Enhancement Mechanisms and Theory of SERS

This chapter starts with a brief introduction to basic Raman Spectroscopy,

its strengths and bottlenecks leading to ineffective utilization of the technique in its

conventional form. Further, the basic principle of Surface Enhanced Raman

Spectroscopy (SERS) has been discussed along with its development as a vibrational

spectroscopic tool of analytical importance. The milestones related to the development

of new methods in SERS have also been covered. The major focus of the chapter is to

describe the enhancement mechanisms responsible for magnificent enhancement

obtained in SERS as compared to normal Raman Spectroscopy. Out of various

mechanisms, the electromagnetic (EM) mechanism has been considered to play the

most significant role in enhancement. Localized Surface Plasmon Resonance (LSPR) is

chiefly responsible for the whole EM enhancement leading to E4 enhancement and

therefore, it has been discussed in detail. Other mechanisms like chemical and

electronic enhancement mechanisms have also been discussed extensively. The

dependence of SERS on various factors like substrate, excitation wavelength, size and

shape of nanoparticles, etc., has been explained with emphasis on the reported data

followed by analysis. Two photon excited SERS has been presented as a special class

of SERS. Towards the end, the application of SERS to achieve the ultimate limit of

detection by probing single molecules has been emphasised. In this context, Hot spots,

the heterogeneous nanoregions causing extremely large enhancements and their various

generations have been presented along with preliminary theoretical and experimental

results.

Keywords: Analyte, Anti-Stokes, Enhancement Factor, Enhancement Mechanism, Excitation Wavelength, Nanoparticle, Raman Scattering, Resonance, SERS Intensity, SERS Spectrum, Single Molecule etc.

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