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:

Narrow-band single-photon emission through selective aryl functionalization of zigzag carbon nanotubes

Nature Chemistry volume 10, pages 1089–1095 (2018)Cite this article

Subjects

Abstract

The introduction of sp3 defects into single-walled carbon nanotubes through covalent functionalization can generate new light-emitting states and thus dramatically expand their optical functionality. This may open up routes to enhanced imaging, photon upconversion, and room-temperature single-photon emission at telecom wavelengths. However, a significant challenge in harnessing this potential is that the nominally simple reaction chemistry of nanotube functionalization introduces a broad diversity of emitting states. Precisely defining a narrow band of emission energies necessitates constraining these states, which requires extreme selectivity in molecular binding configuration on the nanotube surface. We show here that such selectivity can be obtained through aryl functionalization of so-called ‘zigzag’ nanotube structures to achieve a threefold narrowing in emission bandwidth. Accompanying density functional theory modelling reveals that, because of the associated structural symmetry, the defect states become degenerate, thus limiting emission energies to a single narrow band. We show that this behaviour can only result from a predominant selectivity for ortho binding configurations of the aryl groups on the nanotube lattice.

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

Fig. 1: Chirality dependence of aryl diazonium binding configurations.
Fig. 2: Chirality dependence of defect-state photoluminescence spectra.
Fig. 3: Single-tube photoluminescence spectra of 13 aryl-functionalized (11,0) nanotubes.
Fig. 4: Calculated defect-state photoluminescence spectra.
Fig. 5: Chirality-dependent aryl-diazonium reaction kinetics.

Similar content being viewed by others

References

  1. Michler, P. et al. Quantum correlation among photons from a single quantum dot at room temperature. Nature 406, 968–970 (2000).

    Article  CAS  PubMed  Google Scholar 

  2. Miyazawa, T. et al. Single-photon emission at 1.5 μm from an InAs/InP quantum dot with highly suppressed multi-photon emission probabilities. Appl. Phys. Lett. 109, 132106 (2016).

    Article  CAS  Google Scholar 

  3. Srivastava, A. et al. Optically active quantum dots in monolayer WSe2. Nat. Nanotech. 10, 491–496 (2015).

    Article  CAS  Google Scholar 

  4. He, Y.-M. et al. Single quantum emitters in monolayer semiconductors. Nat. Nanotech. 10, 497–501 (2015).

    Article  CAS  Google Scholar 

  5. Koperski, M. et al. Single photon emitters in exfoliated WSe2 structures. Nat. Nanotech. 10, 503–506 (2015).

    Article  CAS  Google Scholar 

  6. Chakraborty, C., Kinnischtzke, L., Goodfellow, K. M., Beams, R. & Vamivakas, A. N. Voltage-controlled quantum light from an atomically thin semiconductor. Nat. Nanotech. 10, 507–512 (2015).

    Article  CAS  Google Scholar 

  7. Tran, T. T., Bray, K., Ford, M. J., Toth, M. & Aharonovich, I. Quantum emission from hexagonal boron nitride monolayers. Nat. Nanotech. 11, 37–41 (2016).

    Article  CAS  Google Scholar 

  8. Hogele, A., Galland, C., Winger, M. & Imamoglu, A. Photon antibunching in the photoluminescence spectra of a single carbon nanotube. Phys. Rev. Lett. 100, 217401 (2008).

    Article  CAS  PubMed  Google Scholar 

  9. Walden-Newman, W., Sarpkaya, I. & Strauf, S. Quantum light signatures and nanosecond spectral diffusion from cavity-embedded carbon nanotubes. Nano Lett. 12, 1934–1941 (2012).

    Article  CAS  PubMed  Google Scholar 

  10. Hofmann, M. S. et al. Bright, long-lived, and coherent excitons in carbon nanotube quantum dots. Nat. Nanotech. 8, 502–505 (2013).

