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.

  • Article
  • Published:

Wafer-scale monodomain films of spontaneously aligned single-walled carbon nanotubes

Nature Nanotechnology volume 11, pages 633–638 (2016)Cite this article

Subjects

Abstract

The one-dimensional character of electrons, phonons and excitons in individual single-walled carbon nanotubes leads to extremely anisotropic electronic, thermal and optical properties. However, despite significant efforts to develop ways to produce large-scale architectures of aligned nanotubes, macroscopic manifestations of such properties remain limited. Here, we show that large (>cm2) monodomain films of aligned single-walled carbon nanotubes can be prepared using slow vacuum filtration. The produced films are globally aligned within ±1.5° (a nematic order parameter of ∼1) and are highly packed, containing 1 × 106 nanotubes in a cross-sectional area of 1 μm2. The method works for nanotubes synthesized by various methods, and film thickness is controllable from a few nanometres to ∼100 nm. We use the approach to create ideal polarizers in the terahertz frequency range and, by combining the method with recently developed sorting techniques, highly aligned and chirality-enriched nanotube thin-film devices. Semiconductor-enriched devices exhibit polarized light emission and polarization-dependent photocurrent, as well as anisotropic conductivities and transistor action with high on/off ratios.

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: Fabrication and characterization of wafer-scale monodomain films of aligned CNTs.
Figure 2: Characterization of aligned CNT films through polarization-dependent optical spectroscopy.
Figure 3: Optoelectronic devices made from aligned and (6,5)-enriched CNT films.
Figure 4: Electronic devices made from aligned CNT films.

Similar content being viewed by others

References

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

    Book  Google Scholar 

  2. Ma, Y., Wang, B., Wu, Y., Huang, Y. & Chen, Y. The production of horizontally aligned single-walled carbon nanotubes. Carbon 49, 4098–4110 (2011).

    Article  CAS  Google Scholar 

  3. Liu, B., Wang, C., Liu, J., Che, Y. & Zhou, C. Aligned carbon nanotubes: from controlled synthesis to electronic applications. Nanoscale 5, 9483–9502 (2013).

    Article  CAS  Google Scholar 

  4. De Heer, W. A. et al. Aligned carbon nanotube films: production and optical and electronic properties. Science 268, 845–847 (1995).

    Article  CAS  Google Scholar 

  5. Murakami, Y. et al. Growth of vertically aligned single-walled carbon nanotube films on quartz substrates and their optical anisotropy. Chem. Phys. Lett. 385, 298–303 (2004).

    Article  CAS  Google Scholar 

  6. Pint, C. L., Xu, Y., Pasquali, M. & Hauge, R. H. Formation of highly dense, aligned ribbons and ultra-thin films of single-walled carbon nanotubes from carpets. ACS Nano 2, 1871–1878 (2008).

    Article  CAS  Google Scholar 

  7. Lynch, M. D. & Patrick, D. L. Organizing carbon nanotubes with liquid crystals. Nano Lett. 2, 1197–1201 (2002).

    Article  CAS  Google Scholar 

  8. Lagerwall, J. P. F. & Scalia, G. Carbon nanotubes in liquid crystals. J. Mater. Chem. 18, 2890–2898 (2008).

    Article  CAS  Google Scholar 

  9. Zamora-Ledezma, C. et al. Anisotropic thin films of single-wall carbon nanotubes from aligned lyotropic nematic suspensions. Nano Lett. 8, 4103–4107 (2008).

    Article  CAS  Google Scholar 

  10. Kim, Y., Minami, N. & Kazaoui, S. Highly polarized absorption and photoluminescence of stretch-aligned single-wall carbon nanotubes dispersed in gelatin films. Appl. Phys. Lett. 86, 073103 (2005).

    Article  Google Scholar 

  11. Shaver, J. et al. Magnetic brightening of carbon nanotube photoluminescence through symmetry breaking. Nano Lett. 7, 1851–1855 (2007).

    Article  CAS  Google Scholar 

  12. Mclean, R. S., Huang, X., Khripin, C., Jagota, A. & Zheng, M. Controlled two-dimensional pattern of spontaneously aligned carbon nanotubes. Nano Lett. 6, 55–60 (2006).

    Article  CAS  Google Scholar 

  13. Dan, B., Ma, A. W. K., Hároz, E. H., Kono, J. & Pasquali, M. Nematic-like alignment in SWNT thin films from aqueous colloidal suspensions. Ind. Eng. Chem. Res. 51, 10232–10237 (2012).

