Interaction between concentric tubes in DWCNTs

A detailed investigation of the Raman response of the inner tube radial breathing modes (RBMs) in double-wall carbon nanotubes is reported. It revealed that the number of observed RBMs is two to three times larger than the number of possible tubes in the studied frequency range. This unexpected increase in Raman lines is attributed to a splitting of the inner tube response. It originates from the possibility that one type of inner tubes may form in different types of outer tubes. In this case, a splitting of lines results since the inner tube RBM frequency depends on the diameter of the outer tube. Finally, a comparison of the inner tube RBMs and the RBMs of tubes in bundles gave clear evidence for a stronger interaction between tubes in a bundle as compared to the interaction between inner and outer tubes.Received: 15 September 2004, Published online: 23 December 2004PACS: 81.07.De Nanotubes - 81.05.Tp Fullerenes and related materials - 78.30.Na Fullerenes and related materials     

High-energy phonon branches of an individual metallic carbon nanotube

We present excitation-energy dependent Raman measurements between 2.05 and 2.41 eV on the same individual carbon nanotube. We find a change in the Raman frequencies of both the D mode (63 cm(-1)/eV) and the high-energy modes. The observed frequencies of the modes at approximately 1600 cm(-1) as a function of laser-energy map the phonon dispersion relation of a metallic tube near the Gamma point of the Brillouin zone. Our results prove the entire first-order Raman spectrum in single-wall carbon nanotubes to originate from double-resonant scattering. Moreover, we confirm experimentally the phonon softening in metallic tubes by a Peierls-like mechanism.     

多壁碳纳米管的拉曼散射

本文报导了用直流碳弧放电方法制备的多层碳纳米管的拉曼光谱。和ＨＯＰＧ相比,由于碳纳米管的量子尺寸效应和碳纳米管直径的分布,在纯化和未纯化的碳纳米管中均存在Ｅ２ｇ模的软化,其红移范围分布在２～１３ｃｍ １范围内。     

Isotope engineering of carbon nanotube systems

The synthesis of a unique isotope engineered system, double-wall carbon nanotubes with natural carbon outer and highly 13C enriched inner walls, is reported from isotope enriched fullerenes encapsulated in single-wall carbon nanotubes (SWCNTs). The material allows the observation of the D line of the highly defect-free inner tubes that can be related to a curvature induced enhancement of the electron-phonon coupling. Ab initio calculations explain the inhomogeneous broadening of inner tube Raman modes due to the distribution of different isotopes. Nuclear magnetic resonance shows a significant contrast of the isotope enriched inner SWCNTs compared to other carbon phases and provides a macroscopic measure of the inner tube mass content. The high curvature of the small diameter inner tubes manifests in an increased distribution of the chemical shift tensor components.     

碳纳米管晶格振动模及拉曼光谱的研究进展

本文介绍了碳纳米管的结构特征和晶格振动模的理论研究 ,综述了不同方法生长的多壁碳纳米管和单壁碳纳米管拉曼光谱的研究进展。另外 ,还简单描述了单壁碳纳米管的应用前景     

Anti‐Stokes Raman spectroscopy as a method to identify the metallic and semiconducting configurations of double‐walled carbon nanotubes

Although Raman spectra reveal, as a signature of double‐walled carbon nanotubes (DWCNTs), two radial breathing mode (RBM) lines associated with the inner and outer tubes, the specification of their nature as metallic or semiconducting remains a topic for debate. Investigating the spectral range of the RBM lines, we present a new procedure of the indexing of the semiconducting or metallic nature of the inner and outer shell that forms the DWCNT. The procedure exploits the difference between the intensities of recorded anti‐Stokes Raman spectrum and the anti‐Stokes spectrum calculated by applying the Boltzmann formulae to the recorded Stokes spectrum. The results indicate that the two spectra do not coincide with what should happen in a normal Raman process, namely, that there are RBM lines of the same intensity in both spectra, as well as RBM lines of higher intensity that are observed in the calculated spectrum. This discrepancy results from the surface‐enhanced Raman scattering mechanism that operates differently on metallic or semiconducting nanotubes. In this context, the analysis of the RBM spectrum can reveal pairs of lines associated with the inner/outer shell structure of DWCNT, and when the intensities between the recorded and calculated spectra coincide, the nanotube is metallic; otherwise, the nanotube is semiconducting. Copyright © 2014 John Wiley & Sons, Ltd.     