    Article  CAS  Google Scholar 

  11. Ma, X., Hartmann, N. F., Baldwin, J. K. S., Doorn, S. K. & Htoon, H. Room-temperature single-photon generation from solitary dopants of carbon nanotubes. Nat. Nanotech. 10, 671–675 (2015).

    Article  CAS  Google Scholar 

  12. He, X. et al. Tunable room-temperature single-photon emission at telecom wavelengths from sp 3 defects in carbon nanotubes. Nat. Photon. 11, 577–582 (2017).

    Article  CAS  Google Scholar 

  13. Aharonovich, I., Englund, D. & Toth, M. Solid-state single-photon emitters. Nat. Photon. 10, 631–641 (2016).

    Article  CAS  Google Scholar 

  14. Bachilo, S. M. et al. Structure-assigned optical spectra of single-walled carbon nanotubes. Science 298, 2361–2366 (2002).

    Article  CAS  PubMed  Google Scholar 

  15. Zheng, M. Sorting carbon nanotubes. Top. Curr. Chem. 375, 13 (2017).

    Article  CAS  Google Scholar 

  16. Ghosh, S., Bachilo, S. M., Simonette, R. A., Beckingham, K. M. & Weisman, R. B. Oxygen doping modifies near-infrared band gaps in fluorescent single-walled carbon nanotubes. Science 330, 1656–1659 (2010).

    Article  CAS  PubMed  Google Scholar 

  17. Ma, X. et al. Electronic structure and chemical nature of oxygen dopant states in carbon nanotubes. ACS Nano 8, 10782–10789 (2014).

    Article  CAS  PubMed  Google Scholar 

  18. Kwon, H. et al. Molecularly tunable fluorescent quantum defects. J. Am. Chem. Soc. 138, 6878–6885 (2016).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  19. Piao, Y. M. et al. Brightening of carbon nanotube photoluminescence through the incorporation of sp 3 defects. Nat. Chem. 5, 840–845 (2013).

    Article  CAS  PubMed  Google Scholar 

  20. Miyauchi, Y. et al. Brightening of excitons in carbon nanotubes on dimensionality modification. Nat. Photon. 7, 715–719 (2013).

    Article  CAS  Google Scholar 

  21. Akizuki, N., Aota, S., Mouri, S., Matsuda, K. & Miyauchi, Y. Efficient near-infrared up-conversion photoluminescence in carbon nanotubes. Nat. Commun. 6, 8920 (2015).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  22. He, X. et al. Low-temperature single carbon nanotube spectroscopy of sp 3 quantum defects. ACS Nano 11, 10785–10796 (2017).

    Article  CAS  PubMed  Google Scholar 

  23. Shiraki, T., Shiraishi, T., Juhász, G. & Nakashima, N. Emergence of new redshifted carbon nanotube photoluminescence based on proximal doped-site design. Sci. Rep. 6, 28393 (2016).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  24. Maeda, Y. et al. Tuning of the photoluminescence and up-conversion photoluminescence properties of single-walled carbon nanotubes by chemical functionalization. Nanoscale 8, 16916–16921 (2016).

    Article  CAS  PubMed  Google Scholar 

  25. Gifford, B. J., Kilina, S., Htoon, H., Doorn, S. K. & Tretiak, S. Exciton localization and optical emission in aryl-functionalized carbon nanotubes. J. Phys. Chem. C 122, 1828–1838 (2017).

    Article  CAS  Google Scholar 

  26. Strano, M. S. et al. Electronic structure control of single-walled carbon nanotube functionalization. Science 301, 1519–1522 (2003).

    Article  CAS  PubMed  Google Scholar 

  27. Niyogi, S. et al. Chemistry of single-walled carbon nanotubes. Acc. Chem. Res. 35, 1105–1113 (2002).

    Article  CAS  PubMed  Google Scholar 

  28. Bekyarova, E. et al. Effect of covalent chemistry on the electronic structure and properties of carbon nanotubes and graphene. Acc. Chem. Res. 46, 65–76 (2013).

