First-principles study of ZnO cluster-decorated carbon nanotubes

We have investigated the structural, electronic and carbon monoxide (CO) detection properties of the ZnO cluster-decorated single-walled carbon nanotubes (SWCNTs) by using density functional theory (DFT). The stable structures of hybrid ZnO/SWCNT materials are that the ZnO cluster plane is perpendicular to the surface of SWCNTs with the Zn atoms towards the SWCNTs (Zn atom above axial C-C bond or above the C atom). For the ZnO cluster-decorated semiconducting SWCNTs, the SWCNTs present p-type characteristics which may lead to the decrease of conductance upon illumination with ultraviolet (UV) light. The CO can be adsorbed on the hybrid ZnO/SWCNT materials due to the charge transfer between them. Compared with isolated ZnO clusters or bare SWCNTs, the ZnO/SWCNT network would have excellent CO detection ability due to their suitable adsorption energy and conductivity.     

First-principles study of electronic structure of deformed carbon nanotubes

On the basis of density functional theory, we study the electronic structures of five types of carbon nanotubes: the non-deformed (6,6) tube, the uniformly stretched tube along the tube axis, the uniformly compressed tube, the partially stretched tube and the partially compressed tube. The electron charge density increases at the compressed C-C bond of the partially stretched tube, while the density decreases at the stretched C-C bond of the partially stretched tube. In addition, the a₁ and e₁ states of the (6,6) tube contribute to the bonding along the tube axis and the a₂ and e₂ states are the bonds connecting the atoms in the same layers. Thus, the energy bands of the a₁ and e₁ states are sensitively affected by the deformation of the tubes along the tube axis.     

First-principles study of physisorption of nucleic acid bases on small-diameter carbon nanotubes

We report the results of our first-principles study based on density functional theory on the interaction of the nucleic acid base molecules adenine (A), cytosine (C), guanine (G), thymine (T), and uracil (U), with a single-walled carbon nanotube (CNT). Specifically, the focus is on the physisorption of base molecules on the outer wall of a (5, 0) metallic CNT possessing one of the smallest diameters possible. Compared to the case for CNTs with large diameters, the physisorption energy is found to be reduced in the high-curvature case. The base molecules exhibit significantly different interaction strengths and the calculated binding energies follow the hierarchy G>A>T>C>U, which appears to be independent of the tube curvature. The stabilizing factor in the interaction between the base molecule and CNT is dominated by the molecular polarizability that allows a weakly attractive dispersion force to be induced between them. The present study provides an improved understanding of the role of the base sequence in deoxyribonucleic acid (DNA) or ribonucleic acid (RNA) in their interactions with carbon nanotubes of varying diameters.     

Labeling the defects of carbon nanotubes with thiol groups

Herein, we investigate the reactivity of perfect and defective single-wall carbon nanotubes (SWCNTs) with the SH group using first principle periodic calculations. The presence of Stone–Wales (SW) defect sites significantly increases the reactivity of SWCNTs against the thiol group. The most reactive site for the addition of the SH radical is the single vacancy defect; the sulfur atom reconstructs the SWCNT framework and the hydrogen atom becomes attached to a carbon atom. The cluster model calculations performed for perfect SWCNTs confirmed a very low reactivity with the thiol group, even for the small diameter and metallic SWCNTs. The reaction between the perfect SWCNT and SH results thermodynamically unfavorable. The different reactivities observed for perfect and defective SWCNTs suggest that the SH group can be employed to perform a chemical labeling of the defect sites present in carbon nanotubes. The SH radical group is quite unique because, even though it has an unpaired electron, it does not react with sp ² carbon frameworks, unless they have defects or curvature similar to C60. The results are discussed in terms of the recent experimental investigations about thiolated SWCNTs. We were able to explain the Transmission Electron Microscopy images of thiolated nanotubes and the lack of reactivity at the tips. Finally, we discuss a possible route to synthesize sulfur-doped SWCNTs using thiol groups and their electronic properties.     

