Skip to main content

Thank you for visiting 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.

Giant Raman scattering from J-aggregated dyes inside carbon nanotubes for multispectral imaging


Raman spectroscopy uses visible light to acquire vibrational fingerprints of molecules, thus making it a powerful tool for chemical analysis in a wide range of media. However, its potential for optical imaging at high resolution is severely limited by the fact that the Raman effect is weak. Here, we report the discovery of a giant Raman scattering effect from encapsulated and aggregated dye molecules inside single-walled carbon nanotubes. Measurements performed on rod-like dyes such as α-sexithiophene and β-carotene, assembled inside single-walled carbon nanotubes as highly polarizable J-aggregates, indicate a resonant Raman cross-section of (3 ± 2) × 10−21 cm2 sr−1, which is well above the cross-section required for detecting individual aggregates at the highest optical resolution. Free from fluorescence background and photobleaching, this giant Raman effect allows the realization of a library of functionalized nanoprobe labels for Raman imaging with robust detection using multispectral analysis.

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

Relevant articles

Open Access articles citing this article.

Access options

Rent or buy this article

Prices vary by article type



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

Figure 1: Schematic representation of 6T@f-SWNT.
Figure 2: Absorbance and Raman spectra of SWNTs, 6T, 6T@SWNTs and 6T@f-SWNTs.
Figure 3: Polarized micro-Raman spectroscopy of individual SWNTs.
Figure 4: Demonstration of dyes@SWNTs as Raman nanoprobes.
Figure 5: Raman multiplexing, protein recognition and tagged bacteria with dyes@SWNTs nanoprobes.


  1. Le Ru, E. C. & Etchegoin, P. G. Principle of Surface-Enhanced Raman Spectroscopy (Elsevier, 2009).

    Google Scholar 

  2. Aroca, R. Surface-Enhanced Vibrational Spectroscopy (Wiley, 2006).

    Book  Google Scholar 

  3. Shim, S., Stuart, C. M. & Mathies, R. A. Resonance Raman cross-sections and vibronic analysis of Rhodamine 6G from broadband stimulated Raman spectroscopy. ChemPhysChem 9, 697–699 (2008).

    Article  Google Scholar 

  4. Stiles, P. L., Dieringer, J. A., Shah, N. C. & Van Duyne, R. P. Surface-enhanced Raman spectroscopy. Annu. Rev. Anal. Chem. 1, 601–626 (2008).

    Article  Google Scholar 

  5. Moskovits, M. Surface-enhanced spectroscopy. Rev. Mod. Phys. 57, 783–826 (1985).

    Article  ADS  Google Scholar 

  6. Kingston, C. T., Jakubek, Z. J., Dénommé, S. & Simard, B. Efficient laser synthesis of single-walled carbon nanotubes through laser heating of the condensing vaporization plume. Carbon 42, 1657–1664 (2004).

    Article  Google Scholar 

  7. Hasobe, T., Fukuzumi, S. & Kamat, P. V. Ordered assembly of protonated porphyrin driven by single-wall carbon nanotubes: J- and H-aggregates to nanorods. J. Am. Chem. Soc. 127, 11884–11885 (2005).

    Article  Google Scholar 

  8. Loi, M. A. et al. Encapsulation of conjugated oligomers in single-walled carbon nanotubes: towards nanohybrids for photonic devices. Adv. Mater. 22, 1635–1640 (2010).

    Article  Google Scholar 

  9. Gao, J. et al. Electronic interactions between ‘pea’ and ‘pod’: the case of oligothiophenes encapsulated in carbon nanotubes. Small 7, 1807–1815 (2011).

    Article  Google Scholar 

  10. Kalbac, M., Kavan, L., Gorantla, S., Gemming, T. & Dunsch, L. Sexithiophene encapsulated in a single-walled carbon nanotube: an in situ Raman spectroelectrochemical study of a peapod structure. Chem. Eur. J. 16, 11753–11759 (2010).

    Article  Google Scholar 

  11. Alvarez, L. et al. Charge transfer evidence between carbon nanotubes and encapsulated conjugated oligomers. J. Phys. Chem. C 115, 11898–11905 (2011).

    Article  Google Scholar 

  12. Yanagi, K., Miyata, Y. & Kataura, H. Highly stabilized β-carotene in carbon nanotubes. Adv. Mater. 18, 437–441 (2006).

    Article  Google Scholar 

  13. Yanagi, K. et al. Light-harvesting function of β-carotene inside carbon nanotubes. Phys. Rev. B 74, 155420 (2006).

    Article  ADS  Google Scholar 

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

    Article  ADS  Google Scholar 

  15. Esposti, A. D., Fanti, M., Muccini, M., Taliani, C. & Ruani, G. The polarized infrared and Raman spectra of α-T6 single crystal: an experimental and theoretical study. J. Chem. Phys. 112, 5957–5969 (2000).