    Article  CAS  PubMed  Google Scholar 

  29. Chua, C. K. & Pumera, M. Covalent chemistry on graphene. Chem. Soc. Rev. 42, 3222–3233 (2013).

    Article  CAS  PubMed  Google Scholar 

  30. Vora, P. M., Tu, X., Mele, E. J., Zheng, M. & Kikkawa, J. M. Chirality dependence of the K-momentum dark excitons in carbon nanotubes. Phys. Rev. B 81, 155123 (2010).

    Article  CAS  Google Scholar 

  31. Niyogi, S., Densmore, C. G. & Doorn, S. K. Electrolyte tuning of surfactant interfacial behavior for enhanced density-based separations of single-walled carbon nanotubes. J. Am. Chem. Soc. 131, 1144–1153 (2009).

    Article  CAS  PubMed  Google Scholar 

  32. Duque, J. G., Densmore, C. G. & Doorn, S. K. Saturation of surfactant structure at the single-walled carbon nanotube surface. J. Am. Chem. Soc. 132, 16165–16175 (2010).

    Article  CAS  PubMed  Google Scholar 

  33. Tummala, N. R. & Striolo, A. SDS surfactants on carbon nanotubes: aggregate morphology. ACS Nano 3, 595–602 (2009).

    Article  CAS  PubMed  Google Scholar 

  34. 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  PubMed  Google Scholar 

  35. Yarotski, D. et al. Scanning tunneling microscopy of DNA-wrapped carbon nanotubes. Nano Lett. 9, 12–17 (2009).

    Article  CAS  PubMed  Google Scholar 

  36. Shiraki, T., Uchimura, S., Shiraishi, T., Onitsuka, H. & Nakashima, N. Near infrared photoluminescence modulation by defect site design using aryl isomers in locally functionalized single-walled carbon nanotubes. Chem. Commun. 53, 12544–12547 (2017).

    Article  CAS  Google Scholar 

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

    Article  CAS  PubMed  Google Scholar 

  38. Yomogida, Y. et al. Industrial-scale separation of high-purity single-chirality single-wall carbon nanotubes for biological imaging. Nat. Commun. 7, 12056 (2016).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  39. Ao, G., Streit, J. K., Fagan, J. A. & Zheng, M. Differentiating left- and right-handed carbon nanotubes by DNA. J. Am. Chem. Soc. 138, 16677–16685 (2016).

    Article  CAS  PubMed  Google Scholar 

  40. Streit, J. K., Fagan, J. A. & Zheng, M. A low energy route to DNA-wrapped carbon nanotubes via replacement of bile salt surfactants. Anal. Chem. 89, 10496–10503 (2017).

    Article  CAS  PubMed  Google Scholar 

  41. Hartmann, N. F. et al. Photoluminescence imaging of solitary dopant sites in covalently doped single-wall carbon nanotubes. Nanoscale 7, 20521–20530 (2015).

    Article  CAS  PubMed  Google Scholar 

  42. Hartmann, N. F. et al. Photoluminescence dynamics of aryls sp 3 defect states in single-walled carbon nanotubes. ACS Nano 10, 8355–8365 (2016).

    Article  CAS  PubMed  Google Scholar 

  43. Powell, L. R., Piao, Y. & Wang, Y. Optical excitation of carbon nanotubes drives localized diazonium reactions. J. Phys. Chem. Lett. 7, 3690–3694 (2016).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  44. Sanchez, S. R., Bachilo, S. M., Kadria-Vili, Y., Lin, C. W. & Weisman, R. B. (n,m) specific absorption cross sections of single-walled carbon nanotubes measured by variance spectroscopy. Nano Lett. 16, 6903–6909 (2016).

    Article  CAS  PubMed  Google Scholar 

  45. Frisch, M. J et al. Gaussian 09 (Gaussian, Inc., 2009).

  46. Yanai, T., Tew, D. P. & Handy, N. C. A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP). Chem. Phys. Lett. 393, 51–57 (2004).

