Single‐wall carbon nanotube interactions with copper‐oxamato building block of molecule‐based magnets probed by resonance Raman spectroscopy

The electronic interactions between the [Cu(opba)]²⁻ anions (where opba is orthophenylenebis (oxamato)) and single‐wall carbon nanotubes (SWCNTs) were investigated by resonance Raman spectroscopy. The opba can form molecular magnets, and the interactions of opba with SWCNTs can produce materials with very different magnetic/electronic properties. It is observed that the electronic interaction shows a dependence on the SWCNT diameter independent of whether they are metallic or semiconducting, although the interaction is stronger for metallic tubes. The interaction also is dependent on the amount of complex that is probably adsorbed on the carbon surface of the SWCNTs. Some charge transfer can be also occurring between the metallic complex and the SWCNTs. Copyright © 2012 John Wiley & Sons, Ltd.     

Excitonic effects and optical spectra of single-walled carbon nanotubes

Many-electron effects often dramatically modify the properties of reduced dimensional systems. We report calculations, based on an ab initio many-electron Green's function approach, of electron-hole interaction effects on the optical spectra of small-diameter single-walled carbon nanotubes. Excitonic effects qualitatively alter the optical spectra of both semiconducting and metallic tubes. Excitons are bound by approximately 1 eV in the semiconducting (8,0) tube and by approximately 100 meV in the metallic (3,3) tube. These large many-electron effects explain the discrepancies between previous theories and experiments.     

Band structures of carbon nanotube with spin-orbit coupling interaction

We explore the band structures of single-walled carbon nanotubes (SWCNTs) with two types of spin-orbit couplings. The obtained results indicate that weak Rashba spin-orbit coupling interaction can lead to the breaking of four-fold degeneracy in all tubes even though without the intrinsic SO coupling. The asymmetric splitting between conduction bands and valence bands is caused by both SO couplings at the same time. When the ratio of Rashba spin-orbit coupling to the intrinsic spin-orbit coupling is larger than 3, metallic zigzag nanotube is always metallic conductor, on the contrary it becomes semiconducting properties. However, only when this ratio is equal to about 3 or the intrinsic spin-orbit coupling is much weak, the metallic armchair nanotube still holds the metallic behavior in transport.     

Optical transmission enhancement by a sub-wavelength film lens

A new sub-wavelength metallic film lens configuration is proposed, which is embedded in a thin ideal metal film, and its near field optical properties are investigated by finite-difference time-domain (FDTD)method. It is found that the optical transmission is greatly enhanced, and the spot size can be reduced by the sub-wavelength metallic film lens in comparison with the bare aperture. This kind of lens is expected to have practical applications in the very small aperture laser (VSAL), a promising nanosource for near-field optical storage and lithography.     

Electronics and Structural Properties of Single-Walled Carbon Nanotubes Interacting with a Glucose Molecule：ab initio Calculations

The adsorption of glucose molecule on single-walled carbon nanotubes (SWCNTs) is investigated by density functional theory calculations. Adsorption energies and equilibrium distances are evaluated, and glucose binding to the typical semiconducting and metallic nanotubes with various diameters and chirality are compared. We also investigated the role of the structural defects on the adsorption capability of the SWCNTs. We could observe larger adsorption energies for the larger diameters semiconducting CNTs, while the story is paradoxical for the metallic CNTs. The obtained results reveal that the adsorption energy is significantly higher for nanotubes with higher chiral angles. Finally, the adsorption energies are calculated for defected nanotubes for various configurations such as glucose molecule approaching to the pentagon, hexagon, and heptagon sites in the tube surface. We find that the respected defects have a minor contribution to the adsorption mechanism of the glucose on SWNTs. The calculation of electron transfers and the density of states supports that the electronic properties of SWCNTs do not change significantly after the gluycose molecular adsorption. Consequently, one can predict that presence of glucose would neither modify the electronic structure of the SWCNTs nor direct to a change in the conductivity of the intrinsic nanotubes.     

