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Shell-isolated nanoparticle-enhanced Raman spectroscopy


Surface-enhanced Raman scattering (SERS) is a powerful spectroscopy technique that can provide non-destructive and ultra-sensitive characterization down to single molecular level, comparable to single-molecule fluorescence spectroscopy1,2,3,4,5,6,7,8,9,10,11,12,13,14,15. However, generally substrates based on metals such as Ag, Au and Cu, either with roughened surfaces or in the form of nanoparticles, are required to realise a substantial SERS effect, and this has severely limited the breadth of practical applications of SERS. A number of approaches have extended the technique to non-traditional substrates14,16,17, most notably tip-enhanced Raman spectroscopy (TERS)18,19,20 where the probed substance (molecule or material surface) can be on a generic substrate and where a nanoscale gold tip above the substrate acts as the Raman signal amplifier. The drawback is that the total Raman scattering signal from the tip area is rather weak, thus limiting TERS studies to molecules with large Raman cross-sections. Here, we report an approach, which we name shell-isolated nanoparticle-enhanced Raman spectroscopy, in which the Raman signal amplification is provided by gold nanoparticles with an ultrathin silica or alumina shell. A monolayer of such nanoparticles is spread as ‘smart dust’ over the surface that is to be probed. The ultrathin coating keeps the nanoparticles from agglomerating, separates them from direct contact with the probed material and allows the nanoparticles to conform to different contours of substrates. High-quality Raman spectra were obtained on various molecules adsorbed at Pt and Au single-crystal surfaces and from Si surfaces with hydrogen monolayers. These measurements and our studies on yeast cells and citrus fruits with pesticide residues illustrate that our method significantly expands the flexibility of SERS for useful applications in the materials and life sciences, as well as for the inspection of food safety, drugs, explosives and environment pollutants.

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Figure 1: The working principles of SHINERS compared to other modes.
Figure 2: Detection of hydrogen adsorption on single-crystal flat surfaces of Pt and Si by SHINERS.
Figure 3: In situ probing of biological structures by SHINERS.
Figure 4: In situ inspection of pesticide residues on food/fruit.


  1. Nie, S. M. & Emory, S. R. Probing single molecules and single nanoparticles by surface enhanced Raman scattering. Science 275, 1102–1106 (1997)

    Article  CAS  Google Scholar 

  2. Kneipp, K. et al. Single molecule detection using surface-enhanced Raman scattering (SERS). Phys. Rev. Lett. 78, 1667–1670 (1997)

    Article  ADS  CAS  Google Scholar 

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

    Article  ADS  CAS  Google Scholar 

  4. Kneipp, K., Moskovits, M. & Kneipp, H. eds. Surface-enhanced Raman Scattering–Physics and Applications (Springer, 2006)

    Book  Google Scholar 

  5. Camden, J. P., Dieringer, J. A. & Van Duyne, R. P. Controlled plasmonic nanostructures for surface-enhanced spectroscopy and sensing. Acc. Chem. Res. 41, 1653–1661 (2008)

    Article  CAS  Google Scholar 

  6. Baumberg, J. J. et al. Angle-resolved surface-enhanced Raman scattering on metallic nanostructured plasmonic crystals. Nano Lett. 5, 2262–2267 (2005)

    Article  ADS  CAS  Google Scholar 

  7. Cao, Y. W. C., Jin, R. C. & Mirkin, C. A. Nanoparticles with Raman spectroscopic fingerprints for DNA and RNA detection. Science 279, 1536–1540 (2002)

    Article  ADS  Google Scholar 

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

    Article  CAS  Google Scholar 

  9. Jain, P. K., Huang, X., El-Sayed, I. H. & El-Sayed, M. A. Noble metals on the nanoscale: optical and photothermal properties and some applications in imaging, sensing, biology, and medicine. Acc. Chem. Res. 41, 1578–1586 (2008)

    Article  CAS  Google Scholar 

  10. Jackson, J. B. & Halas, N. J. Surface-enhanced Raman scattering on tunable plasmonic nanoparticle substrates. Proc. Natl Acad. Sci. USA 101, 17930–17935 (2004)

    Article  ADS  CAS  Google Scholar 

  11. Graham, D., Thompson, D. G., Smith, W. E. & Faulds, K. Control of enhanced Raman scattering using a DNA-based assembly process of dye-coded nanoparticles. Nature Nanotechnol. 3, 548–551 (2008)

    Article  ADS  CAS  Google Scholar 

  12. Qian, X. et al. In vivo tumor targeting and spectroscopic detection with surface-enhanced Raman nanoparticle tags. Nature Nanotechnol. 26, 83–90 (2008)

    Article  CAS  Google Scholar 

  13. Anker, J. N. et al. Biosensing with plasmonic nanosensors. Nature Mater. 7, 442–453 (2008)

    Article  ADS  CAS  Google Scholar 

  14. Tian, Z. Q., Ren, B., Li, J. F. & Yang, Z. L. Expanding generality of surface-enhanced Raman spectroscopy with borrowing SERS activity strategy. Chem. Commun. 34, 3514–3534 (2007)

