Abstract

Single molecule surface enhanced Raman scattering (SM-SERS) is a highly local effect occurring at sharp edges, interparticle junctions and crevices or other geometries with a sharp nanoroughness of plasmonic nanostructures ("hot spots"). The emission of an individual molecule at SM-SERS conditions depends on the local enhancement field of the hot spots, as well as the binding affinity and positioning at a hot spot region. In this regard, the stability of near-field nano-optics at hot spots is critical, particularly in a biological milieu. In this perspective review, we address recent advances in the experimental and theoretical approaches for the successful development of SM-SERS. Significant progress in the understanding of the interaction between the excitation electromagnetic field and the surface plasmon modes at the metallic or metallic/dielectric interface of various curvatures are described. New knowledge on methodological strategies for positioning the analytes for SM-SERS and Raman-assisted SERS or the SERS imaging of live cells has been acquired and displayed. In the framework of the extensive development of SM-SERS as an advancing diagnostic analytical technique, the real-time SERS chemical imaging of intracellular compartments and tracing of individual analytes has been achieved. In this context, we highlight the tremendous potential of SERS chemical imaging as a future prospect in SERS and SM-SERS for the prediction and diagnosis of diseases.

Highlights

  • Less than forty years have passed since the initial discovery of strong Raman signals enhanced at a rough silver surface,[1,2] which quickly gave rise to a new emerging research field – surface enhanced Raman spectroscopy, or in brief: SERS

  • As we review the major advances in the physico-chemical properties of plasmonic nanostructures as a progressive contribution to SERS, this perspective review will focus on describing successful strategies for the SERS detection of individual molecules in single living cells in vivo or in vitro

  • Sustainable plasmonic hot spots can be formed through a successful combination of the geometry and metal dielectric function in complex nanostructures beyond silver or gold

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Summary

Introduction

Less than forty years have passed since the initial discovery of strong Raman signals enhanced at a rough silver surface,[1,2] which quickly gave rise to a new emerging research field – surface enhanced Raman spectroscopy, or in brief: SERS. A typical single molecule SERS spectrum appears as signals randomly fluctuating with time at local positions with the enhancement on the SERS substrate. For this reason, the single molecule SERS phenomenon is controversial, and there has been much debate about its existence over the years. From a fundamental point of view, it is important to understand how the average enhancement factor can contribute to each molecule under SERS conditions on the surface. In this aspect, one of the critical parameters is an analyte adsorption

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