Controlling growth and Raman spectra of individual suspended single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) were prepared with ethanol chemical vapor deposition (CVD) on SiO₂ flat and pillar-patterned Si substrates. The effect of CVD temperatures from 600 to 800 °C on SWNTs yields was investigated. By virtue of its unperturbed environment, an individual suspended SWNT grown between two different SiO₂ pillars provides a possibility to study the phonon band structure of SWNT itself at a single-nanotube level. Raman spectra of individual SWNTs grown between pillars were investigated systematically.     

Comparison of modification of electronic properties of single-walled carbon nanotubes filled with metal halogenide, chalcogenide, and pure metal

In present work, thulium chloride, gallium selenide, bismuth telluride, and silver were encapsulated into the channels of single-walled carbon nanotubes (SWCNTs). The structural properties of obtained nanostructures were studied by high-resolution transmission electron microscopy, and the modification of electronic properties of nanotubes as result of filling their channels with chosen substances was investigated by Raman spectroscopy and X-ray photoelectron spectroscopy. It was shown that the electronic properties of filled SWCNTs depend on the chemical nature of incorporated materials. The encapsulation of TmCl₃ and GaSe into the carbon nanotube channels leads to acceptor doping of the SWCNTs, and this effect is more prominent for thulium chloride. The incorporation of bismuth telluride into the nanotube cavities does not result in any modification of their electronic properties. The filling of the nanotube channels with silver leads to donor doping of the single-walled carbon nanotubes.     

High-resolution near-field Raman microscopy of single-walled carbon nanotubes

We present near-field Raman spectroscopy and imaging of single isolated single-walled carbon nanotubes with a spatial resolution of approximately 25 nm. The near-field origin of the image contrast is confirmed by the measured dependence of the Raman scattering signal on tip-sample distance and the unique polarization properties. The method is used to study local variations in the Raman spectrum along a single single-walled carbon nanotube.     

Raman modes of index-identified freestanding single-walled carbon nanotubes

Using electron diffraction on freestanding single-walled carbon nanotubes, we have determined the structural indices (n,m) of tubes in the diameter range from 1.4 to 3 nm. On the same freestanding tubes, we have recorded Raman spectra of the tangential modes and the radial breathing mode. For the smaller diameters (1.4-1.7 nm), these measurements confirm previously established radial breathing mode frequency versus diameter relations and would be consistent with the theoretically predicted proportionality to the inverse diameter. However, for extending the relation to larger diameters, either a yet unexplained environmental constant has to be assumed, or the linear relation has to be abandoned.     

Multiphonon Raman scattering from individual single-walled carbon nanotubes

Combinations of up to 6 zone-edge and zone-center optical phonons are observed in the Raman spectra of individual single-walled carbon nanotubes (SWNTs). These multiphonon Raman modes exhibit distinct signatures of the one-dimensional nature of SWNTs and provide information on the phonon structure, exciton-phonon coupling, and excitonic transitions in nanotubes.     

Raman active phonons of identified semiconducting single-walled carbon nanotubes

The resonant Raman spectra of (n, m) semiconducting single-walled carbon nanotubes, unambiguously identified from their electron diffraction patterns, have been measured. The diameter dependence of the frequency of the tangential modes with A symmetry has been obtained in the diameter range from 1.4 to 2.5 nm. The comparison between the excitation energies and the calculated transition energies allowed us to determine precisely the values of the Es33 and Es44 transition energies. Finally, in the debate concerning the dominant process at the origin of the first-order Raman scattering in single-walled carbon nanotubes (single resonance process or double resonance process), our results are well understood in the framework of a single resonance process.     

Resonant Raman scattering of the smallest single-walled carbon nanotubes

We report optical properties of the smallest single-walled carbon nanotubes (SWNTs) with a diameter of only 3 A. These ultrasmall SWNTs are fabricated in the elliptical nanochannels of an AlPO-11 (AEL) single crystal. Polarized and resonant Raman scattering unambiguously revealed that these 0.3 nm SWNTs are of (2,2) armchair symmetry. Interestingly, the (2,2) armchair tube has two metastable ground states corresponding to two slightly different lattice constants in the axial direction: one state is metallic and the other is semiconducting.     

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.     

