Raman spectroscopy of pentyl‐functionalized carbon nanotubes

We present Raman scattering on carbon nanotubes functionalized with pentyl groups. Studies of the intermediate frequency region and the C–H bond stretching signal along with the D mode show evidence of the addition reaction by Raman spectroscopy. From the resonance profiles of the radial breathing mode (RBM) we assign the chiral indices of the tubes and study the influence of the functionalization on the transition energies, shift and intensity of the RBM signal. The largest effect we observe is on the Raman intensity of the radial breathing mode. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

     

Two modes of electroluminescence from single‐walled carbon nanotubes

The electroluminescence from single‐walled carbon nanotube field effect transistors is spectrally resolved, and shows two distinct modes of light emission. The vast majority of nanotubes have spectrally broad emission consistent with the spectrum of blackbody radiation. Much more rarely, superposed on the broad emission is a single narrow (<50 meV) peak which is consistent with expectation for electron–hole recombination. The narrow emission is strong even at lower biases and in general has greater peak intensity than the broadband emission. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

A symmetry-adapted force-constant lattice-dynamical model for single-walled carbon nanotubes

We develop a lattice-dynamical model based on the screw symmetry of single-walled carbon nanotubes that allows for reducing the size of the dynamical matrix to six, for all tube chiralities. The model uses force constants derived from fitting to the phonon dispersion of 2D graphite. We present the calculation procedure in a clear and transparent way, making the model easier to follow. We calculate the phonon dispersions of a number of nanotubes of different chiralities. The splitting of two highest Raman active modes and the radial breathing mode frequency are studied by changing the tube diameter and chirality.     

Laser heating method for estimation of carbon nanotube purity

A new method of a carbon nanotube purity estimation has been developed on the basis of Raman spectroscopy. The spectra of carbon soot containing different amounts of nanotubes were registered under heating from a probing laser beam with a step-by-step increased power density. The material temperature in the laser spot was estimated from a position of the tangential Raman mode demonstrating a linear thermal shift (-0.012 cm^-1/K) from the position 1592 cm^-1 (at room temperature). The rate of the material temperature rise versus the laser power density (determining the slope of a corresponding graph) appeared to correlate strongly with the nanotube content in the soot. The influence of the experimental conditions on the slope value has been excluded via a simultaneous measurement of a reference sample with a high nanotube content (95 vol. %). After the calibration (done by a comparison of the Raman and the transmission electron microscopy data for the nanotube percentage in the same samples) the Raman-based method is able to provide a quantitative purity estimation for any nanotube-containing material. Received: 11 December 2001 / Accepted: 12 December 2001 / Published online: 4 March 2002     

Boron electrical activation in dual B+ + N+ + and B+ + Ar+ ion-implanted silicon

Silicon wafers were implanted with 40 keV B⁺ ions and then with 50 keV N⁺ or 100 keV Ar+ ions to doses from 1.2 x 1014 to 1.2 x 1015 cm^–2. The implanted samples were studied using the Hall effect and standard van der Pauw methods. The dependences of the sheet resistivity and the sheet concentration of charge carriers on the annealing temperature in the range from 700 to 1300 K were obtained. Models describing the influence of additional implantation of nitrogen and argon ions on the process of boron electrical activation during annealing are proposed.     

Raman spectra of single-crystal C60

We have analysed the Raman spectra of C₆₀ single crystals between room temperature and 10K and studied the temperature-induced phase transition in this material. The spectra show crystal field splitting of the internal Raman modes but no evidence for a line shift near the phase transition. The photo-induced transformation of the crystals and its implication on the interpretation of the Raman spectra is discussed. In the low temperature phase we observed two lines at 30 cm^–1 and 41 cm^–1 which we assign to the librational modes of the crystal.     

