Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Controlled synthesis of single-chirality carbon nanotubes

Nature volume 512, pages 61–64 (2014)Cite this article

Subjects

Abstract

Over the past two decades, single-walled carbon nanotubes (SWCNTs) have received much attention because their extraordinary properties are promising for numerous applications1,2. Many of these properties depend sensitively on SWCNT structure, which is characterized by the chiral index (n,m) that denotes the length and orientation of the circumferential vector in the hexagonal carbon lattice. Electronic properties are particularly strongly affected, with subtle structural changes switching tubes from metallic to semiconducting with various bandgaps. Monodisperse ‘single-chirality’ (that is, with a single (n,m) index) SWCNTs are thus needed to fully exploit their technological potential1,2. Controlled synthesis through catalyst engineering3,4,5,6, end-cap engineering7 or cloning strategies8,9, and also tube sorting based on chromatography10,11, density-gradient centrifugation, electrophoresis and other techniques12, have delivered SWCNT samples with narrow distributions of tube diameter and a large fraction of a predetermined tube type. But an effective pathway to truly monodisperse SWCNTs remains elusive. The use of template molecules to unambiguously dictate the diameter and chirality of the resulting nanotube8,13,14,15,16 holds great promise in this regard, but has hitherto had only limited practical success7,17,18. Here we show that this bottom-up strategy can produce targeted nanotubes: we convert molecular precursors into ultrashort singly capped (6,6) ‘armchair’ nanotube seeds using surface-catalysed cyclodehydrogenation on a platinum (111) surface, and then elongate these during a subsequent growth phase to produce single-chirality and essentially defect-free SWCNTs with lengths up to a few hundred nanometres. We expect that our on-surface synthesis approach will provide a route to nanotube-based materials with highly optimized properties for applications such as light detectors, photovoltaics, field-effect transistors and sensors2.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Two-step bottom-up synthesis of SWCNTs.
Figure 2: Formation of (6,6) SWCNT seeds S1.
Figure 3: Epitaxial elongation of singly capped SWCNT with (6,6) chiral index defined by the seed S1.
Figure 4: SWCNT orientation determination and single chirality assessment by Raman spectroscopy.

Similar content being viewed by others

References

  1. Jorio, A., Dresselhaus, G. & Dresselhaus, M. S. Carbon Nanotubes: Advanced Topics in the Synthesis, Structure, Properties, and Applications (Springer, 2008)

    Book  Google Scholar 

  2. Jariwala, D., Sangwan, V. K., Lauhon, L. J., Marks, T. J. & Hersam, M. C. Carbon nanomaterials for electronics, optoelectronics, photovoltaics, and sensing. Chem. Soc. Rev. 42, 2824–2860 (2013)

    Article  CAS  Google Scholar 

  3. Wang, H. et al. Selective synthesis of (9,8) single walled carbon nanotubes on cobalt incorporated TUD-1 catalysts. J. Am. Chem. Soc. 132, 16747–16749 (2010)

    Article  CAS  Google Scholar 

  4. He, M. et al. Selective growth of SWNTs on partially reduced monometallic cobalt catalyst. Chem. Commun. 47, 1219–1221 (2011)

    Article  CAS  Google Scholar 

  5. Chiang, W.-H. & Mohan Sankaran, R. Linking catalyst composition to chirality distributions of as-grown single-walled carbon nanotubes by tuning NixFe1−x nanoparticles. Nature Mater. 8, 882–886 (2009)

    Article  CAS  ADS  Google Scholar 

  6. Hong, G., Chen, Y., Li, P. & Zhang, J. Controlling the growth of single-walled carbon nanotubes on surfaces using metal and non-metal catalysts. Carbon 50, 2067–2082 (2012)

    Article  CAS  Google Scholar 

  7. Yu, X. et al. Cap formation engineering: from opened C60 to single-walled carbon nanotubes. Nano Lett. 10, 3343–3349 (2010)

    Article  CAS  ADS  Google Scholar 

  8. Smalley, R. E. et al. Single wall carbon nanotube amplification: en route to a type-specific growth mechanism. J. Am. Chem. Soc. 128, 15824–15829 (2006)

    Article  CAS  Google Scholar 

  9. Yao, Y., Feng, C., Zhang, J. & Liu, Z. ‘Cloning’ of single-walled carbon nanotubes via open-end growth mechanism. Nano Lett. 9, 1673–1677 (2009)

    Article  CAS  ADS  Google Scholar 

  10. Tu, X., Manohar, S., Jagota, A. & Zheng, M. DNA sequence motifs for structure-specific recognition and separation of carbon nanotubes. Nature 460, 250–253 (2009)

    Article  CAS  ADS  Google Scholar 

  11. Liu, H., Nishide, D., Tanaka, T. & Kataura, H. Large-scale single-chirality separation of single-wall carbon nanotubes by simple gel chromatography. Nature Commun. 2, 309 (2011)

