A DNA-based approach to the carbon nanotube sorting problem

Carbon nanotube sorting, i.e., the separation of a mixture of tubes into different electronic types and further into species with a specific chirality, is a fascinating problem of both scientific and technological importance. It is one of those problems that are easy to describe but difficult to solve. Single-stranded DNA forms stable complexes with carbon nanotubes and disperses them effectively in water. A particular DNA sequence of alternating guanine (G) and thymine (T) nucleotides ((GT) _n , with n = 10 to 45) self-assembles into an ordered supramolecular structure around an individual nanotube, in such a way that the electrostatic properties of the DNA-carbon nanotube hybrid depend on tube structure, enabling nanotube separation by anion-exchange chromatography. This review provides a summary of the separation of metallic and semiconducting tubes, and purification of single (n, m) tubes using the DNA-wrapping approach. We will present our current understanding of the DNA-carbon nanotube hybrid structure and separation mechanisms, and predict future developments of the DNA-based approach. This article is published with open access at Springerlink.com     

金属型和半导体型单壁碳纳米管的分离研究进展

单壁碳纳米管(SWNTs)有优良的电学性能,但是目前制备的单壁碳纳米管都是金属型(met-)和半导体型(sem-)SWNTs的混合物,极大地限制了SWNTs进一步的应用。以物理法和化学法概述了近年来met-和sem-SWNTs的分离方法,并对各方法进行了机理分析和优劣比较。     

Gel-based separation of single-walled carbon nanotubes for metallic and semiconducting fractions

Common technique for biomaterials recovery in genetics is freeze-squeeze procedure. However, this method found a new application in carbon nanotubes field in a selective separation of metallic and semiconducting nanotubes. None-commercial agarose gel acts as a selective absorbent for semiconducting nanotubes and allows to separate them from metallic type of nanotubes. In this work we point out the great potential of freeze-squeeze technique in the field of separation of nanotubes and prove that the post-separation purification procedure is crucial to perform the quality and quantity estimation of the fractionated samples. Furthermore, the detailed quantitative analysis of the efficiency of this process is shown. Additionally, we emphasize that this technique can be used for high-scale separation of metallic counterparts of single-walled carbon nanotubes due to its simplicity and low cost.     

Selective suspension in aqueous sodium dodecyl sulfate according to electronic structure type allows simple separation of metallic from semiconducting single-walled carbon nanotubes

Both density gradient centrifugation and gel electrophoresis have been reported to allow high throughput separation of metallic from semiconducting single-walled carbon nanotubes (SWNTs) when using aqueous sodium dodecyl sulphate (SDS) suspensions. We show here that both methods rely on an initial dispersion-by-sonication step, which is already selective with respect to electronic structure type. The corresponding aqueous SDS “starting” suspensions obtained after sonication and purification by simple centrifugation (70,000 g, 1 h) contain semiconducting SWNTs primarily in the form of small bundles whereas metallic SWNTs are predominantly suspended as individual tubes. Density gradient centrifugation then separates the bundles from the individual tubes on the basis of differences in their overall buoyant densities. Gel electrophoresis separates the longer bundles from the shorter individual tubes on the basis of their different mobilities. We also demonstrate that such starting suspensions can be fractionated according to electronic structure type by even simpler techniques such as size exclusion chromatography or gel filtration, thus opening the way for simple scale-up.      

Chirality-enriched semiconducting carbon nanotubes synthesized on high surface area MgO-supported catalyst

Single-walled carbon nanotubes (SWCNTs) with a narrow diameter distribution were synthesized by radio frequency-Catalytic Chemical Vapor Deposition (RF-CCVD) through the pyrolysis of CH4. Fe-Co bimetallic catalytic nanoclusters were supported on high-surface area MgO nanopowders and used in the nanotube synthesis process. Nanolog absorption fluorescence analysis was used to characterize the chiralities of the as-produced SWCNTs over this nanostructural catalyst. In the final SWCNT sample, the (7,5) semiconducting carbon nanotube species were found to be dominant, with a low chirality variation.     