    Article  CAS  Google Scholar 

  47. Hehre, W. J., Stewart, R. F. & Pople, J. A. Self-consistent molecular-orbital methods. I. Use of Gaussian expansions of Slater-type atomic orbitals. J. Chem. Phys. 51, 2657–2664 (1969).

    Article  CAS  Google Scholar 

  48. Gifford, B. J. et al. Correction scheme for comparison of computed and experimental optical transition energies in functionalized single-walled carbon nanotubes. J. Phys. Chem. Lett. 9, 2460–2468 (2018).

    Article  CAS  PubMed  Google Scholar 

  49. Kilina, S., Ramirez, J. & Tretiak, S. Brightening of the lowest exciton in carbon nanotubes via chemical functionalization. Nano Lett. 12, 2306–2312 (2012).

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

This work was conducted in part at the Center for Integrated Nanotechnologies, a US Department of Energy, Office of Science user facility, and supported in part by the Center for Nonlinear Studies and by Los Alamos National Laboratory Directed Research and Development funds. S.K. acknowledges financial support from NSF Grant CHE-1413614 for studies of functionalized carbon nanotubes. For computational resources and administrative support, the authors thank the Center for Computationally Assisted Science and Technology (CCAST) at North Dakota State University. The authors also acknowledge the LANL Institutional Computing (IC) Program for providing computational resources. H.K. acknowledges support from JSPS KAKENHI grant no. JP25220602. Correspondence and requests for materials should be addressed to S.K.D. or S.T.

Author information

Author notes

  1. These authors contributed equally to this work: Avishek Saha, Brendan J. Gifford.

Authors and Affiliations

  1. Center for Integrated Nanotechnologies, Materials Physics and Applications Division, Los Alamos National Laboratory, Los Alamos, NM, USA

    Avishek Saha, Brendan J. Gifford, Xiaowei He, Han Htoon, Sergei Tretiak & Stephen K. Doorn

  2. Center for Nonlinear Studies , Los Alamos National Laboratory, Los Alamos, NM, USA

    Brendan J. Gifford

  3. Department of Chemistry and Biochemistry, North Dakota State University, Fargo, ND, USA

    Brendan J. Gifford, Svetlana Kilina & Sergei Tretiak

  4. Materials Science and Engineering Division, National Institute of Standards and Technology, Gaithersburg, MD, USA

    Geyou Ao & Ming Zheng

  5. Nanomaterials Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki, Japan

    Hiromichi Kataura

  6. Theoretical Division, Los Alamos National Laboratory, Los Alamos, NM, USA

    Sergei Tretiak

Authors
  1. Avishek Saha
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Brendan J. Gifford
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xiaowei He
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Geyou Ao
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ming Zheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Hiromichi Kataura
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Han Htoon
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Svetlana Kilina
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Sergei Tretiak
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Stephen K. Doorn
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

S.K.D. conceived and designed the experiments. Nanotube separations, functionalization, and spectroscopic characterization were performed by A.S. with assistance from X.H. under the supervision of S.K.D. Single-nanotube spectroscopy was performed by X.H. under the supervision of H.H. Additional purified nanotube material was provided by G.A., M.Z. and H.K. Theoretical modelling was performed by B.J.G. under the supervision of S.T. and S.K. All authors contributed to the analysis and interpretation of results. A.S., B.J.G., S.T. and S.K.D. wrote the manuscript with assistance from all co-authors.

Corresponding authors

Correspondence to Sergei Tretiak or Stephen K. Doorn.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figures 1–5, Supplementary Table 1, Supplementary Computational Methods

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Saha, A., Gifford, B.J., He, X. et al. Narrow-band single-photon emission through selective aryl functionalization of zigzag carbon nanotubes. Nature Chem 10, 1089–1095 (2018). https://doi.org/10.1038/s41557-018-0126-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41557-018-0126-4

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