    Article  ADS  Google Scholar 

  12. Hersam, M. C. Progress towards monodisperse single-walled carbon nanotubes. Nature Nanotechnol. 3, 387–394 (2008)

    Article  CAS  ADS  Google Scholar 

  13. Mueller, A., Amsharov, K. Y. & Jansen, M. Synthesis of end-cap precursor molecules for (6, 6) armchair and (9, 0) zig-zag single-walled carbon nanotubes. Tetrahedr. Lett. 51, 3221–3225 (2010)

    Article  CAS  Google Scholar 

  14. Bunz, U. H. F., Menning, S. & Martín, N. para-Connected cyclophenylenes and hemispherical polyarenes: building blocks for single-walled carbon nanotubes? Angew. Chem. Int. Edn Engl. 51, 7094–7101 (2012)

    Article  CAS  Google Scholar 

  15. Mueller, A. & Amsharov, K. Y. Synthesis of precursors for large-diameter hemispherical buckybowls and precursors for short carbon nanotubes. Eur. J. Org. Chem. 2012, 6155–6164 (2012)

    Article  CAS  Google Scholar 

  16. Omachi, H., Segawa, Y. & Itami, K. Synthesis of cycloparaphenylenes and related carbon nanorings: a step toward the controlled synthesis of carbon nanotubes. Acc. Chem. Res. 45, 1378–1389 (2012)

    Article  CAS  Google Scholar 

  17. Mueller, A., Amsharov, K. Y. & Jansen, M. End-cap precursor molecules for the controlled growth of single-walled carbon nanotubes. Fullerenes Nanotubes Carbon Nanostruct. 20, 401–404 (2012)

    Article  CAS  ADS  Google Scholar 

  18. Omachi, H., Nakayama, T., Takahashi, E., Segawa, Y. & Itami, K. Initiation of carbon nanotube growth by well-defined carbon nanorings. Nature Chem. 5, 572–576 (2013)

    Article  CAS  ADS  Google Scholar 

  19. Otero, G. et al. Fullerenes from aromatic precursors by surface-catalysed cyclodehydrogenation. Nature 454, 865–868 (2008)

    Article  CAS  ADS  Google Scholar 

  20. Amsharov, K. et al. Towards the isomer-specific synthesis of higher fullerenes and buckybowls by the surface-catalyzed cyclodehydrogenation of aromatic precursors. Angew. Chem. Int. Edn Engl. 49, 9392–9396 (2010)

    Article  CAS  Google Scholar 

  21. Rim, K. T. et al. Forming aromatic hemispheres on transition-metal surfaces. Angew. Chem. Int. Edn Engl. 46, 7891–7895 (2007)

    Article  CAS  Google Scholar 

  22. Gavillet, J. et al. Root-growth mechanism for single-wall carbon nanotubes. Phys. Rev. Lett. 87, 275504 (2001)

    Article  CAS  Google Scholar 

  23. Dresselhaus, M. S., Dresselhaus, G., Saito, R. & Jorio, A. Raman spectroscopy of carbon nanotubes. Phys. Rep. 409, 47–99 (2005)

    Article  ADS  Google Scholar 

  24. Jorio, A. et al. Quantifying carbon-nanotube species with resonance Raman scattering. Phys. Rev. B 72, 075207 (2005)

    Article  ADS  Google Scholar 

  25. Soares, J. S. & Jorio, A. Study of carbon nanotube-substrate interaction. J. Nanotechnol. 2012, 1–10 (2012)

    Article  Google Scholar 

  26. Jorio, A. et al. Linewidth of the Raman features of individual single-wall carbon nanotubes. Phys. Rev. B 66, 115411 (2002)

    Article  ADS  Google Scholar 

  27. Telg, H. et al. Chiral index dependence of the G+ and G– Raman modes in semiconducting carbon nanotubes. ACS Nano 6, 904–911 (2012)

    Article  CAS  Google Scholar 

  28. Piscanec, S., Lazzeri, M., Robertson, J., Ferrari, A. & Mauri, F. Optical phonons in carbon nanotubes: Kohn anomalies, Peierls distortions, and dynamic effects. Phys. Rev. B 75, 035427 (2007)

    Article  ADS  Google Scholar 

  29. Rao, A. M. et al. Diameter-selective Raman scattering from vibrational modes in carbon nanotubes. Science 275, 187–191 (1997)

    Article  CAS  Google Scholar 

  30. Xu, Y.-Q. et al. Vertical array growth of small diameter single-walled carbon nanotubes. J. Am. Chem. Soc. 128, 6560–6561 (2006)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This research was supported in part by the Swiss National Science Foundation and by the State Secretariat for Education, Research and Innovation via the COST Action MP0901 ‘NanoTP’. K.A. acknowledges financial support from Deutsche Forschungsgemeinschaft.

