We have used resonant Raman scattering spectroscopy to fully analyze the relative abundances of different (n,m) species in single-walled carbon nanotube samples that are metallically enriched by density gradient ultracentrifugation. Strikingly, the data clearly show that our density gradient ultracentrifugation process enriches the metallic fractions in armchair and near-armchair species. We observe that armchair carbon nanotubes constitute more than 50% of each (2n + m) family.
We have used post-synthesis separation methods based on density gradient ultracentrifugation and DNA-based ion-exchange chromatography to produce aqueous suspensions strongly enriched in armchair nanotubes for spectroscopic studies. Through resonant Raman spectroscopy of the radial breathing mode phonons, we provide macroscopic and unambiguous evidence that density gradient ultracentrifugation can enrich armchair nanotubes. Furthermore, using conventional, optical absorption spectroscopy in the near-infrared and visible range, we show that interband absorption in armchair nanotubes is strongly excitonic. Lastly, by examining the G-band mode in Raman spectra, we determine that observation of the broad, lower frequency (G^{-}) feature is a result of resonance with non-armchair metallic nanotubes. These findings regarding the fundamental optical absorption and scattering processes in metallic carbon nanotubes lay the foundation for further spectroscopic studies to probe many-body physical phenomena in one dimension.
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 have studied the coherent dynamics of G-band phonons in single-walled carbon nanotubes through impulsive stimulated Stokes and anti-Stokes Raman scattering. The probe energy dependence of phonon amplitude as well as preferential occurrence between Stokes and anti-Stokes components in response to chirped-pulse excitation are well explained within our model. The temperature dependence of the observed dephasing rate clearly exhibits a thermally-activated component, with an activation energy that coincides with the frequency of the radial breathing mode (RBM). This fact provides a clear picture for the dephasing of optical phonons by random frequency modulation via interaction with the RBM through anharmonicity.
We have studied emission properties of high-density excitons in single-walled carbon nanotubes through nonlinear photoluminescence excitation spectroscopy. As the excitation intensity was increased, all emission peaks arising from different chiralities showed clear saturation in intensity. Each peak exhibited a saturation value that was independent of the excitation wavelength, indicating that there is an upper limit on the exciton density for each nanotube species. We developed a theoretical model based on exciton diffusion and exciton-exciton annihilation that successfully reproduced the saturation behavior, allowing us to estimate exciton densities. These estimated densities were found to be still substantially smaller than the expected Mott density even in the saturation regime, in contrast to conventional semiconductor quantum wires.
The colors of suspended metallic colloidal particles are determined by their size-dependent plasma resonance, while those of semiconducting colloidal particles are determined by their size-dependent band gap. Here, we present a novel case for armchair carbon nanotubes, suspended in aqueous medium, for which the color depends on their size-dependent excitonic resonance, even though the individual particles are metallic. We observe distinct colors of a series of armchair-enriched nanotube suspensions, highlighting the unique coloration mechanism of these one-dimensional metals.
E. H. Haroz
,W. D. Rice
,B. Y. Lu
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(2009)
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"Enrichment of Armchair Carbon Nanotubes via Density Gradient Ultracentrifugation: Raman Spectroscopy Evidence"
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Junichiro Kono
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