Electronics and Structural Properties of Single-Walled Carbon Nanotubes Interacting with a Glucose Molecule: ab initio Calculations

The adsorption of glucose molecule on single-walled carbon nanotubes(SWCNTs)is investigated by density functional theory calculations.Adsorption energies and equilibrium distances are evaluated,and glucose binding to the typical semiconducting and metallic nanotubes with various diameters and chirality are compared.We also investigated the role of the structural defects on the adsorption capability of the SWCNTs.We could observe larger adsorption energies for the larger diameters semiconducting CNTs,while the story is paradoxical for the metallic CNTs.The obtained results reveal that the adsorption energy is significantly higher for nanotubes with higher chiral angles.Finally,the adsorption energies are calculated for defected nanotubes for various configurations such as glucose molecule approaching to the pentagon,hexagon,and heptagon sites in the tube surface.We find that the respected defects have a minor contribution to the adsorption mechanism of the glucose on SWNTs.The calculation of electron transfers and the density of states supports that the electronic properties of SWCNTs do not change significantly after the gluycose molecular adsorption.Consequently,one can predict that presence of glucose would neither modify the electronic structure of the SWCNTs nor direct to a change in the conductivity of the intrinsic nanotubes.     

Interaction of Methane with Single-Walled Carbon Nanotubes： Role of Defects,Curvature and Nanotubes Type

We investigate the interaction of single-walled carbon nanotubes （SWCNTs） and methane molecule from the first principles. Adsorption energies are calculated, and methane affinities for the typical semiconducting and metallic nanotubes are compared. We also discuss role of the structural defects and nanotube curvature on the adsorption capability of the SWCNTs. We could observe larger adsorption energies for the metallic CNTs in comparison with the semiconducting CNTs. The obtained results for the zig zag nanotubes with various diameters reveal that the adsorption energy is higher for nanotubes with larger diameters. For defected tubes the adsorption energies are calculated for various configurations such as methane molecule approaching to the defect sites pentagon, hexagon, and heptagon in the tube surface. The results show that the introduce defects have an important contribution to the adsorption mechanism of the methane on SWNTs.     

Optical polarization response at gold nanosheet edges probed by scanning near-field optical microscopy

Optical properties of metallic edge-like structures known as knife-edges are a topic of interest and possess potential applications in enhanced Raman scattering, optical trapping, etc. In this work, we investigate the near-field optical polarization response at the edge of a triangular gold nanosheet, which is synthesized by a wet chemical method. A homemade scanning near-field optical microscope(SNOM) in collection mode is adopted, which is able to accurately locate its probe at the edge during experiments. An uncoated straight fiber probe is used in the SNOM, because it still preserves the property of light polarization though it has the depolarization to some extent. By comparing near-field intensities at the edge and glass substrate, detected in different polarization directions of incident light, the edge-induced depolarization is found,which is supported by the finite differential time domain(FDTD) simulated results. The depolarized phenomenon in the near-field is similar to that in the far-field.     

On the encapsulation of azafullerenes inside the single-walled carbon nanotubes: Density-functional theory based treatments

We theoretically studied the encapsulation of azafullerene (C₅₉N) inside the single-walled carbon nanotubes (SWCNTs) from the first-principles. Adsorption energy is calculated, and the azafullerene affinities for the typical semiconducting and metallic nanotubes are investigated and compared with those of pure C₆₀ fullerene. It has been found that the azafullerene as well as the fullerene affinity for the semiconducting nanotubes is stronger than that for the metallic ones, and the energy values and binding distances are typical for the physisorption. Our first-principles results indicate that the interaction between SWCNTs and azafullerenes is comparable with the nanotubes-C₆₀ system. The charge analysis shows, however, that the charges have been transferred from the cage to the tube in the azafullerene peapods, while in the fullerene peapods the charges were found to be transferred from the tube to the fullerene nanocage. Furthermore, it was found that the interaction between the considered fullerenes and host nanotubes strongly depends on the tube diameters.     