Author information

Author notes

  1. Juan Ramon Sanchez-Valencia, Andreas Mueller & Konstantin Amsharov

    Present address: Present addresses: Nanotechnology on Surfaces Laboratory, Instituto de Ciencia de Materiales de Sevilla (CSIC-US), Avenida Américo Vespucio 49, E-41092 Sevilla, Spain (J.R.S.-V.); BASF SE, GVM/I–L 544, 67056 Ludwigshafen, Germany (A.M.); University Erlangen-Nuremberg, Institut für Organische Chemie II, Henkestrasse 42, 91054 Erlangen, Germany (K.A.).,

Authors and Affiliations

  1. nanotech@surfaces Laboratory, Empa, Swiss Federal Laboratories for Materials Science and Technology, 8600 Dübendorf, Switzerland,

    Juan Ramon Sanchez-Valencia, Thomas Dienel, Oliver Gröning, Pascal Ruffieux & Roman Fasel

  2. Laboratory for Reliability Science and Technology, Empa, Swiss Federal Laboratories for Materials Science and Technology, 8600 Dübendorf, Switzerland,

    Ivan Shorubalko

  3. Max Planck Institute for Solid State Research, Heisenbergstrasse 1, 70569 Stuttgart, Germany,

    Andreas Mueller, Martin Jansen & Konstantin Amsharov

  4. Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, 3012 Bern, Switzerland,

    Roman Fasel

Authors
  1. Juan Ramon Sanchez-Valencia
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Thomas Dienel
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Oliver Gröning
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Ivan Shorubalko
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Andreas Mueller
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Martin Jansen
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Konstantin Amsharov
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Pascal Ruffieux
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Roman Fasel
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

K.A., M.J. and R.F. initiated and conceived this work. K.A. designed the precursor molecules and the corresponding synthetic routes, K.A. and A.M. synthesised precursor molecules and performed HPLC, NMR and MS analyses. J.R.S.-V. carried out on-surface synthesis work. J.R.S.-V. and T.D. performed STM and Raman measurements, I.S. did the He ion microscopy analysis. O.G. performed the calculations. All authors participated in analysis and interpretation of the results. J.R.S.-V. drafted the manuscript, with contributions from P.R. and O.G. R.F. and K.A. edited the manuscript and coordinated the efforts of the research teams.

Corresponding authors

Correspondence to Konstantin Amsharov or Roman Fasel.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Extended data figures and tables

Extended Data Figure 1 Conformations of precursor P1 adsorbed on Pt(111).

a, Sketch of the molecular conformations due to the axial chirality of the benzo[c]phenanthrene moieties. b, c, Simulations of the extended HOMO (LUMO shows a similar structure) with the outer biphenyls at a lower (b) or higher (c) elevation (left), and with the corresponding molecular structure superposed (right). d–h, Conformational analysis of P1 (top) and STM images of observed conformations of the P1 molecules on Pt(111) (bottom). i, Statistical analysis of the different molecular conformations shows that at least 50% of the molecules adopt a configuration suitable for a correct dehydrogenation pathway (red square).

Extended Data Figure 2 Dehydrogenation pathways for ‘right’ and ‘wrong’ conformations of P1.

a–d, Molecular dehydrogenation pathways for a ‘right’ conformation (a), and for ‘wrong’ conformations with 1 (b), 2 (c) and 3 (d) biphenyl arms rotated. Cases b, c, and d do not lead to a completed singly capped SWCNT and do not act as seeds for nanotube growth on epitaxial elongation.

Extended Data Figure 3 Scanning helium ion microscopy images.

SHIM images of epitaxially elongated SWCNTs obtained by exposing seeds S1 to 1 × 10−7 mbar of ethanol for 1 h (270 L) at 770 K. Long carbon nanotubes can be observed to lie on the surface, and in some cases to shake under the ion beam (indicated by light green arrows, bottom). Top left, lower-magnification view of surface: numbered coloured boxes are shown at higher magnification to the right. The unnumbered grey-scale images show different surface locations at higher magnifications. The rightmost panel gives a higher magnification image of the long SWCNT seen in panel 1.

Extended Data Figure 4 Synthesis of SWCNT precursor P1.

Details are given in Methods: here we describe reaction steps a to j. a, PPh3, toluene, reflux, 95%; b, BrPh3PCH2PhBr, KOtBu, EtOH, reflux, 81%; c, I2, hv, propylene oxide, cyclohexane, 72%; d, Pd(PPh3)4, Cs2CO3, toluene/MeOH, 110°C, 79%; e, NBS, DBPO, CCl4, reflux, 70%; f, NaCN, DMSO, RT, 40%; g, H2SO4, H2O, HOAc, reflux, 98%; h, SOCl2, 65 °C; i, AlCl3, CH2Cl2, RT, 57%; j, propanoic acid, TsOH, o-DCB, 180 °C, 65%.

Extended Data Figure 5 LDI mass spectra of precursor P1 (C96H54).

a, b, LDI mass spectra of P1 before (a) and after (b) sublimation. Computed and experimentally observed isotope distribution patterns for C96H54 are given in the inset of b.

Related audio

PowerPoint slides

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sanchez-Valencia, J., Dienel, T., Gröning, O. et al. Controlled synthesis of single-chirality carbon nanotubes. Nature 512, 61–64 (2014). https://doi.org/10.1038/nature13607

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature13607

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing