Odako growth of dense arrays of single-walled carbon nanotubes attached to carbon surfaces

A novel process is demonstrated whereby dense arrays of single-walled carbon nanotubes (SWNT) are grown directly at the interface of a carbon material or carbon fiber. This growth process combines the concepts of SWNT tip growth and alumina-supported SWNT base growth to yield what we refer to as “odako” growth. In odako growth, an alumina flake detaches from the carbon surface and supports catalytic growth of dense SWNT arrays at the tip, leaving a direct interface between the carbon surface and the dense SWNT arrays. In addition to being a new and novel form of SWNT array growth, this technique provides a route toward future development of many important applications for dense aligned SWNT arrays. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. This article is published with open access at Springerlink.com     

Continued growth of single-walled carbon nanotubes

We demonstrate the continued growth of single-walled carbon nanotubes (SWNTs) from ordered arrays of open-ended SWNTs in a way analogous to epitaxy. Nanometer-sized metal catalysts were docked to the SWNT open ends and subsequently activated to restart growth. SWNTs thus grown inherit the diameters and chirality from the seeded SWNTs, as indicated by the closely matched frequencies of Raman radial breathing modes before and after the growth.     

Copper catalyzing growth of single-walled carbon nanotubes on substrates

Metallic copper, which is normally considered as a contaminant in the growth of single-walled carbon nanotubes (SWNTs), was found to be an efficient catalyst to grow SWNTs under suitable conditions. It showed very high catalytic activity for the growth of both random SWNT networks and horizontally aligned SWNT arrays. Especially, high-quality SWNT arrays were obtained when monodispersed copper nanoparticles were used. The catalytic behavior of copper for the growth of SWNTs was discussed. The weaker interaction between the copper and silica surfaces plays an important role in the growth of high-quality horizontally aligned SWNT arrays. This new synthesis process of SWNTs with a non-ferromagnetic catalyst brings more convenience to the study of magnetic properties of SWNTs and gives more insight in structure-controlled synthesis of SWNTs.     

Size engineering of metal nanoparticles to diameter-specified growth of single-walled carbon nanotubes with horizontal alignment on quartz

The electronic, physical and optical properties of single-walled carbon nanotubes (SWNTs) are governed by their diameter and chirality, and thus much research has been focused on controlling the diameter and chirality of SWNTs. To date, control of the catalyst particle size has been thought to be one of the most promising approaches to control the diameter or chirality of SWNTs owing to the correlation between catalyst particle size and tube diameter.In this study, we demonstrate the size engineering of catalytic nanoparticles for the controlled growth of diameter-specified and horizontally aligned SWNTs on quartz substrates. Uniformly sized iron nanoparticles derived from ferritin molecules were used as a catalyst, and their size was intentionally decreased via thermal heat treatment at 900?°C under atmospheric Ar ambient. ST-cut quartz wafers were used as growth substrates in order to elucidate the effect of the size of the nanoparticles on the tube diameter and the effect of catalyst size on the degree of parallel alignment on the quartz substrates. SWNTs grown by chemical vapor deposition using methane as feedstock exhibited a high degree of horizontal alignment when the particle density was low enough to produce individual SWNTs without bundling. Annealing for 60?min at 900?°C produced a reduction of nanoparticle diameter from 2.6 to 1.8?nm and a decrease in the mean tube diameter from 1.2 to 0.8?nm, respectively. Raman spectroscopy results corroborated the observation that prolonged heat treatment of nanoparticles yields thinner tubes with narrower size distributions. The results of this work suggest that straightforward thermal annealing can be a facile way to obtain uniform-sized SWNTs as well as catalytic nanoparticles.     

Controlled growth of single-walled carbon nanotubes for unique nanodevices

The controlled growth of bent and horizontally aligned single-walled carbon nanotubes (SWNTs) is demonstrated in this study. The bent SWNTs growth is attributed to the interaction between van der Waals force with substrate and aerodynamic force from gas flow. The curvature of bent SWNTs can be tailored by adjusting the angle between gas flow and step-edge direction. Electrical characterization shows that the one-dimensional resistivity of bent SWNTs is correlated with the curvature, which is due to strain induced energy bandgap variation. Additionally, a downshift of 10 cm(-1) in G-band is found at curved part by Raman analysis, which may be resulted from the bending induced carbon-carbon bond variation. In addition, horizontally aligned SWNTs and crossbar SWNTs were demonstrated. To prove the possibility of integrating the SWNTs having controllable morphology in carbon nanotube based electronics, an inverter with a gain of 2 was built on an individual horizontally aligned carbon nanotube.     

