at sub-atmospheric pressures. Silicon substrates decorated with islands of iron were directly inserted into a preheated furnace in which a hot filament is activating the gas. Vertical arrays of SWNTs are produced with diameters ranging from 0.78 to 1.6 nm. The samples were characterized with Raman and fluorescence spectroscopy and SEM and TEM microscopy.     

Bioelectrochemical single-walled carbon nanotubes

Metalloproteins and enzymes can be immobilized on SWNTs of different surface chemistry. The combination of high surface area, robust immobilization and inherent nanotube electrochemical properties is of promising application in bioelectrochemistry.     

Crystal plane dependent growth of aligned single-walled carbon nanotubes on sapphire

On single-crystal substrates, such as sapphire (alpha-Al 2O 3) and quartz (SiO 2), single-walled carbon nanotubes (SWNTs) align along specific crystallographic axes of the crystal, indicating that the SWNT growth is influenced by the crystal surface. Here, we show that not only the orientation, but also the diameter and chirality of SWNTs are affected by the crystal plane of the sapphire substrate. The aligned SWNTs grown on the A- and R-planes of sapphire have narrower diameter distributions than randomly oriented tubes produced on the C-plane sapphire and amorphous SiO 2. Photoluminescence measurements reveal a striking difference between the aligned SWNTs: near-zigzag tubes are observed on the A-plane and near-armchair tubes on the R-plane. This study shows the route for the diameter and chirality control of SWNTs by surface atomic arrangements of a single-crystal substrate.     

Soluble ultra-short single-walled carbon nanotubes

Soluble, ultra-short (length < 60 nm), carboxylated, single-walled carbon nanotubes (SWNTs) have been prepared by a scalable process. This process, predicated on oleum's (100% H2SO4 with excess SO3) ability to intercalate between individual SWNTs inside SWNT ropes, is a procedure that simultaneously cuts and functionalizes SWNTs using a mixture of sulfuric and nitric acids. The solubility of these ultra-short SWNTs (US-SWNTs) in organic solvents, superacid and water is about 2 wt %. The availability of soluble US-SWNTs could open opportunities for forming high performance composites, blends, and copolymers without inhibiting their processibility.     

Template-free directional growth of single-walled carbon nanotubes on a- and r-plane sapphire

We report high-throughput growth of highly aligned single-walled carbon nanotube arrays on a-plane and r-plane sapphire substrates. This is achieved using chemical vapor deposition with ferritin as the catalyst. The nanotubes are aligned normal to the [0001] direction for growth on the a-plane sapphire. They are typically tens of micrometers long, with a narrow diameter distribution of 1.34 +/- 0.30 nm. In contrast, no orientation was achieved for growth on the c-plane and m-plane sapphire, or when Fe films, instead of ferritin, were used as the catalyst. Such orientation control is likely related to the interaction between carbon nanotubes and the sapphire substrate, which is supported by the observation that when a second layer of nanotubes was grown, they followed the gas flow direction. These aligned nanotube arrays may enable the construction of integrable and scalable nanotube devices and systems.     

Controlled orientation and alignment in films of single-walled carbon nanotubes using inkjet printing

An inkjet printing procedure for depositing films of carbon nanotubes (CNTs) that exhibit a very high degree of long-range mutual alignment as well as a controlled orientation with respect to the printed geometry is presented. CNT self-assembly was induced by the intrinsic lyotropic liquid crystallinity of CNT suspensions. Sufficient concentrations are reached by matching the inkjet deposition rate to the numerically modeled local evaporation rate of the printed feature and enable the CNT suspension to be printed using standard inkjet printing. Surface alignment was verified using scanning electron microscopy (SEM) and polarized light microscopy. In addition, the bulk morphology was investigated and found to be composed of stacked planar layers that did not necessarily have the same long-range orientation found on the surface. The bulk morphology was characterized by removing layers through an elastomeric peeling process and by observing cross sections of the films using SEM. CNT concentration and length were spanned experimentally, and it was found that very short and very long CNTs as well as low concentration suspensions did not yield long-range alignment.     