Direct identification of metallic and semiconducting single-walled carbon nanotubes in scanning electron microscopy

Because of their excellent electrical and optical properties, carbon nanotubes have been regarded as extremely promising candidates for high-performance electronic and optoelectronic applications. However, effective and efficient distinction and separation of metallic and semiconducting single-walled carbon nanotubes are always challenges for their practical applications. Here we show that metallic and semiconducting single-walled carbon nanotubes on SiO(2) can have obviously different contrast in scanning electron microscopy due to their conductivity difference and thus can be effectively and efficiently identified. The correlation between conductivity and contrast difference has been confirmed by using voltage-contrast scanning electron microcopy, peak force tunneling atom force microscopy, and field effect transistor testing. This phenomenon can be understood via a proposed mechanism involving the e-beam-induced surface potential of insulators and the conductivity difference between metallic and semiconducting SWCNTs. This method demonstrates great promise to achieve rapid and large-scale distinguishing between metallic and semiconducting single-walled carbon nanotubes, adding a new function to conventional SEM.     

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     

Strengthening and toughening of aluminum by single-walled carbon nanotubes

Effects of single-walled carbon nanotubes (SWNTs) on strengthening and toughening behaviors of aluminum-based composites with grain sizes ranging from nano- to micrometer have been investigated. The strength of composites is enhanced as an increase in SWNT volume and a decrease in grain size. Nanocrystalline composite containing 3.5 vol.% SWNTs exhibits good ductility of ∼5% tensile elongation to failure as well as superior yield stress of ∼600 MPa. However, the strengthening efficiency of SWNTs becomes half of the theoretical prediction for nanocrystalline composites due to the recovery process around the interface. Nanocrystalline composite containing 2.0 vol.% SWNTs shows the fracture toughness of ∼57 MPa mm^1/2, which is five times higher than that of starting aluminum. SWNTs may effectively block the propagation of necks and cracks, providing much improved ductility and toughness.     

Structure of chiral single-walled carbon nanotubes under hydrostatic pressure

We investigate the structural parameters, i.e., bond lengths and bond angles of chiral tubes of various chiralities using a procedure based on helical and rotational symmetries and Tersoff potential. The results indicate that at ambient conditions, there are equal bond lengths and three unequal bond angles in the structure of chiral tubes. This bond length depends significantly on the chirality and insignificantly on the tube radius. Length of the tubes does not play very significant role on bond length and bond angles. These C–C bonds were recalculated under hydrostatic pressure. The bond length compresses with pressure while the bond angles remain practically unchanged. We also carry out analysis regarding the cross sectional shape of chiral tubes and its pressure dependence. It is found that at some pressures, transition from circular to oval cross section takes place. The transition pressure is found to strongly depend on the radius and chirality of tube. At this transition, corresponding to given elliptical cross section, the bond length for all chiral tubes of various chiralities and radius approaches nearly a fixed value of 1.434 Å.     

Random networks and aligned arrays of single-walled carbon nanotubes for electronic device applications

Singled-walled carbon nanotubes (SWNTs), in the form of ultrathin films of random networks, aligned arrays, or anything in between, provide an unusual type of electronic material that can be integrated into circuits in a conventional, scalable fashion. The electrical, mechanical, and optical properties of such films can, in certain cases, approach the remarkable characteristics of the individual SWNTs, thereby making them attractive for applications in electronics, sensors, and other systems. This review discusses the synthesis and assembly of SWNTs into thin film architectures of various types and provides examples of their use in digital electronic circuits with levels of integration approaching 100 transistors and in analog radio frequency (RF) systems with operating frequencies up to several gigahertz, including transistor radios in which SWNT transistors provide all of the active functionality. The results represent important steps in the development of an SWNT-based electronics technology that could find utility in areas such as flexible electronics, RF analog devices and others that might complement the capabilities of established systems. This article is published with open access at Springerlink.com     

Surfactant free fractions of metallic and semiconducting single-walled carbon nanotubes via optimised gel chromatography

We report the procedure of sorting/purification of carbon nanotubes by electronic type using chromatographic column with sodium dodecylsulfate (SDS) and sodium deoxycholate (DOC) solutions as the eluents. The non-commercial agarose gel in different concentrations has been tested in the process. It was found that in optimal gel concentration the fractionation resulted in ～96.2% yield of semiconducting species. Importantly, to get surfactant-free fractions the post-separation purification procedure has been carried out. The UV–vis–NIR and Raman spectroscopy have been utilised for the samples analysis. High resolution transmission microscopy and thermogravimetric analysis allowed to study the sample morphology and purity, respectively.     