Extensive limit of a non-extensive entanglement entropy

We report wide-range optical investigations on transparent conducting networks made from separated (semiconducting, metallic) and reference (mixed) single-walled carbon nanotubes, complemented by transport measurements. Comparing the intrinsic frequency-dependent conductivity of the nanotubes with that of the networks, we conclude that higher intrinsic conductivity results in better transport properties, indicating that the properties of the nanotubes are at least as much important as the contacts. We find that HNO₃ doping offers a larger improvement in transparent conductive quality than separation. Spontaneous dedoping occurs in all samples but is most effective in films made of doped metallic tubes, where the sheet conductance returns close to its original value within 24 h.     

Absorption spectra of high purity metallic and semiconducting single-walled carbon nanotube thin films in a wide energy region

Absorption spectra of high purity metallic and semiconducting single-walled carbon nanotubes separated by the density-gradient ultracentrifugation method have been measured in the wide energy region from 1 meV to 5 eV. In the high purity metallic nanotube sample, a strong and broad absorption band has been observed at 0.06 eV. This observation suggests that the optical properties of even high purity metallic nanotube bundles cannot be explained by the simple Drude conduction model. We discuss the origin of these absorption bands for metallic and semiconducting nanotube samples by considering the existence of a small energy gap in metallic nanotube bundles and plasmon resonance.     

Role of thermal treatment on the structural behavior of the arc SWCNTs in the purification system process

The role of thermal oxidation before acid treatment and post high-temperature vacuum annealing of single walled carbon nanotube (SWCNTs) was studied by scanning electron microscopy, high-resolution transmission electron microscopy, thermogravimetric analyses and Raman spectroscopy. An efficient procedure is developed for the purification of SWCNTs with minimal damage to the walls and minimal modification in the length of the tubes. SWCNTs are employed in this study, are synthesized by arc-discharge method containing impurity of amorphous carbon, carbon shells, graphitic particles, metallic nanoparticles and metallic nanoparticles encapsulated inside the amorphous carbon or graphite.     

New features in the anti‐Stokes and Stokes Raman spectra of single‐walled carbon nanotubes that are highly separated into their semiconducting and metallic nanotube components

Surface‐enhanced Raman scattering studies were performed using nonresonant (514.5 nm) and resonant (676.4 nm) optical excitations on single‐walled carbon nanotubes thoroughly separated into semiconducting (pure 99%) and metallic (pure 98%) components. Regardless of the support (Au or Ag), the metallic nanotubes do not present an anomalous anti‐Stokes Raman emission. Regardless of whether an on‐resonant or off‐resonant optical excitation is used, only the semiconducting nanotubes produce an abnormal anti‐Stokes Raman emission that grows when increasing the excitation light intensity or temperature. The Raman studies under light polarized relative to the main nanotube axis demonstrate that only semiconducting nanotubes are sensitive toward changes in the polarization of the excitation light. Copyright © 2014 John Wiley & Sons, Ltd.     

Extraction of semiconducting CNTs by repeated dielectrophoretic filtering

We have separated semiconducting carbon nanotubes from as-grown batch material (HiPco production). A special configuration of electrodes which generates a 3-dimensional electric field gradient was used to filter out and deposit metallic carbon nanotubes by the dielectrophoretic method, leaving the remaining dispersion enriched in semiconducting nanotubes. The efficiency of filtering was determined by Raman spectroscopy. Using repeated deposition cycles, the ratio of semiconducting to metallic tubes was increased. After seven cycles, the proportion of semiconducting tubes in the remaining dispersion reached 94%. PACS 61.46.+w; 81.07.De     

Study on the electronic structure and hydrogen adsorption by transition metal decorated single wall carbon nanotubes

The ground state geometry and electronic structure of various 4d transition metal (TM) atom (Y, Zr, Nb and Mo) decorated single wall carbon nanotubes (SWCNTs) are obtained using density functional theory and the projector augmented wave (PAW) method. We found a systematic change in the adsorption site of the transition metal atom with increasing number of d electrons. We also predicted that Y and Zr decorated SWCNTs are metallic whereas Nb and Mo decorated SWCNTs are semiconducting. From detailed electronic structure and Bader charge analysis we found that the systematic variation of the adsorption site with the number of d electrons is related to the decreasing amount of charge transfer from the TM atom to the SWCNT along the 4d series. We have also studied the hydrogen adsorption capabilities of these decorated SWCNTs to understand the role of transition metal d electrons in binding the hydrogen molecules to the system. We found that metallic SWCNT + TM systems are better hydrogen adsorbers. We showed that the hydrogen adsorption by a TM decorated SWCNT will be maximum when all the adsorptions are physisorption and that the retention of magnetism by the system is crucial for physisorption.     