Magnetoresistance devices based on single-walled carbon nanotubes

We demonstrate the physical principles for the construction of a nanometer-sized magnetoresistance device based on the Aharonov-Bohm effect [Phys. Rev. 115, 485 (1959)]. The proposed device is made of a short single-walled carbon nanotube (SWCNT) placed on a substrate and coupled to a tip/contacts. We consider conductance due to the motion of electrons along the circumference of the tube (as opposed to the motion parallel to its axis). We find that the circumference conductance is sensitive to magnetic fields threading the SWCNT due to the Aharonov-Bohm effect, and show that by retracting the tip/contacts, so that the coupling to the SWCNT is reduced, very high sensitivity to the threading magnetic field develops. This is due to the formation of a narrow resonance through which the tunneling current flows. Using a bias potential the resonance can be shifted to low magnetic fields, allowing the control of conductance with magnetic fields of the order of 1 T.     

On the origin of preferential growth of semiconducting single-walled carbon nanotubes

A correlation is observed between the diameters (d) of single-walled carbon nanotubes and the percentages of metallic and semiconducting tubes synthesized at 600 degrees C by plasma-assisted chemical vapor deposition. Small tubes (d approximately 1.1 nm) show semiconductor percentages that are much higher than expected for a random chirality distribution. Density functional theory calculations reveal differences in the heat of formation energies for similar-diameter metallic, quasi-metallic, and semiconducting nanotubes. Semiconducting tubes exhibit the lowest energies and the stabilization scales with approximately 1/d(2). This could be a thermodynamic factor in the preferential growth of small semiconducting nanotubes.     

Protein-assisted solubilization of single-walled carbon nanotubes

We report a simple method that uses proteins to solubilize single-walled carbon nanotubes (SWNTs) in water. Characterization by a variety of complementary techniques including UV-Vis spectroscopy, Raman spectroscopy, and atomic force microscopy confirmed the dispersion at the individual nanotube level. A variety of proteins differing in size and structure were used to generate individual nanotube solutions by this noncovalent functionalization procedure. Protein-mediated solubilization of nanotubes in water may be important for biomedical applications. This method of solubilization may also find use in approaches for controlling the assembly of nanostructures, and the wide variety of functional groups present on the adsorbed proteins may be used as orthogonal reactive handles for the functionalization of carbon nanotubes.     

Discrete dispersion of single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) have been effectively wetted and dispersed in saturated sodium hydroxide (NaOH) alcohol-water solutions with little surface damage or shortening of the tubes; the treated material was dissolvable as individual tubes in many common organic solvents.     

Fluorimetric characterization of single-walled carbon nanotubes

Single-walled carbon nanotubes (SWCNTs) are a family of structurally related artificial nanomaterials with unusual properties and many potential applications. Most SWCNTs can emit spectrally narrow near-IR fluorescence at wavelengths that are characteristic of their precise diameter and chiral angle. Near-IR fluorimetry therefore offers a powerful approach for identifying the structural species present in SWCNT samples. Such characterization is increasingly important for nanotube production, study, separation, and applications. General-purpose and specialized instruments suitable for SWCNT fluorimetric analysis are described, and methods for interpreting fluorimetric data to deduce the presence and relative abundances of different SWCNT species are presented. Fluorescence methods are highly effective for detecting SWCNTs in challenging samples such as complex environmental or biological specimens because of the methods’ high sensitivity and selectivity and the near absence of interfering background emission at near-IR wavelengths. Current limitations and future prospects for fluorimetric characterization of SWCNTs are discussed.     

Long super-bundles of single-walled carbon nanotubes

200 nm-thick super bundles showing a novel polygonization and densely aligned arrangement are found in long single-walled carbon nanotube (SWNT) strands prepared by the vertical floating catalytic method.     

Stability of supershort single-walled carbon nanotubes

How short can single-walled carbon nanotubes (SWNTs) be? How stable are such supershort SWNTs (ss-SWNTs)? This work is the first to address these questions. On the basis of binding energy (E(B)), standard heats of formation , and strain energy (E(S)), we found that SWNTs with only one benzene ring in the axial direction, which we refer to as supershort SWNTs (ss-SWNTs), can be thermodynamically stable. On the basis of the data of E(B), , and E(S), the relative stabilities of ss-SWNTs, fullerenes, polycyclic aromatic hydrocarbons, and butadiyne are discussed. This study has laid a theoretical foundation for the possible synthesis of ss-SWNTs.     

Infrared spectroscopy of single-walled carbon nanotubes

By using the spectral moments method, we calculate the infrared spectra of chiral and achiral single-walled carbon nanotubes (SWCNTs) of different diameters and lengths. We show that the number of the infrared modes, their frequencies, and intensities depend on the length and chirality of the nanotubes. Furthermore, the dependence of the infrared spectrum as a function of the size of the SWCNT bundle is analyzed. These predictions are useful to interpret the experimental infrared spectra of SWCNTs.