First-principles study of Co-doped single-walled silicon nanotubes

We performed spin-polarized density functional calculations to study the stable configurations, energetics and electronic structures of Co-doped single-walled silicon nanotubes (CoSi(2)NTs) with the stoichiometry of CoSi(2). We found that the incorporation of Co atoms into the wall of SiNTs not only effectively stabilizes the tubes but also tunes their electronic properties. The formation energies of the CoSi(2)NTs are much lower than those of pristine SiNTs, indicating the plausibility of these tubes. The electronic structures of the CoSi(2)NTs display the characters of metals. This provides a promising synthetic route to stable SiNTs which may find potential applications in building nanoscale devices.     

Mechanical behaviors of carbon nanotubes with randomly located vacancy defects

In this paper, (10, 0) zigzag nanotubes and (6, 6) armchair nanotubes are considered to investigate the effects of randomly distributed vacancy defects on mechanical behaviors of single-walled carbon nanotubes. A spatial Poisson point process is employed to randomly locate vacancy defects on nanotubes. Atomistic simulations indicate that the presence of vacancy defects result in reducing nanotube strength but improving nanotube bending stiffness. In addition, the studies of nanotube torsion indicate that vacancy defects prevent nanotubes from being utilized as torsion springs.     

Identifying and counting point defects in carbon nanotubes

The prevailing conception of carbon nanotubes and particularly single-walled carbon nanotubes (SWNTs) continues to be one of perfectly crystalline wires. Here, we demonstrate a selective electrochemical method that labels point defects and makes them easily visible for quantitative analysis. High-quality SWNTs are confirmed to contain one defect per 4 microm on average, with a distribution weighted towards areas of SWNT curvature. Although this defect density compares favourably to high-quality, silicon single-crystals, the presence of a single defect can have tremendous electronic effects in one-dimensional conductors such as SWNTs. We demonstrate a one-to-one correspondence between chemically active point defects and sites of local electronic sensitivity in SWNT circuits, confirming the expectation that individual defects may be critical to understanding and controlling variability, noise and chemical sensitivity in SWNT electronic devices. By varying the SWNT synthesis technique, we further show that the defect spacing can be varied over orders of magnitude. The ability to detect and analyse point defects, especially at very low concentrations, indicates the promise of this technique for quantitative process analysis, especially in nanoelectronics development.     

Bundling up carbon nanotubes through Wigner defects

We show, using ab initio total energy density functional theory, that the so-called Wigner defects, an interstitial carbon atom right beside a vacancy, which are present in irradiated graphite, can also exist in bundles of carbon nanotubes. Due to the geometrical structure of a nanotube, however, this defect has a rather low formation energy, lower than the vacancy itself, suggesting that it may be one of the most important defects that are created after electron or ion irradiation. Moreover, they form a strong link between the nanotubes in bundles, increasing their shear modulus by a sizable amount, clearly indicating its importance for the mechanical properties of nanotube bundles.     

Imaging active topological defects in carbon nanotubes

A single-walled carbon nanotube (SWNT) is a wrapped single graphene layer, and its plastic deformation should require active topological defects--non-hexagonal carbon rings that can migrate along the nanotube wall. Although in situ transmission electron microscopy (TEM) has been used to examine the deformation of SWNTs, these studies deal only with diameter changes and no atomistic mechanism has been elucidated experimentally. Theory predicts that some topological defects can form through the Stone-Wales transformation in SWNTs under tension at 2,000 K, and could act as a dislocation core. We demonstrate here, by means of high-resolution (HR)-TEM with atomic sensitivity, the first direct imaging of pentagon-heptagon pair defects found in an SWNT that was heated at 2,273 K. Moreover, our in situ HR-TEM observation reveals an accumulation of topological defects near the kink of a deformed nanotube. This result suggests that dislocation motions or active topological defects are indeed responsible for the plastic deformation of SWNTs.     

Femtosecond laser nanosurgery of defects in carbon nanotubes

All self-assembled nanostructures, like carbon nanotubes, exhibit structural imperfections that affect their electronic and mechanical properties and constitute a serious problem for the development of novel electronic nanodevices. Very common defects in nanotubes are pentagon-heptagon pairs, in which the replacement of four hexagons by two pentagons and two heptagons disrupts the perfect hexagonal lattice. In this work, we demonstrate that these defects can be eliminated efficiently with the help of femtosecond laser pulses. By performing nonadiabatic molecular dynamics simulations, we show that in the laser-induced electronic nonequilibrium the pentagon-heptagon pair is transformed back into four hexagons without producing any irreversible damage to the rest of the nanotube.     

