Understanding the surface-enhanced Raman spectroscopy “background”

Mahajan, S., Cole, R.M., Speed, J.D., Pelfrey, S.H., Russell, A.E., Bartlett, P.N., Barnett, S.M. and Baumberg, J.J. (2010) Understanding the surface-enhanced Raman spectroscopy “background”. Journal of Physical Chemistry C, 114(16), pp. 7242-7250. (doi: 10.1021/jp907197b)

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Abstract

Even 35 years after the discovery of surface-enhanced Raman spectroscopy (SERS) much remains to be learned about the phenomenon.(1-3) Despite broad consensus on the mechanism of SERS, many features remain poorly understood and in particular much less effort has been put into understanding the continuum emission called the “background” observed in SERS spectra. Here the SERS background is studied systematically on sphere segment void (SSV) plasmonic substrates. We establish the physicochemical dependence of the background on plasmons, the identity of the adsorbate, adsorbate coverage and electrochemical potential. In particular, by exchanging electron-donating and electron-withdrawing adsorbates, we demonstrate predictable modulation of the SERS background. Using these observations, we propose a model for the origin of the SERS background. Finally, we test the proposed model against its predictions for anti-Stokes SERS spectra.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Barnett, Professor Stephen
Authors: Mahajan, S., Cole, R.M., Speed, J.D., Pelfrey, S.H., Russell, A.E., Bartlett, P.N., Barnett, S.M., and Baumberg, J.J.
College/School:College of Science and Engineering > School of Physics and Astronomy
Journal Name:Journal of Physical Chemistry C
Publisher:American Chemical Society
ISSN:1932-7447
ISSN (Online):1932-7455

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