Cutting single-walled carbon nanotubes

A two-step process is utilized for cutting single-walled carbon nanotubes (SWNTs). The first step requires the breakage of carbon-carbon bonds in the lattice while the second step is aimed at etching at these damage sites to create short, cut nanotubes. To achieve monodisperse lengths from any cutting strategy requires control of both steps. Room-temperature piranha and ammonium persulfate solutions have shown the ability to exploit the damage sites and etch SWNTs in a controlled manner. Despite the aggressive nature of these oxidizing solutions, the etch rate for SWNTs is relatively slow and almost no new sidewall damage is introduced. Carbon-carbon bond breakage can be introduced through fluorination to ～C(2)F, and subsequent etching using piranha solutions has been shown to be very effective in cutting nanotubes. The final average length of the nanotubes is approximately?100?nm with carbon yields as high as 70-80%.     

Formylation of single-walled carbon nanotubes

We report an improved, elegant method for the covalent formylation of single-wall carbon nanotubes (SWNTs) via formyl transfer from N-formylpiperidine, which could potentially open the gateway for more versatile chemical modification of carbon nanotube (CNT) walls than is possible via other reported functionalisation methods. The formylation reaction does not inflict damage upon the pristine CNT structure, unlike the currently commonly used carboxylation route, and involves much fewer steps, and takes considerably less time, than most other reported routes. The modified SWNTs have been characterised by Raman spectroscopy, ultraviolet-visible-near infrared (UV-vis-NIR) spectroscopy and "covalent tagging" with derivatising groups followed by thermogravimetric analysis-mass spectroscopy (TGA-MS). UV-vis-NIR spectroscopy shows that there is only limited disruption of the intrinsic electronic structure of the SWNTs. This is confirmed from estimates of the extent of functionalisation from TGA-MS, which suggest that it may be as low as 2 atomic per cent.     

Attachment of functionalized single-walled carbon nanotubes (SWNTs) to silicon surfaces

Single-walled carbon nanotubes (SWNTs) were functionalized by direct fluorination and subsequent reaction with 6-aminohexanoic acid for water-soluble carboxylic acid functionalized SWNTs (AHA-SWNTs). Both of the compounds were used as precursors to attach SWNTs to APTES coated silicon surfaces. AHA-SWNTs in aqueous solution were reacted with APTES self-assembled monolayers (SAMs) with coupling reagents N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDC) and N-hydroxysuccinimide (NHS). The surface coverage is a function of concentration of AHA-SWNTs, solvent and coupling method. While for the fluorinated SWNTs (F-SWNTs), direct addition of F-SWNTs to preformed APTES SAMs at 90 degrees C shows essentially no reaction, in contrast to the one-pot reaction of F-SWNTs with APTES molecules in the presence of SWNTs on a silicon substrate. This reaction route provides a convenient method to attach SWNTs to silicon surfaces.     

Purification of single-walled carbon nanotubes

The discovery of carbon nanotubes (CNTs) created much excitement and stimulated extensive research into the properties of nanometer-scale cylindrical networks. From then on, various methods for the synthesis and characterization of aligned CNTs-both single-walled (SWCNTs) and multi-walled (MWCNTs) by different methods have been hotly pursued. Unfortunately, most methods currently in use produce raw multi component solid products, only a small fraction of which contains carbon nanotubes. The balance of the material is composed of residual catalyst particles (some of which are encased in concentric graphitic shells), fullerenes, other graphitic materials and amorphous carbon. These impurities cause a serious impediment for their detailed characterization and applications. If the carbon nanotube is ever to fulfill its promise as an engineering material, large, high quality aliquots will be required. A number of purification methods involving elimination processes such as physical separation, gas phase and liquid phase oxidation in combination with chemical treatments have been developed for nanotube materials. Though the quantitative determination of purity remains controversial, reported yields are best regarded with an appropriate level of skepticism on the method of assay. In this article, a review is given on the past and recent advances in purification of SWCNTs.     