    Article  CAS  Google Scholar 

  14. Oh, J. Y. et al. Easy preparation of self-assembled high-density buckypaper with enhanced mechanical properties. Nano Lett. 15, 190–197 (2015).

    Article  CAS  Google Scholar 

  15. Puech, N. et al. Highly ordered carbon nanotube nematic liquid crystals. J. Phys. Chem. C 115, 3272–3278 (2011).

    Article  CAS  Google Scholar 

  16. Zakri, C. et al. Liquid crystals of carbon nanotubes and graphene. Phil. Trans. R. Soc. A 371, 20120499 (2013).

    Article  Google Scholar 

  17. Walters, D. A. et al. In-plane-aligned membranes of carbon nanotubes. Chem. Phys. Lett. 338, 14–20 (2001).

    Article  CAS  Google Scholar 

  18. Zaric, S. et al. Estimation of magnetic susceptibility anisotropy of carbon nanotubes using magneto-photoluminescence. Nano Lett. 4, 2219–2221 (2004).

    Article  CAS  Google Scholar 

  19. Beyer, S. T. & Walus, K. Controlled orientation and alignment in films of single-walled carbon nanotubes using inkjet printing. Langmuir 28, 8753–8759 (2012).

    Article  CAS  Google Scholar 

  20. Cao, Q. et al. Arrays of single-walled carbon nanotubes with full surface coverage for high-performance electronics. Nature Nanotech. 8, 180–186 (2013).

    Article  CAS  Google Scholar 

  21. Wu, Z. et al. Transparent, conductive nanotube films. Science 305, 1273–1276 (2004).

    Article  CAS  Google Scholar 

  22. Zhang, Q. et al. Plasmonic nature of the terahertz conductivity peak in single-wall carbon nanotubes. Nano Lett. 13, 5991–5996 (2013).

    Article  CAS  Google Scholar 

  23. Ajiki, H. & Ando, T. Aharonov–Bohm effect in carbon nanotubes. Physica B 201, 349–352 (1994).

    Article  CAS  Google Scholar 

  24. Miyauchi, Y., Oba, M. & Maruyama, S. Cross-polarized optical absorption of single-walled nanotubes by polarized photoluminescence excitation spectroscopy. Phys. Rev. B 74, 205440 (2006).

    Article  Google Scholar 

  25. Lefebvre, J. & Finnie, P. Polarized photoluminescence excitation spectroscopy of single-walled carbon nanotubes. Phys. Rev. Lett. 98, 167406 (2007).

    Article  CAS  Google Scholar 

  26. Ren, L. et al. Carbon nanotube terahertz polarizer. Nano Lett. 9, 2610–2613 (2009).

    Article  CAS  Google Scholar 

  27. Onsager, L. The effects of shape on the interaction of colloidal particles. Ann. NY Acad. Sci. 51, 627–659 (1949).

    Article  CAS  Google Scholar 

  28. Yang, P. Nanotechnology: wires on water. Nature 425, 243–244 (2003).

    Article  CAS  Google Scholar 

  29. Sharma, R., Lee, C. Y., Choi, J. H., Chen, K. & Strano, M. S. Nanometer positioning, parallel alignment, and placement of single anisotropic nanoparticles using hydrodynamic forces in cylindrical droplets. Nano Lett. 7, 2693–2700 (2007).

    Article  CAS  Google Scholar 

  30. Khripin, C. Y., Fagan, J. A. & Zheng, M. Spontaneous partition of carbon nanotubes in polymer-modified aqueous phases. J. Am. Chem. Soc. 135, 6822–6825 (2013).

    Article  CAS  Google Scholar 

  31. Subbaiyan, N. K. et al. Role of surfactants and salt in aqueous two-phase separation of carbon nanotubes toward simple chirality isolation. ACS Nano 8, 1619–1628 (2014).

    Article  CAS  Google Scholar 

  32. Fagan, J. A. et al. Isolation of specific small-diameter single-wall carbon nanotube species via aqueous two-phase extraction. Adv. Mater. 26, 2800–2804 (2014).

    Article  CAS  Google Scholar 

  33. Nanot, S. et al. Broadband, polarization-sensitive photodetector based on optically-thick films of macroscopically long, dense, and aligned carbon nanotubes. Sci. Rep. 3, 1335 (2013).

