Fundamental understanding and applications of plasmon-enhanced Raman spectroscopy

Abstract

Plasmon-enhanced Raman spectroscopy (PERS), including surface-enhanced Raman spectroscopy, shell-isolated nanoparticle-enhanced Raman spectroscopy and tip-enhanced Raman spectroscopy, has witnessed substantial development over the past 20 years. These techniques can provide fingerprint information on target materials with sensitivities down to the single-molecule level and with sufficient spatial resolution to observe individual vibrational modes. PERS has thus found applications in diverse areas, ranging from bioanalysis to materials characterization. In this Technical Review, we survey the fundamental principles, advantages and limitations of using localized surface plasmon resonance to enhance the Raman signal in PERS. We discuss the issues that influence the sensitivity and interpretation of PERS results and provide an overview of state-of-the-art PERS applications in materials characterization, bioanalysis and the study of surfaces and interfaces. We also troubleshoot common experimental issues, largely based on our own experience. Finally, we conclude by examining future directions and issues to be addressed for the further development of PERS techniques.

Key points

  • Plasmon-enhanced Raman spectroscopy (PERS) can provide fingerprint information with single-molecule sensitivity and subnanometre spatial resolution for various targets, including small molecules, biomolecules, living cells and 2D materials.

  • The Raman signal in PERS is mainly enhanced through localized surface plasmon resonance (LSPR) of nanostructures, and vibrational modes appearing at LSPR wavelengths with different scattering strengths may experience different enhancements.

  • Although chemical enhancement is generally weak, it significantly changes the relative intensities of the Raman peaks of different vibrational modes.

  • Plasmonic enhancement requires the design of appropriate nanostructures, with LSPR showing optimal enhancement at the excitation wavelength under the detection configuration.

  • Target species need to be located or selectively trapped in the hot spots formed in the plasmonic nanogaps to achieve the highest sensitivity; <1% of a surface contributes to 80% of the signal.

  • Challenges in the field include realizing single-molecule detection in complex matrices, avoiding interference from impurities and, for tip-enhanced Raman spectroscopy, achieving a high spatial resolution by using the tip alone without electromagnetic coupling with a substrate.

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Fig. 1: Working configurations of PERS techniques.
Fig. 2: Engineering SERS substrates.
Fig. 3: Issues in the practical use of plasmon-enhanced Raman spectroscopy.
Fig. 4: Application of plasmon-enhanced Raman spectroscopy for the analysis of surfaces and interfaces.
Fig. 5: Application of TERS for nanoscale and atomic-scale materials characterization.
Fig. 6: Application of plasmon-enhanced Raman spectroscopy for bioanalysis.

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Acknowledgements

The authors thank S. Matthew for help in editing the manuscript before submission. The authors acknowledge financial support from the National Natural Science Foundation of China (grant nos 21633005, 21790354 and 21711530704), the Ministry of Science and Technology of China (grant no. 2016YFA0200601), the China Postdoctoral Science Foundation (grant no. 2017M622062) and the Natural Science Foundation of Fujian Province (grant no. 2016J05046).

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B.R. and X.W. conceived the idea for this article. All authors have read, discussed and contributed to the writing of the manuscript.

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Glossary

Optical antenna

A device, typically made of a metal nanostructure or nanoparticles, that can efficiently couple the energy of free-space electromagnetic waves into a subwavelength region.

Optical cavity

An arrangement of mirrors that forms a standing wave for light of certain frequency, owing to the constructive and destructive interference of multiple reflected light.

Raman reporter molecules

Molecules with a large Raman cross section that can be used to report the presence of target molecules with small Raman cross sections, or molecules that are sensitive to the environment and can be used to monitor environmental changes.

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Wang, X., Huang, S., Hu, S. et al. Fundamental understanding and applications of plasmon-enhanced Raman spectroscopy. Nat Rev Phys 2, 253–271 (2020). https://doi.org/10.1038/s42254-020-0171-y

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