Surface-enhanced Raman scattering from the individual metallic single-walled carbon nanotubes

A new experimental technique has been presented to investigate the surface-enhanced Raman scattering (SERS) on “individual and untouched” single-walled carbon nanotubes (SWNTs) deposited onto gold or silver film-covered substrate through a direct CVD method. It was found that the radial breathing mode for SERS shows a narrower linewidth than the normal Raman spectroscopy (NRS). Relative to NRS, the SERS spectra also revealed a preferable contribution to some metallic component of the G line. However no obvious difference for D and G′ between SERS and NRS has been revealed, which is different from the previous results on bulk SWNT samples.     

Growth of single-walled carbon nanotubes from size-selected catalytic metal particles

Single-walled carbon nanotubes (SWNTs) were synthesized using size-controlled catalyst nanoparticles created by the pulsed laser ablation method. Specifically, the alloy particles (Co/Mo or Co/Pt) were prepared by ablation of the target alloy materials in an inert gas atmosphere. Size selection was performed using a differential mobility analyzer (DMA). The obtained nanoparticles were deposited on a quartz substrate from which SWNTs were grown by the alcohol catalytic CVD (ACCVD) technique that was developed by the authors group. AFM and Raman scattering analysis revealed that SWNTs were successfully synthesized. It seems the Co/Mo alloy catalyst was more effective for the synthesis of SWNTs than the Co/Pt catalyst, though this is a preliminary result to be further investigated. PACS 36.40.-c; 61.46.+w; 65.80.+n; 78.30.Na; 81.07.de     

Radial breathing modes of single-walled carbon nanotubes in resonance Raman spectra at high temperature and their chiral index assignment

Radial breathing modes (RBMs) in resonance Raman spectra from single-walled carbon nanotubes (SWCNTs) on a SiO₂/Si (0 0 1) substrate are studied between 25 and 720 °C. A change in the relative intensity of each RBM peak with temperature is observed, which originates from the temperature dependence of the resonance condition of nanotubes. For 25 °C, each RBM peak is reasonably assigned on the basis of data in the literature [J. Maultzsch, H. Telg, S. Reich, F. Hennrich, C. Thomsen, Phys. Rev. B 72 (2005) 205438]. By taking into account the temperature-dependent behavior of the relative intensity of the RBM peaks, each RBM peak is successfully assigned even for 720 °C. It is found that most of the observed RBM peaks for a laser excitation energy of E_exc = 1.96 eV are from chiral SWCNTs. These results make it possible to discuss further details of the chirality-dependent growth behavior observed for in situ Raman spectroscopy.     

Resonance Raman spectra of carbon nanotubes by cross-polarized light

Resonance Raman studies on single wall carbon nanotubes (SWNTs) show that resonance with cross polarized light, i.e., with the E(mu,mu+/-1) van Hove singularities in the joint density of states needs to be taken into account when analyzing the Raman and optical absorption spectra from isolated SWNTs. This study is performed by analyzing the polarization, laser energy, and diameter dependence of two Raman features, the tangential modes (G band) and a second-order mode (G' band), at the isolated SWNT level.     

Determination of exciton-phonon coupling elements in single-walled carbon nanotubes by Raman overtone analysis

Raman excitation profiles are obtained and compared for carbon nanotube radial breathing mode (RBM) fundamental and overtone vibrations for 5 specific chiralities. Fitting of the Raman excitation data is performed using Raman transform theory. The Huang-Rhys factors obtained from the modeling are directly related to the magnitude of the RBM exciton-phonon coupling element, which is shown to be in a weak coupling limit. The values of exciton-phonon coupling strengths and the possible role of revealed non-Condon effects are in agreement with quantum-chemical modeling.     

Surface-enhanced and normal stokes and anti-stokes Raman spectroscopy of single-walled carbon nanotubes

Surface enhancement factors of at least 10(12) for the Raman scattering of single-walled carbon nanotubes in contact with fractal silver colloidal clusters result in measuring very narrow Raman bands corresponding to the homogeneous linewidth of the tangential C-C stretching mode in semiconducting nanotubes. Normal and surface-enhanced Stokes and anti-Stokes Raman spectra are discussed in the framework of selective resonant Raman contributions of semiconducting or metallic nanotubes to the Stokes or anti-Stokes spectra, respectively, of the population of vibrational levels due to the extremely strong surface-enhanced Raman process, and of phonon-phonon interactions.     