Towards processing of carbon nanotubes for technical applications

Production methods for carbon nanotubes are now well established and allow their synthesis on a scale of grams per day. For many potential applications of this unique material, its purification still remains a crucial problem. In this article various purification methods for single- and multi-wall carbon nanotubes are reviewed. These methods are compared in terms of their capacity, efficiency, and effects on the tubes. In addition, the use of Raman spectroscopy for monitoring the chromatographic purification of single-wall nanotubes is described. Received: 17 May 1999 / Accepted: 18 May 1999 / Published online: 29 July 1999     

Probing disorder and charged impurities in graphene by Raman spectroscopy

Disorder and doping can strongly affect the properties of graphene. Here we analyze these effects on several samples by Raman spectroscopy. In particular, we show that pristine and unprocessed graphene samples deposited on silicon, covered with a thin silicon oxide layer, show strong variations in their Raman spectra, even in absence of disorder. The variation in the Raman parameters is assigned to charged impurities. This shows that as‐deposited graphene is unintentionally doped, reaching charge concentrations up to 10¹³ cm^–2 under ambient conditions. The doping varies from sample to sample and the charges are inhomogeneously distributed on a submicron scale. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Raman mode shifts correlated with conductivity and Young's modulus changes in modified carbon nanotube networks

We have discovered a remarkable correlation between frequency shifts in G⁺, D and D* Raman modes and changes in the conductivity and Young's modulus of freestanding single‐wall carbon nanotube (SWNT) networks. On ion irradiation, all these properties show similar peaks as a function of irradiation dose. On acceptor doping that increases conductivity, increases are also observed in the Raman mode frequencies that are analogous to the irradiation effects. We discuss possible mechanisms for these correlated changes in properties. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Excitonic absorption spectra and ultrafast dephasing dynamics in arbitrary carbon nanotubes

We illustrate the potential of the density matrix theory for investigation of optical properties of arbitrary single‐walled carbon nanotubes (CNTs). We have performed microscopic calculations of excitonic absorption spectra for CNTs of different chiral angles and diameters. The obtained results are in good agreement with experiments, in particular the excitonic binding energies match well both experiments and ab initio calculations. Furthermore, we show the strength of our approach by presenting calculations of the ultrafast Coulomb driven non‐equilibrium dynamics in CNTs. We find excitation induced dephasing on the picosecond time scale depending on the excitation strength. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Review on the symmetry-related properties of carbon nanotubes

In this work we review the basic properties of carbon nanotubes from the standpoint of group theory. The zone folding scheme is reviewed in the light of the helical symmetry of the nanotube. The group theory for chiral and achiral nanotubes is reviewed, and the representations of the factor group of the wavevector k are obtained. The similarities and differences between the formalism of the group of the wavevector and that of line groups are addressed with respect to the irreducible representations and quantum numbers associated with linear and angular momenta. Finally, we extend the results of group theory to illuminate the electronic and vibrational properties of carbon nanotubes. Selection rules for the optical absorption and double resonance Raman scattering are discussed for the case where the electron–electron interaction is negligible (metallic nanotubes) and for the case where exciton binding energies are strong and cannot be neglected.     

Analysis of the concentration of C60 fullerenes in single wall carbon nanotubes

Single wall carbon nanotubes filled with C₆₀ were analyzed using resonance Raman scattering and electron energy loss spectroscopy. In order to obtain concentrations of the fullerene molecules inside the tubes, the scattering intensity from the fullerenes relative to that from the tubes was used. Since the scattering intensity from the tubes is subject to strong fluctuations, the determination of the concentrations is shown to require averaging of results from different lasers and from all observable Raman lines. The fluctuations are shown to be intrinsic and a consequence of photoselective resonance scattering. Calibration of absolute concentrations can be obtained from electron energy loss spectroscopy performed on the same samples. Samples with three different diameters were analyzed and good agreement between the fullerene concentrations measured by the two methods was obtained. Received: 20 September 2002 / Accepted: 4 November 2002 / Published online: 10 March 2003 RID="*" ID="*"Corresponding author. Fax: +43-1/4277-51375, E-mail: kuzman@ap.univie.ac.at     

Raman Spectroscopy of Irradiation Effect in Three Carbon Allotropes Induced by Low Energy B Ions

Irradiation effect in three carbon allotropes C60, diamond and highly oriented pyrolytic graphite （HOPG） induced by 170keV B ions, mainly including the process of the damage creation, is investigated by means of Raman spectroscopy technique. The differences on irradiation sensitivity and structural stability for C60, HOPG and diamond are compared. The analysis results indicate that C60 is the most sensitive for B ions irradiation, diamond is the second one and the structure of HOPG is cross sections σ of C60, diamond and HOPG deduced from 1.31 × 10^-15 cm^2, respectively. the most stable under B ion irradiation. The damage the Raman spectra are 7.78 × 10^-15, 6.38 × 10^-15 and1.31 x 10-15 cm^2, respectively.     

