Letter | Published:

Modulation of thermal and thermoelectric transport in individual carbon nanotubes by fullerene encapsulation

Nature Materials volume 16, pages 892897 (2017) | Download Citation

Abstract

The potential impact of encapsulated molecules on the thermal properties of individual carbon nanotubes (CNTs) has been an important open question since the first reports of the strong modulation of electrical properties in 20021,2. However, thermal property modulation has not been demonstrated experimentally because of the difficulty of realizing CNT-encapsulated molecules as part of thermal transport microstructures. Here we develop a nanofabrication strategy that enables measurement of the impact of encapsulation on the thermal conductivity (κ) and thermopower (S) of single CNT bundles that encapsulate C 60, Gd@C 82 and Er 2@C 82. Encapsulation causes 35–55% suppression in κ and approximately 40% enhancement in S compared with the properties of hollow CNTs at room temperature. Measurements of temperature dependence from 40 to 320 K demonstrate a shift of the peak in the κ to lower temperature. The data are consistent with simulations accounting for the interaction between CNTs and encapsulated fullerenes.

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References

  1. 1.

    et al. Mapping the one-dimensional electronic states of nanotube peapod structures. Science 295, 828–831 (2002).

  2. 2.

    et al. Bandgap modulation of carbon nanotubes by encapsulated metallofullerenes. Nature 415, 1005–1008 (2002).

  3. 3.

    et al. Tailored semiconducting carbon nanotube networks with enhanced thermoelectric properties. Nat. Energy 1, 16033 (2016).

  4. 4.

    et al. Temperature-dependent phonon conduction and nanotube engagement in metalized single wall carbon nanotube films. Nano Lett. 10, 2395–2400 (2010).

  5. 5.

    , & Encapsulated C60 in carbon nanotubes. Nature 396, 323–324 (1998).

  6. 6.

    et al. Synthesis and transformation of linear adamantane assemblies inside carbon nanotubes. ACS Nano 6, 8674–8683 (2012).

  7. 7.

    , , & Fabrication of metal nanowires in carbon nanotubes via versatile nano-template reaction. Nano Lett. 8, 693–699 (2008).

  8. 8.

    et al. Design of covalently functionalized carbon nanotubes filled with metal oxide nanoparticles for imaging, therapy, and magnetic manipulation. ACS Nano 8, 11290–11304 (2014).

  9. 9.

    , , & Thermal transport measurements of individual multiwalled nanotubes. Phys. Rev. Lett. 87, 215502 (2001).

  10. 10.

    , , , & Thermal conductance and thermopower of an individual single-wall carbon nanotube. Nano Lett. 5, 1842–1846 (2005).

  11. 11.

    et al. Measuring thermal and thermoelectric properties of one-dimensional nanostructures using a microfabricated device. J. Heat Transfer 125, 881–888 (2003).

  12. 12.

    & Thermal and structural characterizations of individual single-, double-, and multi-walled carbon nanotubes. Adv. Funct. Mater. 19, 3918–3925 (2009).

  13. 13.

    et al. Ambipolar field-effect transistor behavior of Gd@C82 metallofullerene peapods. Appl. Phys. Lett. 81, 4067–4069 (2002).

  14. 14.

    , , & Solid C60: a new form of carbon. Nature 347, 354–358 (1990).

  15. 15.

    et al. Confirmation by X-ray diffraction of the endohedral nature of the metallofullerene Y@C82. Nature 377, 46–49 (1995).

  16. 16.

    , , , & Thermal conductance of an individual single-wall carbon nanotube above room temperature. Nano Lett. 6, 96–100 (2006).

  17. 17.

    et al. Measuring the thermal conductivity of a single carbon nanotube. Phys. Rev. Lett. 95, 065502 (2005).

  18. 18.

    , , & Thermal conductivity of single-walled carbon nanotubes. Phys. Rev. B 59, R2514–R2516 (1999).