Chirality distribution and transition energies of carbon nanotubes

From resonant Raman scattering on isolated nanotubes we obtained the optical transition energies, the radial breathing mode frequency, and the Raman intensity of both metallic and semiconducting tubes. We unambiguously assigned the chiral index (n(1),n(2)) of approximately 50 nanotubes based solely on a third-neighbor tight-binding Kataura plot and find omega(RBM)=(214.4+/-2) cm(-1) nm/d+(18.7+/-2) cm(-1). In contrast to luminescence experiments we observe all chiralities including zigzag tubes. The Raman intensities have a systematic chiral-angle dependence confirming recent ab initio calculations.     

Effect of van der Waals interactions on the Raman modes in single walled carbon nanotubes

We have measured the Raman spectrum of individual single walled carbon nanotubes in solution and compare it to that obtained from the same starting material where the tubes are present in ordered bundles or ropes. Interestingly, the radial mode frequencies for the tubes in solution are found to be approximately 10 cm (-1) higher than those observed for tubes in a rope, in apparent contradiction to lattice dynamics predictions. We suggest that there is no such contradiction, and propose that the upshift is due rather to a decreased energy spacing of the Van Hove singularities in isolated tubes over the spacings in a rope, thereby allowing the same laser excitation to excite different diameter tubes in these two samples.     

Phonon and thermal properties of achiral single wall carbon nanotubes

A detailed theoretical study of the phonon and thermal properties of achiral single wall carbon nanotubes has been carried out using force constant model considering up to third nearest-neighbor interactions. We have calculated the phonon dispersions, density of states, radial breathing modes (RBM) and the specific heats for various zigzag and armchair nanotubes, with radii ranging from 2.8 Å to 11.0 Å. A comparative study of phonon spectrum with measured Raman data reveals that the number of Raman active modes for a tube does not depend on the number of atoms present in the unit cell but on its chirality. Calculated phonon modes at the zone center more or less accurately predicted the Raman active modes. The radial breathing mode is of particular interest as for a specific radius of a nanotube it is found to be independent of its chirality. We have also calculated the variation of RBM and G-band modes for tubes of different radii. RBM shows an inverse dependence on the radius of the tube. Finally, the values of specific heat are calculated for various nanotubes at room temperature and it was found that the specific heat shows an exponential dependence on the diameter of the tube.     

高温下单壁碳纳米管的拉曼光谱研究

本文采用对样品进行直接加热和测温的方法,对单壁碳纳米管(SWNT)高温下的拉曼光谱进行了研究。在不同的激发波长下,观测了SWNT拉曼光谱的切向振动模频率随温度的变化,发现其频率随温度增加而降低,基本呈线性变化,温度系数约-0.014cm-1/K。不同的激发波长下,切向振动模频率随温度的变化行为基本一致。     

Raman and SERS studies of carbon nanotube systems

In this paper, we report on Raman studies carried out on different carbon nanotube systems, namely single-walled and multi-walled carbon nanotubes and polymer/nanotube composites. We focus on different types of interactions which can take place in these materials. In single-walled nanotubes, the introduction of van der Waals interactions between tubes when arranged in bundles leads to an upshift of the radial breathing mode (RBM) ranging from 11 to 16 cm⁻¹ depending on the size of the bundle. In multi-walled carbon nanotubes, similar interactions between concentric tubes permit to interpret the low frequency Raman modes. In composites, PMMA/nanotubes, an upshift of the RBM is also observed, explained by the dynamical strain applied by the polymer on the bundles, in response to the breathing vibration. In addition, surface enhanced Raman scattering experiments have demonstrated the occurrence of interfacial reactions between the nanotubes and the metallic support. This is put in evidence by the degradation of tubes, especially metallic ones, and reconstruction of C₆₀-like molecules are in some cases observed.     

