Abstract
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.
-
Tailoring the superradiant and subradiant nature of two coherently coupled quantum emitters
Nature Communications Open Access 26 May 2022
-
Spin-state-dependent electrical conductivity in single-walled carbon nanotubes encapsulating spin-crossover molecules
Nature Communications Open Access 11 March 2021
-
Extended-conjugation π-electron systems in carbon nanotubes
Scientific Reports Open Access 25 May 2018
Access options
Subscribe to this journal
Receive 12 print issues and online access
$209.00 per year
only $17.42 per issue
Rent or buy this article
Prices vary by article type
from$1.95
to$39.95
Prices may be subject to local taxes which are calculated during checkout





References
Le Ru, E. C. & Etchegoin, P. G. Principle of Surface-Enhanced Raman Spectroscopy (Elsevier, 2009).
Aroca, R. Surface-Enhanced Vibrational Spectroscopy (Wiley, 2006).
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).
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).
Moskovits, M. Surface-enhanced spectroscopy. Rev. Mod. Phys. 57, 783–826 (1985).
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).
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).
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).
Gao, J. et al. Electronic interactions between ‘pea’ and ‘pod’: the case of oligothiophenes encapsulated in carbon nanotubes. Small 7, 1807–1815 (2011).
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).
Alvarez, L. et al. Charge transfer evidence between carbon nanotubes and encapsulated conjugated oligomers. J. Phys. Chem. C 115, 11898–11905 (2011).
Yanagi, K., Miyata, Y. & Kataura, H. Highly stabilized β-carotene in carbon nanotubes. Adv. Mater. 18, 437–441 (2006).
Yanagi, K. et al. Light-harvesting function of β-carotene inside carbon nanotubes. Phys. Rev. B 74, 155420 (2006).
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).
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).
Takenobu, T. et al. Stable and controlled amphoteric doping by encapsulation of organic molecules inside carbon nanotubes. Nature Mater. 2, 683–688 (2003).
Garrot, D. et al. Time-resolved investigation of excitation energy transfer in carbon nanotube–porphyrin compounds. J. Phys. Chem. C 115, 23283–23292 (2011).
Huang, C. et al. Spectroscopic properties of nanotube–chromophore hybrids. ACS Nano 5, 7767–7774 (2012).
Bohn, J. E. et al. Estimating the Raman cross sections of single carbon nanotubes. ACS Nano 4, 3466–3470 (2010).
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).
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).
Klar, P. et al. Raman scattering efficiency of graphene. Phys. Rev. B 87, 205435 (2013).
Joh, D. Y. et al. Single-walled carbon nanotubes as excitonic optical wires. Nature Nanotech. 6, 51–56 (2011).
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).
Tian, J. et al. Study of resonance Raman cross section of aqueous β-carotene at low concentrations. Appl. Phys. B 87, 727–730 (2007).
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).
Cabana, J., Lavoie, S. & Martel, R. Thermal chemistry of methylene- and phenyl-functionalized carbon nanotubes. J. Am. Chem. Soc. 132, 1389–1394 (2010).
Chen, Z. et al. Protein microarrays with carbon nanotubes as multicolor Raman labels. Nature Biotechnol. 26, 1285–1292 (2008).
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).
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).
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).
Acknowledgements
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
Contributions
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
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Supplementary information
Supplementary information
Supplementary information (PDF 2749 kb)
Rights 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). https://doi.org/10.1038/nphoton.2013.309
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nphoton.2013.309
This article is cited by
-
Tailoring the superradiant and subradiant nature of two coherently coupled quantum emitters
Nature Communications (2022)
-
Synthesis of Carbon Nanohorns by Inductively Coupled Plasma
Plasma Chemistry and Plasma Processing (2022)
-
Spin-state-dependent electrical conductivity in single-walled carbon nanotubes encapsulating spin-crossover molecules
Nature Communications (2021)
-
Extended-conjugation π-electron systems in carbon nanotubes
Scientific Reports (2018)
-
Preserving π-conjugation in covalently functionalized carbon nanotubes for optoelectronic applications
Nature Communications (2017)