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Register a new userThe Raman response of double wall carbon nanotubes
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Raman spectroscopy on carbon nanotubes (CNT) yields a rich variety of information owing to the close interplay between electronic and vibrational properties. In this paper, we review the properties of double wall carbon nanotubes (DWCNTs). In particular, it is shown that SWCNT encapsulating C$_{60}$, so-called peapods, are transformed into DWCNTs when subject to a high temperature treatment. The inner tubes are grown in a catalyst free environment and do not suffer from impurities or defects that are usually encountered for as-grown SWCNTs or DWCNTs. As a consequence, the inner tubes are grown with a high degree of perfection as deduced from the unusually narrow radial breathing mode (RBM) lines. This apostrophizes the interior of the SWCNTs as a nano-clean room. The mechanism of the inner nanotube production from C$_{60}$ is discussed. We also report recent studies aimed at the simplification and industrial scaling up of the DWCNT production process utilizing a low temperature peapod synthesis method. A splitting of the RBMs of inner tubes is observed. This is related to the interaction between the two shells of the DWCNTs as the same inner tube type can be encapsulated in different outer ones. The sharp appearance of the inner tube RBMs allows a reliable assignment of the tube modes to (n,m) indexes and thus provides a precise determination of the relation between the tube diameter and the RBM frequencies.
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Mixtures containing different weight ratios of single wall carbon nanotubes (SWCNT) and double wall carbon nanotubes (DWCNT) were prepared and studied by in-situ Raman spectroelectrochemistry. Two components of the G-prime mode in the Raman spectra, which can be resolved at high electrode potentials, were assigned to the signals from inner tubes of DWCNT and outer tubes of DWCNT together with SWCNT. The dependence of the ratios of these two components of the G-prime mode on the nominal amount of SWCNT and DWCNT in the samples was simulated so that the residual amount of SWCNT in the original DWCNT could be determined. Additionally, the individual contributions of all components of carbon nanotubes into the total area of the G-prime mode at high electrode potentials were estimated from the simulation.
With the empirical bond polarizability model, the nonresonant Raman spectra of the chiral and achiral single-wall carbon nanotubes (SWCNTs) under uniaxial and torsional strains have been systematically studied by textit{ab initio} method. It is found that both the frequencies and the intensities of the low-frequency Raman active modes almost do not change in the deformed nanotubes, while their high-frequency part shifts obviously. Especially, the high-frequency part shifts linearly with the uniaxial tensile strain, and two kinds of different shift slopes are found for any kind of SWCNTs. More interestingly, new Raman peaks are found in the nonresonant Raman spectra under torsional strain, which are explained by a) the symmetry breaking and b) the effect of bond rotation and the anisotropy of the polarizability induced by bond stretching.
We present an analysis of deep-UV Raman measurements of graphite, graphene and carbon nanotubes. For excitation energies above the strong optical absorption peak at the $M$ point in the Brillouin zone ($approx 4.7,text{eV}$), we partially suppress double-resonant scattering processes and observe the two-phonon density of states of carbon nanomaterials. The measured peaks are assigned to contributions from LO, TO, and LA phonon branches, supported by calculations of the phonon dispersion. Moreover, we gain access to the infrared-active $E_{1u}$ mode in graphite. By lowering the excitation energy and thus allowing double-resonant scattering processes, we demonstrate the rise of the textit{2D} mode in graphite with ultra-short phonon wave vectors.
The circular dichroism (CD) spectra of single-wall carbon nanotubes are calculated using a dipole approximation. The calculated CD spectra show features that allow us to distinguish between nanotubes with different angles of chirality, and diameters. These results provide theoretical support for the quantification of chirality and its measurement, using the CD lineshapes of chiral nanotubes. It is expected that this information would be useful to motivate further experimental studies.
A novel method is presented which allows the characterization of diameter selective phenomena in SWCNTs. It is based on the transformation of fullerene peapod materials into double-wall carbon nanotubes and studying the diameter distribution of the latter. The method is demonstrated for the diameter selective healing of nanotube defects and yield from C$_{70}$ peapod samples. Openings on small diameter nanotubes are closed first. The yield of very small diameter inner nanotubes from C$_{70}$ peapods is demonstrated. This challenges the theoretical models of inner nanotube formation. An anomalous absence of mid-diameter inner tubes is observed and explained by the suppressed amount of C$_{70}$ peapods due to the competition of the two almost equally stable standing and lying C$_{70}$ peapod configurations.
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