Effect of annealing on the optical absorption spectra of single-walled carbon nanotubes

The thermal stability of initial and purified samples of single-walled carbon nanotubes prepared through gas-phase disproportionation of carbon monoxide CO in the presence of iron particles under high pressure (the HiPCO method) is investigated using optical absorption spectroscopy and thermogravimetry. An analysis of the optical absorption spectra demonstrates that thermal oxidation of the initial material proceeds rather rapidly and uniformly owing to the catalytic effect caused by the presence of iron particles in the sample. The destruction of the carbon nanotubes contained in the as-prepared and purified samples begins at temperatures of ～250 and ～300°C, respectively. It is shown that single-walled metallic nanotubes undergo faster oxidation as compared to the single-walled semiconducting nanotubes.     

Conductivity of single-walled carbon nanotubes

In a system of N interacting single-level quantum dots (QDs), we study the relaxation dynamics and the current–voltage characteristics determined by symmetry properties of the QD arrangement. Different numbers of dots, initial charge configurations, and various coupling regimes to reservoirs are considered. We reveal that effective charge trapping occurs for particular regimes of coupling to the reservoir when more than two dots form a ring structure with the C_N spatial symmetry. We reveal that the effective charge trapping caused by the C_N spatial symmetry of N coupled QDs depends on the number of dots and the way of coupling to the reservoirs. We demonstrate that the charge trapping effect is directly connected with the formation of dark states, which are not coupled to reservoirs due to the system spatial symmetry C_N. We also reveal the symmetry blockade of the tunneling current caused by the presence of dark states.     

Manifestation of auger processes in C1s-satellite spectra of single-walled carbon nanotubes

Using the equipment of the Russian-German beamline of the synchrotron radiation at the BESSY II electron storage ring, satellite spectra accompanying the C1s core lines in the cases of single-walled carbon nanotubes and highly ordered pyrolytic graphite have been measured with a high energy resolution. The Auger spectra corresponding to shaking of the valence system of carbon by the core vacancy have been found and investigated. The Auger spectra of the studied single-walled carbon nanotubes and highly ordered pyrolytic graphite are caused by annihilation of the excited π* electron with a hole in the π subband. It has been established that the electron states in the conduction band have 3π* (gT, K, M) symmetry; i.e., they correspond to flat 3π* subband, which is localized by 12–13 eV above the Fermi level. It has been revealed that the general regularities of the distribution of electron states in the valence system insignificantly change during its shake-up by the excited core.     

Nucleation of single-walled carbon nanotubes

The nucleation pathway for single-wall carbon nanotubes on a metal surface is demonstrated by a series of total energy calculations using density functional theory. Incorporation of pentagons at an early stage of nucleation is energetically favorable as they reduce the number of dangling bonds and facilitate curvature of the structure and bonding to the metal. In the presence of the metal surface, nucleation of a closed cap or a capped single-wall carbon nanotube is overwhelmingly favored compared to any structure with dangling bonds or to a fullerene.     

Hydrogenation of single-walled carbon nanotubes

Towards the development of a useful mechanism for hydrogen storage, we have studied the hydrogenation of single-walled carbon nanotubes with atomic hydrogen using core-level photoelectron spectroscopy and x-ray absorption spectroscopy. We find that atomic hydrogen creates C-H bonds with the carbon atoms in the nanotube walls, and such C-H bonds can be completely broken by heating to 600 degrees C. We demonstrate approximately 65 +/- 15 at % hydrogenation of carbon atoms in the single-walled carbon nanotubes, which is equivalent to 5.1 +/- 1.2 wt % hydrogen capacity. We also show that the hydrogenation is a reversible process.     

Piezoresistive effect in single-walled carbon nanotubes

This paper reports on the results of the theoretical investigation of the piezoresistive effect in single-walled carbon nanotubes of two structural modifications: arm-chair type and zig-zag type. The variation in the band gap of semiconducting nanotubes under the influence of the compressive and tensile deformations has been analyzed. The main quantitative characteristic of the piezoresistive effect—the longitudinal component of the elastic conductivity tensor—has been calculated, and its dependence on the diameter of semiconducting nanotubes has been shown. The variants of practical implementation of the effect under study have been proposed.