Abstract

In the near future, single-molecule surface-enhanced Raman spectroscopy (SERS) is expected to expand the family of popular analytical tools for single-molecule characterization. We provide a roadmap for achieving single molecule SERS through different enhancement strategies for diverse applications. We introduce some characteristic features related to single-molecule SERS, such as Raman enhancement factor, intensity fluctuation, and data analysis. We then review recent strategies for enhancing the Raman signal intensities of single molecules, including electromagnetic enhancement, chemical enhancement, and resonance enhancement strategies. To demonstrate the utility of single-molecule SERS in practical applications, we present several examples of its use in various fields, including catalysis, imaging, and nanoelectronics. Finally, we specify current challenges in the development of single-molecule SERS and propose corresponding solutions.

Highlights

  • Raman spectroscopy is a powerful analytical tool that probes vibrational fingerprints of molecules and enables high-content analysis of composite systems of physical, chemical, and biological interests by virtue of its inherent specificity

  • We have provided a roadmap for achieving singlemolecule SERS through different enhancement strategies for diverse applications

  • Starting from basic concepts and mechanisms of SERS, we introduced some characteristic features related to single-molecule SERS, such as Raman enhancement factor, intensity fluctuation, and data analysis

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Summary

Introduction

Raman spectroscopy is a powerful analytical tool that probes vibrational fingerprints of molecules and enables high-content analysis of composite systems of physical, chemical, and biological interests by virtue of its inherent specificity. In addition to noble metals, two-dimensional (2-D) materials including graphene, MoS2, and h-BN as well as semiconducting metal oxides including TiO2, CuO, and Ta2O5 have been explored for SERS applications by virtue of charge transfer resonance.[6,20,21,22,23,24] A state-of-the-art chemical enhancement factor up to ∼107 has been demonstrated recently.[25] such an enhancement factor achieved by the CM is still much smaller than that of the EM counterpart (above ∼1010),[26] the CM offers a parallel path to enhance Raman signals, which enables synergic Raman enhancement by combination of EM and CM and relaxes the extreme requirement of electromagnetic-field enhancement for single-molecule SERS.

Single-Molecule SERS
Enhancement Factor of Single-Molecule SERS
Experimental Evidences of Single-Molecule SERS
Data Analysis of Single-Molecule SERS
Strategies for Single-Molecule SERS
Electromagnetic Enhancement
Plasmonic nanogaps with precise size control
Plasmonic sharp tips
Plasmonic complex nanostructures
Plasmonic substrates that enable delivery of single molecules to hotspots
Chemical Enhancement
Resonance Enhancement
Other Potential Strategies
Process Monitoring of Chemical Catalysis
Imaging of Vibrational Modes
Observation of Charge Transfer in Nanoelectronics
Combination with Other Techniques
Challenges for Single-Molecule SERS
Findings
Summary
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