Letter | Published:

Pressure-assisted tip-enhanced Raman imaging at a resolution of a few nanometres

Nature Photonics volume 3, pages 473477 (2009) | Download Citation

Subjects

Abstract

Scanning probe microscopy methods1,2 can image samples with extremely high resolutions, opening up a wide range of applications in physics3, chemistry4 and biology5. However, these passive techniques, which trace the sample surface softly, give indirect topographic information. Here, we show an active imaging technique that has the potential to achieve optically a molecular resolution by directly interacting and perturbing the sample molecules. This technique makes use of an external pressure, applied selectively on a nanometric volume of the sample through the apex of a sharp nanotip, to obtain a local distortion of only those molecules that are pressurized. The vibrational frequencies of these molecules are distinctly different from those of unpressurized molecules. By sensing this difference, our active microscopic technique can achieve extremely high resolution. Using an isolated single-walled carbon nanotube and a two-dimensional adenine nanocrystal, we demonstrate a spatial resolution of 4 nm.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

References

  1. 1.

    , , & 7  ×  7 reconstruction on Si (111) resolved in real space. Phys. Rev. Lett. 50, 120–123 (1982).

  2. 2.

    , & Atomic force microscope. Phys. Rev. Lett. 56, 930–933 (1986).

  3. 3.

    & Positioning single atoms with a scanning tunneling microscope. Nature 344, 524–526 (1990).

  4. 4.

    et al. Alignment and sensitive detection of DNA by a moving interface. Science 265, 2096–2098 (1994).

  5. 5.

    et al. Chemical identification of individual surface atoms by atomic force microscopy. Nature 446, 64–67 (2007).

  6. 6.

    , , , & STED microscopy reveals that synaptotagmin remains clustered after synaptic vesicle exocytosis. Nature 440, 935–939 (2006).

  7. 7.

    et al. Imaging intracellular fluorescent proteins at nanometer resolution. Science 313, 1642–1645 (2006).

  8. 8.

    , , & Three-dimensional super-resolution imaging by stochastic optical reconstruction microscopy. Science 319, 810–813 (2008).

  9. 9.

    , & Optical stethoscopy: image recording with resolution λ/20. Appl. Phys. Lett. 44, 651–653 (1984).

  10. 10.

    , & Apertureless near-eld optical microscope. Appl. Phys. Lett. 65, 1623–1625 (1994).

  11. 11.

    , & Near-field optical microscope based on local perturbation of a diffraction spot. Opt. Lett. 20, 1924–1926 (1995).

  12. 12.

    , , & Metallized tip amplification of near-field Raman scattering. Opt. Commun. 183, 333–336 (2000).

  13. 13.

    , , & Nanoscale chemical analysis by tip-enhanced Raman spectroscopy. Chem. Phys. Lett. 318, 131–136 (2000).

  14. 14.

    Locally enhanced Raman spectroscopy with an atomic force microscope. Appl. Phys. Lett. 76, 3130–3132 (2000).

  15. 15.

    , & Near-field fluorescence microscopy based on two-photon excitation with metal tips. Phys. Rev. Lett. 82, 4014–4017 (1999).

  16. 16.

    , , & Single molecule tip-enhanced Raman spectroscopy with silver tips. J. Phys. Chem. C 111, 1733–1738 (2007).

  17. 17.

    , , & Scanning probe Raman spectroscopy with single molecule sensitivity. Phys. Rev. B 73, 193406 (2006).

  18. 18.

    & Tip-enhanced Raman spectroscopy and microscopy on single dye molecules with 15 nm resolution. Phys. Rev. Lett. 100, 236101 (2008).

  19. 19.

    , , , & Tip-enhanced coherent anti-Stokes Raman scattering for vibrational nano-imaging. Phys. Rev. Lett. 92, 220801 (2004).

  20. 20.

    , , & High-resolution near-field Raman microscopy of single-walled carbon nanotubes. Phys. Rev. Lett. 90, 095503 (2003).

  21. 21.

    , , & Nanoscale vibrational analysis of single-walled carbon nanotubes. J. Am. Chem. Soc. 127, 2533–2537 (2005).

  22. 22.

    , & Phonon-enhanced light–matter interaction at the nanometre scale. Nature 418, 159–162 (2002).

  23. 23.

    & Material-specific mapping of metal/semiconductor/dielectric nanosystems at 10-nm resolution by backscattering near-field optical microscopy. Appl. Phys. Lett. 80, 25–27 (2002).

  24. 24.

    et al. Temporal uctuation of tip-enhanced Raman spectra of adenine molecules. J. Phys. Chem. C 111, 9460–9464 (2007).

  25. 25.

    , , , & Near-eld Raman scattering investigation of tip effects on C60 molecules. Phys. Rev. B 73, 045416 (2006).

  26. 26.

    , & Nanoscale uniaxial pressure effect of a carbon nanotube bundle on tip-enhanced near field Raman spectra. Nano Lett. 6, 1269–1273 (2006).

  27. 27.

    et al. Subnanometric near-field Raman investigation in the vicinity of the metallic nanostructure. Phys. Rev. Lett. 102, 186101 (2009).

  28. 28.

    , & Phonon eigenvectors of chiral nanotubes. Phys. Rev. B 64, 195416 (2001).

  29. 29.

    & Advanced Mechanics of Materials (John Wiley & Sons, 1985).

  30. 30.

    et al. Size control of metal nanoparticle catalysts for the gas-phase synthesis of single-walled carbon nanotubes. J. Phys. Chem. B 109, 10647–10652 (2005).

  31. 31.

    et al. Supermolecular catalysts for the gas-phase synthesis of single-walled carbon nanotubes. J. Phys. Chem. B 110, 5849–5853 (2006).

Download references

Acknowledgements

The authors would like to thank Y. Inouye (Osaka University, Japan) for fruitful discussions, S. Fujii and F. Futamatsu (Osaka University, Japan) for their valuable help during some of the experiments, and T. Saito (Advanced Industrial Science and Technology, Japan) for supplying the high-quality SWNTs used in the present study. This research was financially supported by the Core Research for Educational Science and Technology (CREST) project of Japan Science and Technology Corporation.

Author information

Affiliations

  1. Department of Applied Physics, Osaka University, Suita, Osaka 565-0871, Japan

    • Taka-aki Yano
    • , Prabhat Verma
    • , Taro Ichimura
    •  & Satoshi Kawata
  2. Department of Frontier Biosciences, Osaka University, Suita, Osaka 565-0871, Japan

    • Prabhat Verma
  3. Frontier Research Center, Osaka University, Suita, Osaka 565-0871, Japan

    • Yuika Saito
  4. Nanophotonics Laboratory, RIKEN, Wako, Saitama 351-0198, Japan

    • Satoshi Kawata

Authors

  1. Search for Taka-aki Yano in:

  2. Search for Prabhat Verma in:

  3. Search for Yuika Saito in:

  4. Search for Taro Ichimura in:

  5. Search for Satoshi Kawata in:

Corresponding authors

Correspondence to Taka-aki Yano or Prabhat Verma.

Supplementary information

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/nphoton.2009.74

Further reading