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Surface analysis using shell-isolated nanoparticle-enhanced Raman spectroscopy

Nature Protocols volume 8, pages 52–65 (2013)Cite this article

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Abstract

Surface-enhanced Raman scattering (SERS) is a powerful fingerprint vibrational spectroscopy with a single-molecule detection limit, but its applications are generally restricted to 'free-electron–like' metal substrates such as Au, Ag and Cu nanostructures. We have invented a shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) technique, using Au-core silica-shell nanoparticles (Au@SiO2 NPs), which makes SERS universally applicable to surfaces with any composition and any morphology. This protocol describes how to prepare shell-isolated nanoparticles (SHINs) with different well-controlled core sizes (55 and 120 nm), shapes (nanospheres, nanorods and nanocubes) and shell thicknesses (1–20 nm). It then describes how to apply SHINs to Pt and Au single-crystal surfaces with different facets in an electrochemical environment, on Si wafer surfaces adsorbed with hydrogen, on ZnO nanorods, and on living bacteria and fruit. With this method, SHINs can be prepared for use in ∼3 h, and each subsequent procedure for SHINERS measurement requires 1–2 h.

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Figure 1
Figure 2: HR-TEM images of Au@SiO2 NPs.
Figure 3: Images of 120-nm Au@SiO2 SHINs.
Figure 4: HR-TEM images of nanorod and nanocube SHINs.
Figure 5: Correlation of the SHINERS intensity and the shell thickness.
Figure 6: Pinhole test for SHINs.
Figure 7: Stability comparison of SHINs and bare Au NPs.
Figure 8: Schematic illustration of our homemade spectroelectrochemical cell.
Figure 9: 3D-FDTD modeling of four SHINs on an Au substrate.

Change history

  • 02 January 2013

     In the version of this article initially published online, the Acknowledgments statement was incomplete. It should also have included an acknowledgment of funding from the National Natural Science Foundation of China (NSFC; nos. 21033007, 21021002 and 20825313). The error has been corrected in all versions of the article.

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Acknowledgements

We thank N.F. Zheng for thoughtful discussions. This work was supported by the Ministry of Science and Technology (MOST) of China (2011YQ030124, 2010IM040100 and 2009CB930703), and by the National Natural Science Foundation of China (NSFC) (21033007, 21021002 and 20825313).

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Author notes

  1. Jian Feng Li and Xiang Dong Tian: These authors contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China

    Jian Feng Li, Xiang Dong Tian, Song Bo Li, Jason R Anema, Zhi Lin Yang, Yuan Fei Wu, Yong Ming Zeng, Qi Zhen Chen, Bin Ren & Zhong Qun Tian

  2. Canadian Conservation Institute, Ottawa, Ontario, Canada

    Jason R Anema

  3. School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia, USA

    Yong Ding & Zhong Lin Wang

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Contributions

Z.Q.T., Z.L.W., J.F.L. and B.R. conceived and designed the experiments, analyzed the results and participated in writing the manuscript. J.F.L., X.D.T., S.B.L., J.R.A., Y.D., Y.F.W., Q.Z.C. and Y.M.Z. performed the experiments and analyzed the results. Z.L.Y. contributed the theoretical calculations.

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Correspondence to Zhong Lin Wang or Zhong Qun Tian.

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Supplementary information

Supplementary Figure 1

Detection of hydrogen adsorption on Pt single-crystal surface. SHINERS spectra of hydrogen adsorbed on Pt(111) at -1.2 V (a), at -1.6 V (b), at -1.9 V (c), without Au@SiO2 NPs at -1.9 V (d), and with the thicker-shell NPs at -1.9 V (e). (PDF 216 kb)

Supplementary Figure 2

Detection of hydrogen adsorption on Si single-crystal surface. SHINERS spectra obtained from Si(111) treated with (a) sulphuric acid, (b) a 30% HF solution, and (c) an oxygen plasma. (PDF 214 kb)

Supplementary Figure 3

Comparison of the adsorption of SCN− on Au single-crystal surface with different facets. SHINERS spectra of SCN− adsorbed on Au(100) (red curves) and Au(111) (black curves) at 0.0 V. (PDF 211 kb)

Supplementary Figure 4

SERS or SHINERS spectra of PATP molecules in different sandwich configurations. (a) Au/PATP/Au NPs, (b) ZnO nanorods/PATP/Au NPs, (c) Au/PATP/Au@SiO2 NPs, and (d) ZnO nanorods/PATP/Au@SiO2 NPs. (PDF 224 kb)

Supplementary Figure 5

SERS or SHINERS study of CO adsorbed on Pt single-crystal surface. The SERS spectrum of CO on Pt(111) at 0.0 V using bare Au NPs (top), and the SHINERS spectrum of CO on Pt(111) at 0.0 V using Au@SiO2 NPs (bottom). (PDF 212 kb)

Supplementary Figure 6

In-situ probing biology structures by SHINERS. (a, b, c) SHINERS spectra obtained from different locations on a sample consisting of yeast cells incubated with Au@SiO2 NPs on a quartz slide. (d) The spectrum of Au@SiO2 NPs, but without yeast cells, on a quartz slide. (e) An ordinary Raman spectrum of yeast cells on a quartz slide. The peaks marked with red asterisks are related to mannoproteins. (PDF 225 kb)

Supplementary Figure 7

In situ detection of a pesticide residue on an orange skin. The Raman signals were collected using a Raman microscope (A) and a portable Raman spectrometer (B). The spectra shown were obtained from a clean orange skin (a), an orange skin contaminated with parathion (b), and an orange skin contaminated with parathion and then modified by addition of Au@SiO2 NPs (c). The Raman spectrum of solid parathion is provided for comparison (d). (PDF 225 kb)

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Li, J., Tian, X., Li, S. et al. Surface analysis using shell-isolated nanoparticle-enhanced Raman spectroscopy. Nat Protoc 8, 52–65 (2013). https://doi.org/10.1038/nprot.2012.141

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