Pressure effects on bond lengths and shape of zigzag single-walled carbon nanotubes

We investigate structural parameters, i.e., bond lengths and bond angles of isolated uncapped zigzag single-wall nanotubes in detail. The bond lengths and bond angles are determined for several radii tubes by using a theoretical procedure based on the helical and rotational symmetry for atom coordinates generation, coupled with Tersoff potential for interaction energy calculations. Results show that the structure of zigzag tubes is governed by two bond lengths. One bond length is found to have a value equal to that of graphite, while the other one is larger. Furthermore, the tube length is found to have significant effect only on larger bond length in zigzag tubes. With the application of the pressure, only the larger bond length compresses, the other one remaining practically constant. At some critical pressure, this bond length becomes equal to constant bond length. This behavior of bond lengths is different from those of armchair tubes. An analysis regarding the cross sectional shape has also been done. At some higher pressure, transition from circular to oval cross section takes place. This transition pressure is found to be equal 2.06 GPa for (20,0) tube. Some comparison with chiral tubes has also been made and important differences on bond length behavior have been observed.     

A framework for stress computation in single-walled carbon nanotubes under uniaxial tension

A procedure is proposed for computing the stresses in an armchair single-walled carbon nanotube (SWCNT) under uniaxial tension. Computation is based on molecular dynamics simulations and the virial stress theorem. The proposed approach is compared with other methods used in the literature for calculating the stresses in CNTs. The loading is applied under two different boundary conditions and different strain rates and the results are compared. It is shown that the method commonly used in the literature for calculating the stresses in CNTs under estimates the ultimate strength by around 35%. It is shown that the value of the displacement increment used to apply the tensile strain is crucial. A convergence study is done to eliminate the computational error due to large displacement increments.     

Direct discrimination between semiconducting and metallic single-walled carbon nanotubes with high spatial resolution by SEM

Single-walled carbon nanotube (SWCNT) films with a high density exhibit broad functionality and great potential in nanodevices,as SWCNTs can be either metallic or semiconducting in behavior.The films greatly benefit from characterization technologies that can efficiently identify and group SWCNTs based on metallic or semiconducting natures with high spatial resolution.Here,we developed a facile imaging technique using scanning electron microscopy (SEM) to discriminate between semiconducting and metallic SWCNTs based on black and white colors.The average width of the single-SWCNT image was reduced to ～9 nm,～1/5 of previous imaging results.These achievements were attributed to reduced surface charging on the SiO2/Si substrate under enhanced accelerating voltages.With this identification technique,a CNT transistor with an on/off ratio of ＞105 was fabricated by identifying and etching out the white metallic SWCNTs.This improved SEM imaging technique can be widely applied in evaluating the selective growth and sorting of SWCNTs.     

An efficient numerical model for vibration analysis of single-walled carbon nanotubes

This paper presents a linear spring-based element formulation for computation of vibrational characteristics of single-walled carbon nanotubes (CNTs). Three-dimensional nanoscale elements and corresponding elemental equations are developed for the numerical treatment of the dynamic behaviour of single-walled CNTs, including appropriate stiffness and mass characteristics. The atomistic microstructure of nanotubes is used to assemble the elemental equations and construct the dynamic equilibrium equation. The developed elements simulate the relative translations and rotations between atoms as well as the mass of the atoms. In this way, molecular mechanics theory can be applied directly because the atomic bonds are modelled by using exclusively physical variables such as bond stretching. The modelling is regenerative and can provide simulations for different geometric characteristics of the nanotubes. Numerical results are presented that illustrates new natural frequencies and mode shapes, going beyond the usual ones for various nanotubes under different support conditions and defects. Comparisons with corresponding numerical predictions from the literature, where they are possible, show very good agreement.     