Cadmium-catalyzed surface growth of single-walled carbon nanotubes with high efficiency

We demonstrate that cadmium (Cd) can catalyze the growth of single-walled carbon nanotubes (SWNTs) with high efficiency. The Cd nanocatalysts, prepared using a diblock copolymer templating method, were uniformly spaced over a large deposition area with an average diameter of 1.9 nm and narrow size distribution. By using the normal-heating and fast-heating method, random and horizontally aligned arrays of SWNTs can be generated. The density of the SWNTs can be altered by the chemical vapor deposition conditions. The morphology and microstructure of the SWNTs characterized by scanning electron microscopy, Raman spectroscopy, atomic force microscopy, and high-resolution transmission electron microscopy revealed that the grown nanotubes do not have carbonaceous particles and have good crystallinity. In addition, after careful check with superlong nanotubes 735 out of 790 nanotubes were found to be deposited with Ag (93%) and only 7% SWNTs without Ag deposition. While for superlong SWNT arrays from Fe, 32% long SWNTs without Ag deposition was found, the high percentage of SWNTs with Ag deposition from Cd indicates that the SWNTs have better conductivity and better structural uniformity with less defects.     

Three dimensional single-walled carbon nanotubes

We report a simple fabrication method of creating a three-dimensional single-walled carbon nanotube (CNT) architecture in which suspended CNTs are aligned parallel to each other along the conventionally unused third dimension at lithographically defined locations. Combining top-down lithography with the bottom-up block copolymer self-assembly technique and utilizing the excellent film forming capability of polymeric materials, highly uniform catalyst nanoparticles with an average size of 2.0 nm have been deposited on sidewalls for generating CNTs with 1 nm diameter. This three-dimensional platform is useful for fundamental studies as well as technological exploration. The fabrication method described herein is applicable for the synthesis of other very small 1D nanomaterials using the catalytic vapor deposition technique.     

Optically active single-walled carbon nanotubes

The optical, electrical and mechanical properties of single-walled carbon nanotubes (SWNTs) are largely determined by their structures, and bulk availability of uniform materials is vital for extending their technological applications. Since they were first prepared, much effort has been directed toward selective synthesis and separation of SWNTs with specific structures. As-prepared samples of chiral SWNTs contain equal amounts of left- and right-handed helical structures, but little attention has been paid to the separation of these non-superimposable mirror image forms, known as optical isomers. Here, we show that optically active SWNT samples can be obtained by preferentially extracting either right- or left-handed SWNTs from a commercial sample. Chiral 'gable-type' diporphyrin molecules bind with different affinities to the left- and right-handed helical nanotube isomers to form complexes with unequal stabilities that can be readily separated. Significantly, the diporphyrins can be liberated from the complexes afterwards, to provide optically enriched SWNTs.     

单壁碳纳米管束的排布

流体排布法是实现碳纳米管定向排列的一种简单的方法。采用流体排布法在具有浸润性图案化的基底上成功地对单壁碳纳米管(SWNTs)束进行了水平方向上的排布。将SWNTs悬浮液滴入光刻胶制成的微通道中,在流体剪切力作用下,弯曲的SWNTs在一定程度上会被拉伸并且平行地排列在纳米级宽度的微通道中。将排列好的SWNTs阵列转移到一些不同间距的金电极对上面,制作成碳纳米管场效应晶体管(CNTFET)。CNTFET的电性能测试结果表明,制备的SWNTs束可以制造出不同电极间距同时具有良好电性能的CNTFET。     

Band theory of single-walled carbon nanotubes

In this paper, a curvilinear coordinate system is used in space and in k-space to study the energy band of single-walled carbon nanotubes wrapped at a helical angle. Using this method, a general function of the bandgap associated with the radius of the tube and the helical angle is derived based on the tight-binding theory. The three-dimensional hexagonal Brillouin zone of the tube is on the surface of cylinder in the k-space. For two tubes with different diameters, there is a distance between the cylindrical Brillouin zones in the radial direction. The Brillouin zone varies with the radius of the tube and the number of cells on the circumference. For the metallic zigzag tubes, the bandgaps decrease discretely to zero at the corners of the Brillouin zones, and those corners are singular points of zero gaps. With the transformation of coordinates, the metallic zigzag type is proven to be equivalent to an armchair configuration. Electrical characteristics of the chiral effects are briefly highlighted.     

Effect of Rh and Pt on growth and structure of single-walled carbon nanotubes

This work studied a new method to prepare single-walled carbon nanotubes (SWCNTs). The key of this method is to add two kinds of platinum family metals as catalysts to a graphite rod to make a composite graphite anode. The arc discharge was carried out in helium gas, and the collected product was observed and analyzed using high-resolution transmission electron microscopy and Raman spectroscopy. The results showed that straight SWCNTs with uniform diameter could be obtained without the inclusion of any magnetic metal catalysts. This offers the possibility of studying the SWCNT-polymer magnetic functional material. The structure and the growth mechanism of the SWCNTs prepared by this new method were also analyzed. The text was submitted by the authors in English.     