    Article  Google Scholar 

  15. Nie, S. M. & Zare, R. N. Optical detection of single molecules. Annu. Rev. Biophys. Biomed. 26, 567–596 (1997)

    Article  CAS  Google Scholar 

  16. Park, S., Yang, P., Corredor, P. & Weaver, M. J. Transition metal-coated nanoparticle films: vibrational characterization with surface-enhanced Raman scattering. J. Am. Chem. Soc. 124, 2428–2429 (2002)

    Article  CAS  Google Scholar 

  17. Tian, Z. Q. & Ren, B. Adsorption and reaction at electrochemical interfaces as probed by surface-enhanced Raman spectroscopy. Annu. Rev. Phys. Chem. 55, 197–229 (2004)

    Article  ADS  CAS  Google Scholar 

  18. Stöckle, R. M., Suh, Y. D., Deckert, V. & Zenobi, R. Nanoscale chemical analysis by tip-enhanced Raman spectroscopy. Chem. Phys. Lett. 318, 131–136 (2000)

    Article  ADS  Google Scholar 

  19. Pettinger, B., Ren, B., Picardi, G., Schuster, R. & Ertl, G. Nanoscale probing of adsorbed species by tip-enhanced Raman spectroscopy. Phys. Rev. Lett. 92, 096101–096104 (2004)

    Article  ADS  Google Scholar 

  20. Wu, D. Y., Li, J. F., Ren, B. & Tian, Z. Q. Electrochemical surface-enhanced Raman spectroscopy of nanostructures. Chem. Soc. Rev. 37, 1025–1041 (2008)

    Article  CAS  Google Scholar 

  21. Frens, G. Controlled nucleation for regulation of particle-size in monodisperse gold suspension. Nature 241, 20–22 (1973)

    ADS  CAS  Google Scholar 

  22. Liz-Marzán, L. M., Michael, G. & Mulvaney, P. Synthesis of nanosized gold-silica core-shell particles. Langmuir 12, 4329–4335 (1996)

    Article  Google Scholar 

  23. Lu, Y., Yin, Y., Li, Z. Y. & Xia, Y. Synthesis and self-assembly of Au@SiO2 core-shell colloids. Nano Lett. 2, 785–788 (2002)

    Article  ADS  CAS  Google Scholar 

  24. Mulvaney, S. P., Musick, M. D., Keating, C. D. & Natan, M. J. Glass-coated, analyte-tagged nanoparticles: a new tagging system based on detection with surface-enhanced Raman scattering. Langmuir 19, 4784–4790 (2003)

    Article  CAS  Google Scholar 

  25. Smith, W. E. Practical understanding and use of surface enhanced Raman scattering/surface enhanced resonance Raman scattering in chemical and biological analysis. Chem. Soc. Rev. 37, 955–964 (2008)

    Article  CAS  Google Scholar 

  26. Sherry, L. J. et al. Localized surface plasmon resonance spectroscopy of single silver nanocubes. Nano Lett. 5, 2034–2038 (2005)

    Article  ADS  CAS  Google Scholar 

  27. Ren, B. et al. In situ monitoring of Raman scattering and photoluminescence from silicon surfaces in HF aqueous solutions. Appl. Phys. Lett. 72, 933–935 (1998)

    Article  ADS  CAS  Google Scholar 

  28. Sujith, A. et al. Surface enhanced Raman scattering analyses of individual silver nanoaggregates on living single yeast cell wall. Appl. Phys. Lett. 92, 103901 (2008)

    Article  ADS  Google Scholar 

  29. Schulte, F., Mader, J., Kroh, L. W., Panne, U. & Kneipp, J. Characterization of pollen carotenoids with in situ and high-performance thin-layer chromatography supported resonant Raman spectroscopy. Anal. Chem. 81, 8426–8433 (2009)

    Article  CAS  Google Scholar 

  30. Lee, D. et al. Quantitative analysis of methyl parathion pesticides in a polydimethylsiloxane microfluidic channel using confocal surface-enhanced Raman spectroscopy. Appl. Spectrosc. 60, 373–377 (2006)

    Article  ADS  Google Scholar 

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We thank P. Bartlett for suggestions and editing of the English while writing the paper. We thank R. Zare, N. Zheng, B. Mao, U. K. Sur and L. Yang for discussions. We also thank Y. Yu, Y. Wu, M. Zhuang, X. Wang and A. Wang for assistance in experiments. This work was supported by MOST, China (2009CB930703, 2007DFC40440 and 2007CB935603), the NSF of China (20620130427 and 20533040), the BES DOE (DE-FG02-07ER46394) and the US NSF (DMS 0706436, CMMI 0403671).

Author Contributions Z.Q.T., Z.L.W., J.F.L. and B.R. conceived and designed the experiments, analysed the results and participated in writing the manuscript. J.F.L., Y.F.H., Y.D., S.B.L., X.S.Z., F.R.F., W.Z. and Z.Y.Z. performed the experiments and analysed the results. Z.L.Y. and D.Y.W contributed to theoretical calculations.

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Correspondence to Zhong Lin Wang or Zhong Qun Tian.

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This file contains Supplementary Information sections S1-S10 including Supplementary Figures S1-S14 with legends, and Supplementary References. (PDF 786 kb)

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Li, J., Huang, Y., Ding, Y. et al. Shell-isolated nanoparticle-enhanced Raman spectroscopy. Nature 464, 392–395 (2010).

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