不同激发波长下单壁碳纳米管与多壁碳纳米管的拉曼光谱比较

对不同激发波长下单壁和多壁碳纳米管的激光拉曼光谱进行了比较。发现单壁碳纳米管D峰强度和G峰强度的比值(ID/IG)几乎不随激发光子能量的改变而变化,多壁碳纳米管ID/IG值随着激发光子能量的增加以斜率0 3/eV减小。并对此现象进行了初步的分析。此外,还发现在1064nm激发波长下,单壁和多壁碳纳米管2500-3500cm-1之间拉曼峰的相对强度随着入射激光功率的增加而增加。     

Discontinuous tangential stress in double wall carbon nanotubes

We have examined the stability of double wall carbon nanotubes under hydrostatic pressures up to 10 GPa. The tangential optical phonon mode observed by inelastic light scattering is sensitive to the in-plane stress and splits into a contribution associated with the external and internal tube. While the pressure coefficient from the external tube is the same as in single wall carbon nanotubes, the pressure coefficient from the internal tube is found to be 45% smaller. The phonon band from the external tube broadens considerably with applied pressure in contrast with the phonon band of the internal tube which stays constant. These pressure dependent phonon shifts of the external and internal tubes and the contrasting phonon line broadening are explained by the elastic continuum shell model which takes into account both the continuous radial and discontinuous tangential stress components.     

碳纳米管和高取向热解石墨的拉曼光谱对比研究

同时测量了碳纳米管（Ｄ－ＣＮＴ）和高取向热解石墨（ＨＯＰＧ）的拉曼光谱，第一次分别在ＨＯＰＧ和Ｄ－ＣＮＴ中观察到了位于４２６５ｃｍ－１和４２４８ｃｍ－１的（Ｇ＋Ｄ＊）三级模的拉曼散射；拉曼谱的研究显示，Ｄ－ＣＮＴ的结构比ＨＯＰＧ的无序，同时也进一步表明此无序程度主要来源于结构的缺陷，而非石墨层卷曲成筒状之故     

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.     

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     

Luminescence decay and the absorption cross section of individual single-walled carbon nanotubes

The absorption cross section of highly luminescent individual single-walled carbon nanotubes is determined using time-resolved and cw luminescence spectroscopy. A mean value of approximately 1 x 10(-17) cm2 per carbon atom is obtained for (6,5) tubes excited at their second optical transition, and corroborated by single tube photothermal absorption measurements. Biexponential luminescence decays are systematically observed, with short and long lifetimes around 45 and 250 ps. This behavior is attributed to the band edge exciton fine structure with a dark level lying a few meV below a bright one.     

Radial breathing vibration of double-walled carbon nanotubes subjected to pressure

A theoretical vibrational analysis of the radial breathing mode (RBM) of double-walled carbon nanotubes (DWCNTs) subjected to pressure is presented based on an elastic continuum model. The results agree with reported experimental results obtained under different conditions. Frequencies of the RBM in DWCNTs subjected to increasing pressure depend strongly on circumferential wave numbers, but weakly on the aspect ratio and axial half-wave numbers. For the inner and outer tubes of DWCNTs, the frequency of the RBM increases obviously as the pressure increases under different conditions. The range of variation is smaller for the inner tube than the outer tube.     

Carbon nanotube film synthesized from ethanol and its oxidation behavior in air

In this paper, we propose an efficient way to synthesize carbon nanotube films using ferrocene and ethanol. The as-grown film is free-standing, semi-transparent, and of macro scale size. The tubes in the film are mostly singleor double-walled. The oxidation behavior of the film is studied via Raman spectroscopy, and the result indicates that the inner wall of the double-walled tube is effectively protected from oxidation by the outer wall.     

Measuring the uniaxial strain of individual single-wall carbon nanotubes: resonance Raman spectra of atomic-force-microscope modified single-wall nanotubes

Raman spectroscopy is used to measure the strain in individual single-wall carbon nanotubes, strained by manipulation with an atomic-force-microscope tip. Under strains varying from 0.06%-1.65%, the in-plane vibrational mode frequencies are lowered by as much as 1.5% (40 cm(-1)), while the radial breathing mode (RBM) remains unchanged. The RBM Stokes/anti-Stokes intensity ratio remains unchanged under strain. The elasticity of these strain deformations is demonstrated as the down-shifted Raman modes resume their prestrain frequencies after a nanotube is broken under excessive strain.