    Article  Google Scholar 

  34. He, X. et al. Photothermoelectric p–n junction photodetectors with intrinsic polarimetry based on macroscopic carbon nanotube films. ACS Nano 7, 7271–7277 (2013).

    Article  CAS  Google Scholar 

  35. Jakubinek, M. B. et al. Thermal and electrical conductivity of tall, vertically aligned carbon nanotube arrays. Carbon 48, 3947–3952 (2010).

    Article  CAS  Google Scholar 

  36. Bekyarova, E. et al. Electronic properties of single-walled carbon nanotube networks. J. Am. Chem. Soc. 127, 5990–5995 (2005).

    Article  CAS  Google Scholar 

  37. Zhang, D. et al. Transparent, conductive, and flexible carbon nanotube films and their application in organic light-emitting diodes. Nano Lett. 6, 1880–1886 (2006).

    Article  CAS  Google Scholar 

  38. Chen, Z., Appenzeller, J., Knoch, J., Lin, Y. & Avouris, P. The role of metal–nanotube contact in the performance of carbon nanotube field-effect transistors. Nano Lett. 5, 1497–1502 (2005).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Basic Energy Sciences (BES) programme of the US Department of Energy through grant no. DE-FG02-06ER46308 (for the preparation and characterization of aligned carbon nanotube films) and the Robert A. Welch Foundation through grant no. C-1509 (for terahertz and infrared characterization). S.K.D. and E.H.H. acknowledge support from the LANL LDRD programme. Portions of this work were performed at the Center for Integrated Nanotechnologies, a US Department of Energy, Office of Science user facility. The authors thank H. Kasai, A. Zubair, C. Sewell, S. Peters and T. Higashira for their assistance with terahertz characterization measurements and I. Kurganskaya, A. Lüttge, R. Headrick and M. Pasquali for discussions.

Author information

Author notes

  1. John M. Robinson

    Present address: Present address: Department of Physics, University of Colorado, Boulder, Colorado 80302, USA,

  2. Xiaowei He and Weilu Gao: These authors contributed equally to this work

Authors and Affiliations

  1. Department of Electrical and Computer Engineering, Rice University, Houston, 77005, Texas, USA

    Xiaowei He, Weilu Gao, Qi Zhang, John M. Robinson & Junichiro Kono

  2. College of Biosystems Engineering and Food Science, Zhejiang University, Hangzhou, 310058, Zhejiang, China

    Lijuan Xie

  3. Department of Materials Science and NanoEngineering, Rice University, Houston, 77005, Texas, USA

    Bo Li, Sidong Lei, Weipeng Wang, Robert Vajtai, Pulickel M. Ajayan, W. Wade Adams, Robert H. Hauge & Junichiro Kono

  4. Center for Integrated Nanotechnologies, Los Alamos National Laboratory, Los Alamos, 87545, New Mexico, USA

    Erik H. Hároz & Stephen K. Doorn

  5. Department of Chemistry, Rice University, Houston, 77005, Texas, USA

    Robert H. Hauge

  6. Department of Physics and Astronomy, Rice University, Houston, 77005, Texas, USA

    Junichiro Kono

Authors
  1. Xiaowei He
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Weilu Gao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Lijuan Xie
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Bo Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Qi Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Sidong Lei
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. John M. Robinson
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Erik H. Hároz
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Stephen K. Doorn
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Weipeng Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Robert Vajtai
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Pulickel M. Ajayan
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. W. Wade Adams
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Robert H. Hauge
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Junichiro Kono
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

X.H. and W.G. developed the process of making aligned CNT films, performed most of the characterization experiments, and analysed the data obtained, under the supervision and guidance of W.W.A., R.H.H. and J.K. L.X. prepared chirality-enriched SWCNT suspensions, in collaboration with E.H.H. and S.K.D. B.L. made the AFM measurements and B.L. and W.W. performed TEM imaging, under the advisement of R.V. and P.M.A. Q.Z. and J.M.R. participated in the terahertz and infrared spectroscopy measurements. S.L. helped characterize the FET devices. X.H., W.G. and J.K. wrote the manuscript. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Junichiro Kono.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 10089 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

He, X., Gao, W., Xie, L. et al. Wafer-scale monodomain films of spontaneously aligned single-walled carbon nanotubes. Nature Nanotech 11, 633–638 (2016). https://doi.org/10.1038/nnano.2016.44

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nnano.2016.44

This article is cited by

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