Nanometer-scale loop currents and induced magnetic dipoles in carbon nanotubes with defects

In metallic carbon nanotubes with defects, the electric current flow is expected to have characteristic spatial patterns depending on the nature of the defects. Here, we show, using first-principles transport calculations, that locally rotating loop currents in nanometer scale can be generated near defects in carbon nanotubes by quantum interference of conducting and quasi-bound states of electrons. The loop currents appear at energies near transmission dips, having opposite directions at lower- and higher-energy sides of the transmission dips and disappearing exactly at the centers of the dips. Temporal modulations of gate voltage around a transmission dip can produce oscillating magnetic dipoles, inducing magnetic fields that reflect characteristics of defects. This generation of loop currents and magnetic dipoles by quantum interference can generally occur in any nanostructure and it is potentially useful for novel electronic and magnetic nanodevices.     

First-principles study of ZnS nanostructures: nanotubes, nanowires and nanosheets

We performed first-principles calculations to study the energetics, geometric and electronic properties of zinc sulfide (ZnS) nanostructures. ZnS nanowires (ZnSNWs), nanotubes (ZnSNTs) and nanosheets (ZnSNSs) were considered. Both ZnSNWs and ZnSNTs modeled using hexagonal prisms with the atomic arrangement displaying the characters of wurtzite crystal are more stable than the single-walled ZnS nanotubes presented in previous literature. The energy evolution of ZnSNWs and ZnSNTs as a function of tube diameter and wall thickness was calculated and explained using a simple model. The comparison between the energetics and electronic structures of these ZnS nanostructures was also addressed.     

Electron and phonon renormalization near charged defects in carbon nanotubes

Owing to their influence on electrons and phonons, defects can significantly alter electrical conductance, and optical, mechanical and thermal properties of a material. Thus, understanding and control of defects, including dopants in low-dimensional systems, hold great promise for engineered materials and nanoscale devices. Here, we characterize experimentally the effects of a single defect on electrons and phonons in single-wall carbon nanotubes. The effects demonstrated here are unusual in that they are not caused by defect-induced symmetry breaking. Electrons and phonons are strongly coupled in sp(2) carbon systems, and a defect causes renormalization of electron and phonon energies. We find that near a negatively charged defect, the electron velocity is increased, which in turn influences lattice vibrations locally. Combining measurements on nanotube ensembles and on single nanotubes, we capture the relation between atomic response and the readily accessible macroscopic behaviour.     

Minimizing purification-induced defects in single-walled carbon nanotubes gives films with improved conductivity

A method for the non-destructive purification of single-walled carbon nanotubes (SWNTs) using classical coordination chemistry to remove the metal catalyst has been developed. In preliminary tests, the conductivity of films based on the resulting SWNTs was markedly better than that of films prepared from SWNTs purified by treatment with oxidizing acid solutions. The transparent and conducting SWNT films have potential applications in optoelectronic devices.     

Calorimetric study of carbon nanotubes and aluminum

Differential scanning calorimeter (DSC) was used to investigate apparent activation energy and reaction order of the reaction of carbon nanotubes and aluminum by Kissinger equation and Crane equation under non-isothermal condition. The reaction product was examined using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The experimental results show that carbon nanotubes react with aluminum and form Al₄C₃ phases with needle shape. The peak temperature of the reaction of carbon nanotubes and aluminum is found to depend on the heating rate during the continuous heating. Apparent activation energy and reaction order of the reaction of carbon nanotubes and aluminum are 194.01 and 0.92 kJ/mol, respectively.     

First-principles models for phase stability and radiation defects in structural materials for future fusion power-plant applications

Generic materials-related problems foreseen in connection with the operation of a fusion power plant present a major challenge for the development of magnetically confined fusion as a commercial power generation option. In this review, we focus on the predictive capabilities of first-principles-based atomistic models for radiation defects and phase stability of body-centred cubic Fe–Cr-based ferritic-martensitic and ferritic steels and tungsten alloys, which are presently under consideration as candidate structural materials for the first wall and diverter applications. Density-functional calculations predict that low-Cr iron alloys are stabilized by intra-atomic exchange, giving rise to magnetism and changes in interatomic chemical bonding. Magnetic effects are also responsible for the fact that the atomic structure of radiation defects in iron and steels is different from the structure of defects formed under irradiation in non-magnetic body-centred cubic metals, for example vanadium or tungsten. Ab initio-based magnetic cluster expansion-based Monte–Carlo simulations showed unusual non-collinear magnetic configurations forming at interfaces and around Cr precipitates in FeCr alloys. In W–Ta and W–V alloys, ab initio calculations helped to identify several low temperature ordered inter-metallic phases that are not included in the existing phase diagrams based on high-temperature experimental data. Ab initio calculations have also made it possible to predict atomic structures of point defects formed in these alloys under irradiation.     

First-principles study of point defects and Si site preference in Al3Ti

The formation energies of various point defects in Al₃Ti(D0₂₂) have been calculated by using first-principles calculation. The effects of vacancies on Si site preference were examined to better understand Si substitution behavior in Al₃Ti. The results show that, under Al-rich condition, the formation energy of antisite Al_Ti is the lowest than those of other point defects, and Ti vacancy is more preferred than Al vacancy. But Si prefers to occupy Al vacancy compared with Ti vacancy which causes a finite solubility of Si in Al₃Ti system. The calculation is instructive for the further improvements of process of Si removal.     

Filling carbon nanotubes with particles

The filling of carbon nanotubes (CNTs) with fluorescent particles was studied experimentally and theoretically. The fluorescent signals emitted by the particles were visible through the walls of the nanotubes, and the particles inside the tubes were observable with an electron microscope. Taking advantage of the template-grown carbon nanotubes' transparency to fluorescent light, we measured the filling rate of the tubes with particles at room conditions. Liquids such as ethylene glycol, water, and ethylene glycol/water mixtures, laden with 50 nm diameter fluorescent particles, were brought into contact with 500 nm diameter CNTs. The liquid and the particles' transport were observed, respectively, with optical and fluorescence microscopy. The CNTs were filled controllably with particles by the complementary action of capillary forces and the evaporation of the liquid. The experimental results were compared and favorably agreed with theoretical predictions. This is the first report on fluorescence studies of particle transport in carbon nanotubes.     

High-pressure Raman study of debundled single-walled carbon nanotubes

We report the pressure dependence for the radial (omega R) and tangential (omega T) band frequencies in debundled single-walled carbon nanotubes (SWNTs) derived from laser-synthesized SWNT bundles. As previously described, a chemical procedure was used to prepare debundled SWNTs from as-prepared, large SWNT bundles. The normalized pressure coefficient for omega R in the debundled sample was compared with the corresponding value in the bundled sample to quantify the strength of van der Waals interactions between tubes in these nanotube materials. Furthermore, the pressure dependences for the radial (omega R) and tangential (omega T) band frequencies in debundled tubes were also compared with corresponding dependences predicted for isolated SWNTs, obtained with generalized tight binding molecular dynamic (GTBMD) simulations described in our previous work. The results presented here collectively suggest that the van der Waals interaction is still strong in the debundled sample studied here, which contained predominantly small bundles of SWNTs rather than isolated tubes.     

Surface oxidation study of single wall carbon nanotubes

Functionalization of single wall carbon nanotubes (SWCNTs) is desirable to enhance their ability to be incorporated into polymers and enhance their bonding with the matrix. One approach to carbon nanotube functionalization is by oxidation via a strong oxidizing agent or refluxing in strong acids. However, this approach can damage the nanotubes, leading to the introduction of defects and/or shorter nanotubes. Such damage can adversely affect the mechanical, thermal, and electrical properties. A more benign approach to nanotube functionalization has been developed involving photo-oxidation. Chemical analysis by XPS revealed that the oxygen content of the photo-oxidized SWCNTs was 11.3?at.% compared to 6.7?at.% for SWCNTs oxidized by acid treatment. The photo-oxidized SWCNTs produced by this method can be used directly in various polymer matrices or can be further modified by additional chemical reactions.