Femtosecond photon echo spectroscopy of semiconducting single-walled carbon nanotubes

Three-pulse photon echo peak shift measurements were performed on semiconducting single-walled carbon nanotubes embedded in polymer matrix at room temperature. Simultaneous modeling of the peak shift data in the limit of zero-intensity and the linear absorption spectrum enable us to extract an intrinsic homogeneous line width of 178 cm(-1), an inhomogeneous width of 698 cm(-1), and a Huang-Rhys factor of 0.04 for the radial breathing mode vibration. The peak shift data when combined with two-pulse photon echo and pump-probe measurements allows us to determine a pure exciton dephasing time scale of 78 fs at room temperature.     

Length-sorted semiconducting carbon nanotubes for high-mobility thin film transistors

We have developed a process for chemical purification of carbon nanotubes for solution-processable thin-film transistors (TFTs) having high mobility. Films of the purified carbon nanotubes fabricated by simple drop coating showed carrier mobilities as high as 164 cm²V⁻¹s⁻¹, normalized transconductances of 0.78 Sm⁻¹, and on/off current ratios of 10⁶. Such high performance requires the preparation of a suspension of micrometer-long and highly purified semiconducting single-walled carbon nanotubes (SWCNTs). Our purification process includes length and electronic-type selective trapping of SWCNTs using recycling gel filtration with a mixture of surfactants. The results provide an important milestone toward printed high-speed and large-area electronics with roll-to-roll and ink-jet device fabrication.      

Molecular dynamic simulations on tensile mechanical properties of single-walled carbon nanotubes with and without hydrogen storage

Using a bond order potential, molecular dynamics (MD) simulations have been performed to study the mechanical properties of single-walled carbon nanotubes (SWNTs) under tensile loading with and without hydrogen storage. (10,10) armchair and (17,0) zigzag carbon nanotubes have been studied. Up to the necking point of the armchair carbon nanotube, two deformation stages were identified. In the first stage, the elongation of the nanotube was primarily due to the altering of angles between two neighbor carbon bonds. Young's Modulus observed in this stage was comparable with experiments. In the second stage, the lengths of carbon bonds are extended up to the point of fracture. The tensile strength in this stage was higher than that observed in the first stage. Similar results were also found for the zigzag carbon nanotube with a lower tensile strength. Hydrogen molecules stored in the nanotubes reduced the maximum tensile strength of the carbon nanotubes, especially for the armchair type. The effect may be attributed to the competitive formation between the hydrogen–carbon and the carbon–carbon bonds.     

Magnetic nanoparticle-based separation of metallic and semiconducting carbon nanotubes

We report a simple and scalable method for the separation of semiconducting single-walled carbon nanotubes (SWNTs) from metallic SWNTs using magnetic nanoparticles (MNPs) functionalized with polycationic tri-aminated polysorbate 80 (TP80). MNPs-TP80 are selectively adsorbed on acid-treated semiconducting SWNTs, which makes the semiconducting SWNTs be highly concentrated to over 95% under a magnetic field. Almost all the field effect transistor network devices, which were fabricated using separated semiconducting SWNTs, exhibited a p-type semiconducting behavior with an on/off ratio of higher than 10(4).     

Transition of single-walled carbon nanotubes from metallic to semiconducting in field-effect transistors by hydrogen plasma treatment

We report hydrogen plasma treatment results on converting the metallic single-walled carbon nanotubes to semiconducting single-walled carbon nanotubes. We found that the as-grown single-walled carbon nanotubes (SWNTs) can be sorted as three groups which behave as metallic, as-metallic, and semiconducting SWNTs. These three groups have different changes under hydrogen plasma treatment and successive annealing process. The SWNTs can be easily hydrogenated in the hydrogen plasma environment and the as-metallic SWNTs can be transformed to semiconducting SWNTs. The successive annealing process can break the C-H bond, so the conversion is reversible.