Electrical properties of transparent carbon nanotube networks prepared through different techniques

Ultra‐thin, optically transparent and electrically conducting films of pure carbon nanotubes (CNTs) are widely studied thanks to their promise for broad applications. In the present work, we study and compare different deposition techniques for the production of these networks: dip‐coating, spray‐coating, vacuum filtration and electrophoretic deposition on a quartz glass using single‐walled carbon nanotubes (SWCNTs) produced by the HiPCo method. In order to optimize the networks, besides the various deposition techniques we also investigate how the optical and electrical properties vary if the networks are fabricated from different CNTs, all synthesized by the CVD method: SWCNTs, DWCNTs and MWCNTs. As the main criteria for evaluating the quality of these CNT networks we measure the electrical surface resistance at a certain optical transmittance and correlate it to the morphology (homogeneity and roughness) of the networks. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural and electronic properties of endohedral doped SWCNTs: A DFT study

The structural and electronic properties of semiconductors (Si and Ge) and metal (Au and Tl) atoms doped armchair (n, n) and zigzag (n, 0); n=4–6, single wall carbon nanotubes (SWCNTs) have been studied using an ab-initio method. We have considered a linear chain of dopant atoms inside CNTs of different diameters but of same length. We have studied variation of B.E./atom, ionization potential, electron affinity and HOMO–LUMO gap of doped armchair and zigzag CNTs with diameter and dopant type. For armchair undoped CNTs, the B.E./atom increases with the increase in diameter of the tubes. For Si, Ge and Tl doped CNTs, B.E./atom is maximum for (6, 6) CNT whereas for Au doped CNTs, it is maximum for (5, 5) CNTs. For pure CNTs, IP decreases slightly with increasing diameter whereas EA increases with diameter. The study of HOMO–LUMO gap shows that on doping metallic character of the armchair CNTs increases whereas for zigzag CNTs semiconducting character increases. In case of zigzag tubes only Si doped (5, 0), (6, 0) and Ge doped (6, 0) CNTs are stable. The IP and EA for doped zigzag CNTs remain almost independent of tube diameter and dopant type whereas for doped armchair CNTs, maximum IP and EA are observed for (5, 5) tube for all dopants.     

Near-field optical observations of surface plasmon wave interference at subwavelength hole arrays perforated in Au film

We image optical near-field patterns at subwavelength circular hole arrays in Au film by using scanning near-field optical microscopy in near-infrared wavelengths.Periodical oscillation features are found in the near-field images at the air/Au interface and exhibit two typical kinds of standing wave oscillation forms at the wavelengths corresponding to the transmission minimum and maximum in the transmission spectrum,and the latter one originates from the excitation and interference of a surface plasmon wave at the metallic hole arrays.Our work indicates that monitoring optical near-field patterns can help to reveal many interesting properties of surface plasmon waves at metallic nanostructures and understand their underlying physical mechanisms.     

Fast detection of the metallic state of individual single-walled carbon nanotubes using a transient-absorption optical microscope

In spite of the outstanding properties of single-walled carbon nanotubes (SWNTs), the coexistence of metallic and semiconducting SWNTs as a result of synthesis has hindered their electronic and photonic applications. We demonstrate a pump-probe microscopy method for fast, contact-free mapping of metallicity in individual SWNTs. We employ the phase of transient absorption as a contrast to discriminate metallic and semiconducting SWNTs. Furthermore, we have clarified the phase dependence on the pump or probe wavelengths and the energy structure of SWNTs. Our imaging method holds the potential of serving as a high-speed metallicity-mapping tool to assist the development of SWNT-based nanoelectronics.