    Article  ADS  Google Scholar 

  16. Takenobu, T. et al. Stable and controlled amphoteric doping by encapsulation of organic molecules inside carbon nanotubes. Nature Mater. 2, 683–688 (2003).

    Article  ADS  Google Scholar 

  17. Garrot, D. et al. Time-resolved investigation of excitation energy transfer in carbon nanotube–porphyrin compounds. J. Phys. Chem. C 115, 23283–23292 (2011).

    Article  Google Scholar 

  18. Huang, C. et al. Spectroscopic properties of nanotube–chromophore hybrids. ACS Nano 5, 7767–7774 (2012).

    Article  Google Scholar 

  19. Bohn, J. E. et al. Estimating the Raman cross sections of single carbon nanotubes. ACS Nano 4, 3466–3470 (2010).

    Article  Google Scholar 

  20. Jorio, A. et al. Structural (n, m) determination of isolated single-wall carbon nanotubes by resonant Raman scattering. Phys. Rev. Lett. 86, 1118–1121 (2001).

    Article  ADS  Google Scholar 

  21. Duesberg, G. S., Loa, I., Burghard, M., Syassen, K. & Roth, S. Polarized Raman spectroscopy on isolated single-wall carbon nanotubes. Phys. Rev. Lett. 85, 5436–5439 (2000).

    Article  ADS  Google Scholar 

  22. Klar, P. et al. Raman scattering efficiency of graphene. Phys. Rev. B 87, 205435 (2013).

    Article  ADS  Google Scholar 

  23. Joh, D. Y. et al. Single-walled carbon nanotubes as excitonic optical wires. Nature Nanotech. 6, 51–56 (2011).

    Article  ADS  Google Scholar 

  24. OuYang, S. L. et al. Effect of the structural order of all-trans-β-carotene on the Raman scattering cross section at low concentrations. J. Raman Spectrosc. 41, 1650–1654 (2010).

    Article  ADS  Google Scholar 

  25. Tian, J. et al. Study of resonance Raman cross section of aqueous β-carotene at low concentrations. Appl. Phys. B 87, 727–730 (2007).

    Article  ADS  Google Scholar 

  26. Thrall, E. S., Crowther, A. C., Yu, Z. & Brus, L. R6G on graphene: high Raman detection sensitivity, yet decreased Raman cross-section. Nano Lett. 12, 1571–1577 (2012).

    Article  ADS  Google Scholar 

  27. Cabana, J., Lavoie, S. & Martel, R. Thermal chemistry of methylene- and phenyl-functionalized carbon nanotubes. J. Am. Chem. Soc. 132, 1389–1394 (2010).

    Article  Google Scholar 

  28. Chen, Z. et al. Protein microarrays with carbon nanotubes as multicolor Raman labels. Nature Biotechnol. 26, 1285–1292 (2008).

    Article  Google Scholar 

  29. Liu, Z. et al. Multiplexed five-color molecular imaging of cancer cells and tumor tissues with carbon nanotube Raman tags in the near-infrared. Nano Res. 3, 222–233 (2010).

    Article  Google Scholar 

  30. Qi, H. et al. Functionalization of single-walled carbon nanotubes with protein by click chemistry as sensing platform for sensitized electrochemical immunoassay. Electrochim. Acta 63, 76–82 (2012).

    Article  Google Scholar 

  31. Vadeboncoeur, C., Mayrand, D. & Trahan, L. A comparative study of enzymes involved in glucose phosphorylation in oral streptococci. J. Dent. Res. 61, 60–65 (1982).

    Article  Google Scholar 

Download references


The authors thank M. Côté, P. McBreen and C. Silva for discussions, M. Choueb for SEM, B. Simard and his group for providing the SWNTs used for this study, M.A. Loi and E. Menna for sharing samples of 6T@SWNTs and discussions, and J. Barbeau for providing cultures of Candida albicans. This work was possible because of financial support from the Natural Sciences and Engineering Research Council of Canada (NSERC), Nanoquébec and the Canada Research Chair (CRC) programmes.

Author information

Authors and Affiliations



Data were collected and analysed by E.G., N.Y.-Wa.T., F.L., J.C., M.-A.N. and R.M. The experiments were conceived by E.G., N.Y.-Wa.T., J.C., F.L., M.-A.N. and R.M. Calculations were carried out by E.G., T.S. and R.M. Samples were prepared by N.Y.-Wa.T., E.G., N.C., F.L., F.R., J.C. and M.-A.N. All authors contributed to writing the manuscript.

Corresponding author

Correspondence to R. Martel.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 2749 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Gaufrès, E., Tang, NW., Lapointe, F. et al. Giant Raman scattering from J-aggregated dyes inside carbon nanotubes for multispectral imaging. Nature Photon 8, 72–78 (2014).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:

This article is cited by


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