Length-dependent extraction of single-walled carbon nanotubes

A two-phase liquid-liquid extraction process is presented which is capable of extracting water-soluble single-walled carbon nanotubes into an organic phase. The extraction utilizes electrostatic interactions between a common phase transfer agent and the sidewall functional groups on the nanotubes. Large length-dependent van der Waals forces for nanotubes allow the ability to control the length of nanotubes extracted into the organic phase as demonstrated by atomic force microscopy.     

Ozonolysis of functionalized single-walled carbon nanotubes

Room temperature ozonolysis of fluorinated SWNT and phenyl-sulfonated SWNT have been studied in perfluoropolyether (PFPE) solvents. Etching at the end caps (approximately 70 nm/hour for fluorinated SWNT/PFPE suspension with 1 g/l concentration) has been demonstrated to be the dominating effect during the ozonolysis of fluorinated SWNT. Base on characterization by AFM analysis, X-ray Photoelectron Spectroscopy (XPS) and Raman Spectroscopy, fluorination along the SWNT sidewalls protects F-SWNT from extensive functionalization by ozonolysis. An ozone reaction with fluorinated SWNT has been found to improve its solubility in 96% sulfuric acid. This allows oxidative cutting by ammonium peroxydisulfate without defluorination. In comparison to fluorinated SWNT, phenyl-sulfonated SWNT was found to be effectively and homogeneous cut by ozonolysis in a water suspension.     

RF response of single-walled carbon nanotubes

We present for the first time an in-depth study of the RF response of a single-walled carbon nanotube (SWCNT) rope. Our novel electrode design, based on a tapered coplanar approach, allows for single tube measurements well into the GHz regime, minimizing substrate-related parasitics. From the analysis of the S-parameters, the ac transport mechanism in the range 30 kHz to 6 GHz is established. This work is an essential prerequisite for the fabrication of high-speed devices based on bundles of nanowires or low-dimensional structures.     

Co-synthesis of single-walled carbon nanotubes and carbon fibers

A new vertical floating catalytic technique is developed and used to prepare both single-walled carbon nanotubes (SWNTs) and carbon fibers (CFs). Scanning electron microscopy (SEM) observation shows a clear separation of these two materials. Thin films of SWNTs can be peeled easily from the CF substrate which just acts as a catalyst support for the SWNT growth. The production process is also semicontinuous, resulting in a yield of ∼1.0 g h⁻¹ of SWNTs film with high purity. Structure and vibrational properties of these materials are investigated by electron microscopy and Raman spectroscopy, respectively.     

Wiring-up hydrogenase with single-walled carbon nanotubes

Many envision a future where hydrogen is the centerpiece of a sustainable, carbon-free energy supply. For example, the energy in sunlight may be stored by splitting water into H2 and O2 using inorganic semiconductors and photoelectrochemical approaches or with artificial photosynthetic systems that seek to mimic the light absorption, energy transfer, electron transfer, and redox catalysis that occurs in green plants. Unfortunately, large scale deployment of artificial water-splitting technologies may be impeded by the need for the large amounts of precious metals required to catalyze the multielectron water-splitting reactions. Nature provides a variety of microbes that can activate the dihydrogen bond through the catalytic activity of [NiFe] and [FeFe] hydrogenases, and photobiological approaches to water splitting have been advanced. One may also consider a biohybrid approach; however, it is difficult to interface these sensitive, metalloenzymes to other materials and systems. Here we show that surfactant-suspended carbon single-walled nanotubes (SWNTs) spontaneously self-assemble with [FeFe] hydrogenases in solution to form catalytically active biohybrids. Photoluminescence excitation and Raman spectroscopy studies show that SWNTs act as molecular wires to make electrical contact to the biocatalytic region of hydrogenase. Hydrogenase mediates electron injection into nanotubes having appropriately positioned lowest occupied molecular orbital levels when the H2 partial pressure is varied. The hydrogenase is strongly attached to the SWNTs, so mass transport effects are eliminated and the absolute potential of the electronic levels of the nanotubes can be unambiguously measured. Our findings reveal new nanotube physics and represent the first example of "wiring-up" an hydrogenase with another nanoscale material. This latter advance offers a nonprecious metal route to the design of new biohybrid architectures and building blocks for hydrogen-related technologies.