  19. 19.

    et al. Optical absorption and thermal transport of individual suspended carbon nanotube bundles. Nano Lett. 9, 590–594 (2009).

  20. 20.

    et al. Thermal conductivity of multi-walled carbon nanotube sheets: radiation losses and quenching of phonon modes. Nanotechnology 21, 035709 (2010).

  21. 21.

    , & Reduction of phonon lifetimes and thermal conductivity of a carbon nanotube on amorphous silica. Phys. Rev. B 84, 165418 (2011).

  22. 22.

    , , , & Electrical and thermal properties of C60-filled single-wall carbon nanotubes. Appl. Phys. Lett. 80, 1450–1452 (2002).

  23. 23.

    , , & Thermal conductivity of carbon nanotube peapods. Phys. Rev. B 70, 115416 (2004).

  24. 24.

    , & Investigation of the thermal conductivity of a fullerene peapod by molecular dynamics simulation. J. Cryst. Growth 310, 2301–2305 (2008).

  25. 25.

    , & Dependence of thermal conductivity of carbon nanopeapods on filling ratios of fullerene molecules. J. Phys. Chem. A 119, 11226–11232 (2015).

  26. 26.

    et al. Synthesis of carbon nanotube peapods directly on Si substrates. Appl. Phys. Lett. 86, 023109 (2005).

  27. 27.

    , & Energetics and electronic structures of encapsulated C60 in a carbon nanotube. Phys. Rev. Lett. 86, 3835–3838 (2001).

  28. 28.

    et al. Optical band gap modification of single-walled carbon nanotubes by encapsulated fullerenes. J. Am. Chem. Soc. 130, 4122–4128 (2008).

  29. 29.

    et al. Atomically resolved mechanical response of individual metallofullerene molecules confined inside carbon nanotubes. Nat. Nanotech. 3, 337–341 (2008).

  30. 30.

    et al. Wafer-scale monodomain films of spontaneously aligned single-walled carbon nanotubes. Nat. Nanotech. 11, 633–638 (2016).

Download references

Acknowledgements

We thank M. Barako for advice on writing the manuscript; M. Asheghi, J. Cho, J. Li, A. Marconnet, S. Roy and A. Sood for discussions on thermal and thermoelectric measurements; and H. Ishiwata for support on Raman spectroscopic measurement. The experimental part of this work was financially supported by the Air Force Office of Scientific Research (AFOSR, no. FA9550-12-1-0195), the National Science Foundation (NSF, no. 1336734), and JSPS KAKENHI (no. JP16H06722). The theory part was financially supported by JST-CREST (no. JPMJCR16Q5) and JSPS KAKENHI (no. JP16H04274).

Author information

Affiliations

  1. Department of Mechanical Engineering, Stanford University, Stanford, California 94305, USA

    • Takashi Kodama
    • , Woosung Park
    •  & Kenneth E. Goodson
  2. Department of Mechanical Engineering, School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan

    • Masato Ohnishi
    • , Takuma Shiga
    •  & Junichiro Shiomi
  3. Department of Materials Science and Engineering, Stanford University, Stanford, California 94305, USA

    • Joonsuk Park
  4. Institute of Engineering Innovation, School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan

    • Takashi Shimada
  5. Department of Chemistry, Nagoya University, Nagoya 464-8602, Japan

    • Hisanori Shinohara

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Contributions

T.K. led the project and contributed to the experimental works including device design, fabrication, and conduction measurement. M.O., T.Shiga and J.S. contributed to the theoretical work. W.P. contributed to the SEM imaging and conduction measurement. J.P. contributed to the TEM imaging. T.Shimada and H.S. synthesized and provided all of the CNT samples used in the project. K.E.G. served both as PI and primary advisor for the thermal and thermoelectric measurements. T.K., M.O., T.Shiga, J.S. and K.E.G. wrote the paper.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Takashi Kodama or Kenneth E. Goodson.

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DOI

https://doi.org/10.1038/nmat4946

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