Synthesis and Raman characterization of mono-sized single-wall carbon nanotubes in one-dimensional channels of AlPO4-5 crystals

Mono-sized single-wall carbon nanotubes were formed in one-dimensional channels of AlPO₄-5 single crystal (AFI) by pyrolysis of tripropylamine (TPA). Raman spectra have been measured for the TPA-AFI crystals thermally processed at different conditions. TPA molecules are carbonized at 400 °C, and carbon nanotubes were formed at 500 °C or above. The radial-breathing mode, which is special for carbon nanotube geometry, was observed. Three Raman-active modes with symmetry A _1g, E _1g, and E _2g were identified by detailed symmetrical analysis for the polarized-Raman spectra. Received: 29 October 1998 / Accepted: 29 March 1999 / Published online: 24 June 1999     

Optical properties of semiconducting carbon nanotubes under axial magnetic field

The linear polarizability absorption spectra of semiconducting carbon nanotubes under axial magnetic field (B) have been calculated by the π-orbital tight-binding model and sum-over-state method. We have found that the optical spectra are split by the B-induced symmetry breaking and the amount of splitting increases with increase of magnetic field. Although the results are obtained within the noninteracting tight-binding model, the amount of splitting is still consistent with the experimental observation, offering a fast estimation of the B-induced splitting. Our numerical results also indicate that the splitting amounts of the second and third absorption peaks are close to that of the first one, which may be observed by the future experiments.     

Temperature dependence of infrared and Raman modes in polymeric RbC60

Temperature dependence of the intra-molecular vibrational modes of C₆₀ in the quasi-1D polymeric RbC₆₀, across the low temperature transition at ∼50 K, has been probed through infrared (IR) and Raman spectroscopies. With the lowering of temperature, the split IR modes of RbC₆₀ are seen to harden but below 50 K a small but definitive signature of an anomalous softening is observed. In addition, the background IR transmission shows an increase below 50 K with the opening of a well defined gap in the electronic spectrum. The implications of these results, along with those of Raman measurements, are discussed in terms of the interaction of intra-molecular phonons with electrons and spin excitations in the system.     

The origin of polarized blackbody radiation from resistively heated multiwalled carbon nanotubes

We observed very pronounced polarization of light emitted by highly aligned free-standing multiwall carbon nanotube (MWNT) sheet in axial direction which is turned to the perpendicular polarization when a number of layers are increased. The radiation spectrum of resistively heated MWNT sheet closely follows to the Plank's blackbody radiation distribution. The obtained polarization features can be described by a classical dielectric cylindrical shell model, taking into consideration the contribution of delocalized π-electrons (π surface plasmons). In absorption (emission) the optical transverse polarizability, which is much smaller than longitudinal one, is substantially suppressed by depolarization effect due to screening by induced charges. This phenomenon suggests very simple and precise method to estimate the alignment of nanotubes in bundles or large assemblies.     

Direct observation of dark exciton states in single carbon nanotubes

We have studied magneto-photoluminescence (PL) spectra of a single carbon nanotube at low temperatures. A single PL peak arising from optically allowed (bright) exciton state was observed under the zero-magnetic field, and an additional PL peak from optically forbidden (dark) exciton state was enhanced with increasing the magnetic field. Excitons populate in the lower dark state at low temperatures, and the optically forbidden transition is observed due to the Aharonov-Bohm effect.     

Surface characteristics of Ni catalystic films on growth behavior of multi-walled carbon nanotubes

The effect of the surface characteristics of Ni catalyst films on the growth behavior of multi-walled carbon nanotubes (MWCNTs) were investigated using Ni catalyst films prepared by different physical vapor deposition methods, electron-beam evaporation and sputtering. The growth behavior of MWCNTs was dependent upon the surface roughness of the Ni films. After a pretreatment process with NH₃, the root mean squares of surface roughness of e-beam evaporated and sputtered Ni catalyst films increased to 16.6 and 3.2 nm, respectively. Curled-MWCNTs and carbon-encapsulated Ni nanoparticles were formed on the Ni film deposited by e-beam evaporation while vertically aligned-MWCNTs were grown on the sputter-deposited film. In addition, the surface roughness of the Ni films affected the field emission properties of the MWCNTs. This was considered to originate from the specific growth behavior of the MWCNTs which was primarily caused by the initial surface roughness of the Ni films.