Abstract
Double-walled carbon nanotubes (DWCNTs) consist of two coaxially aligned single-walled carbon nanotubes (SWCNTs), and previous sorting methods only achieved outer-wall electronic-type selectivity. Here, a separation technique capable of sorting DWCNTs by semiconducting (S) or metallic (M) inner- and outer-wall electronic type is presented. Electronic coupling between the inner and outer wall is used to alter the surfactant coating around each of the DWCNT types, and aqueous gel permeation is used to separate them. Aqueous methods are used to remove SWCNT species from the raw material and prepare enriched DWCNT fractions. The enriched DWCNT fractions are then transferred into either chlorobenzene or toluene using the copolymer PFO–BPy to yield the four inner@outer combinations of M@M, M@S, S@M and S@S. The high purity of the resulting fractions is verified by absorption measurements, transmission electron microscopy, atomic force microscopy, resonance Raman mapping and high-density field-effect transistor devices.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Rent or buy this article
Prices vary by article type
from$1.95
to$39.95
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Moore, K. E., Tune, D. D. & Flavel, B. S. Double-walled carbon nanotube processing. Adv. Mater. 27, 3105–3137 (2015).
Okada, S. & Oshiyama, A. Curvature-induced metallization of double-walled semiconducting zigzag carbon nanotubes. Phys. Rev. Lett. 91, 216801 (2003).
Zólyomi, V. et al. Semiconductor-to-metal transition of double walled carbon nanotubes induced by inter-shell interaction. Phys. Status Solidi B 243, 3476–3479 (2006).
Kalbac, M., Green, A. A., Hersam, M. C. & Kavan, L. Probing charge transfer between shells of double-walled carbon nanotubes sorted by outer-wall electronic type. Chem. Eur. J. 17, 9806–9815 (2011).
Shi, W. et al. Superconductivity in bundles of double-wall carbon nanotubes. Sci. Rep. 2, 625 (2012).
Noffsinger, J. & Cohen, M. L. Electron–phonon coupling and superconductivity in double-walled carbon nanotubes. Phys. Rev. B 83, 165420 (2011).
Liu, K. et al. Van der Waals-coupled electronic states in incommensurate double-walled carbon nanotubes. Nat. Phys. 10, 737–742 (2014).
Zhang, R. et al. Superlubricity in centimetres-long double-walled carbon nanotubes under ambient conditions. Nat. Nanotech. 8, 912–916 (2013).
Bouilly, D. et al. Wall-selective probing of double-walled carbon nanotubes using covalent functionalization. ACS Nano 5, 4927–4934 (2011).
Green, A. A. & Hersam, M. C. Properties and application of double-walled carbon nanotubes sorted by outer-wall electronic type. ACS Nano 5, 1459–1467 (2011).
Green, A. A. & Hersam, M. C. Processing and properties of highly enriched double-wall carbon nanotubes. Nat. Nanotech. 4, 64–70 (2009).
Moore, K. E. et al. Sorting of double-walled carbon nanotubes according to their outer wall electronic type via a gel permeation method. ACS Nano 9, 3849–3857 (2015).
Streit, J. et al. Separation of double-wall carbon nanotubes by electronic type and diameter. Nanoscale 9, 2531–2540 (2017).
Hároz, E. H. et al. Fundamental optical processes in armchair carbon nanotubes. Nanoscale 5, 1411–1439 (2013).
Weisman, R. B. & Bachilo, S. M. Dependence of optical transition energies on structure for single-walled carbon nanotubes in aqueous suspension: an empirical Kataura plot. Nano Lett. 3, 1235–1238 (2003).
Flavel, B. S. et al. Separation of single-walled carbon nanotubes with a gel permeation chromatography system. ACS Nano 8, 1817–1826 (2014).
Mistry, K. S., Larsen, B. A. & Blackburn, J. L. High-yield dispersions of large-diameter semiconducting single-walled carbon nanotubes with tunable narrow chirality distributions. ACS Nano 7, 2231–2239 (2013).
Nish, A., Hwang, J.-Y., Doig, J. & Nicholas, R. J. Highly selective dispersion of single-walled carbon nanotubes using aromatic polymers. Nat. Nanotech. 2, 640–646 (2007).
O'Connell, M. J. et al. Band gap fluorescence from individual single-walled carbon nanotubes. Science 297, 593–596 (2002).
Chiang, I. et al. Purification and characterization of single-wall carbon nanotubes (SWNTs) obtained from the gas-phase decomposition of CO (HiPco process). J. Phys. Chem. B 105, 8297–8301 (2001).
Maultzsch, J., Telg, H., Reich, S. & Thomsen, C. Radial breathing mode of single-walled carbon nanotubes: optical transition energies and chiral-index assignment. Phys. Rev. B 72, 205438 (2005).
Araujo, P. T. et al. Third and fourth optical transitions in semiconducting carbon nanotubes. Phys. Rev. Lett. 98, 067401 (2007).
Pesce, P. et al. Calibrating the single-wall carbon nanotube resonance Raman intensity by high resolution transmission electron microscopy for a spectroscopy-based diameter distribution determination. Appl. Phys. Lett. 96, 051910 (2010).
Hirschmann, T. C. et al. Role of intertube interactions in double- and triple-walled carbon nanotubes. ACS Nano 8, 1330–1341 (2014).
Tulevski, G. S., Franklin, A. D. & Afzali, A. High purity isolation and quantification of semiconducting carbon nanotubes via column chromatography. ACS Nano 7, 2971–2976 (2013).
Liu, H., Nishide, D., Tanaka, T. & Kataura, H. Large-scale single-chirality separation of single-wall carbon nanotubes by simple gel chromatography. Nat. Commun. 2, 309 (2011).
Wei, X. J. et al. Experimental determination of excitonic band structures of single-walled carbon nanotubes using circular dichroism spectra. Nature Commun. 7, 9 (2016).
Liu, K. et al. Quantum-coupled radial-breathing oscillations in double-walled carbon nanotubes. Nat. Commun. 4, 1375 (2013).
Wang, H. et al. Solvent effects on polymer sorting of carbon nanotubes with applications in printed electronics. Small 11, 126–133 (2015).
Acknowledgements
The authors acknowledge the experimental assistance of J. Zaumseil and S. Grimm and thank K. Moore and A. Blanch for discussions. B.S.F. acknowledges support from the Deutsche Forschungsgemeinschaft (DFG, under grants nos. FL 834/1-1 and FL 834/2-1). R.K. acknowledges funding by the DFG under INST 163/354-1 FUGG. R.K. and F.H. acknowledge support by the Helmholtz Association through the STN programme. G.G. and S.R. acknowledge the German Research Foundation (DFG, via SFB 658, subproject A6) and Focus Area NanoScale of the Freie Universität Berlin for financial support.
Author information
Authors and Affiliations
Contributions
B.S.F., H.L. and F.H. devised and performed the DWCNT separation. G.G., S.W., A.J., R.K., S.R., H.L. and B.S.F. performed and analysed the resonance Raman maps. TEM measurements were performed by V.S.K.C., S.K.C.N., H.L. and B.S.F. All authors contributed to the preparation of the final manuscript.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Supplementary information
Supplementary information
Supplementary information (PDF 16396 kb)
Rights and permissions
About this article
Cite this article
Li, H., Gordeev, G., Wasserroth, S. et al. Inner- and outer-wall sorting of double-walled carbon nanotubes. Nature Nanotech 12, 1176–1182 (2017). https://doi.org/10.1038/nnano.2017.207
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nnano.2017.207