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Understanding the surface-enhanced Raman spectroscopy “background”

Understanding the surface-enhanced Raman spectroscopy “background”
Understanding the surface-enhanced Raman spectroscopy “background”
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.
optical, electron, mass spectroscopy, other related properties
1932-7447
7242-7250
Mahajan, Sumeet
b131f40a-479e-4432-b662-19d60d4069e9
Cole, Robin M.
29fa4536-7e68-43ee-acfa-673f0768af9c
Speed, Jonathon
e6b5c806-9b04-4045-8061-3bb380e47808
Pelfrey, Suzanne H.
650d43ac-e77f-49ad-9b04-8ed732159c97
Russell, Andrea E.
b6b7c748-efc1-4d5d-8a7a-8e4b69396169
Bartlett, Philip N.
d99446db-a59d-4f89-96eb-f64b5d8bb075
Barnett, Stephen M.
138bdd7f-b0ec-4d93-b113-7bb5be7faabd
Baumberg, Jeremy J.
51423b5f-bdb8-4851-8d50-472253ceb12c
Mahajan, Sumeet
b131f40a-479e-4432-b662-19d60d4069e9
Cole, Robin M.
29fa4536-7e68-43ee-acfa-673f0768af9c
Speed, Jonathon
e6b5c806-9b04-4045-8061-3bb380e47808
Pelfrey, Suzanne H.
650d43ac-e77f-49ad-9b04-8ed732159c97
Russell, Andrea E.
b6b7c748-efc1-4d5d-8a7a-8e4b69396169
Bartlett, Philip N.
d99446db-a59d-4f89-96eb-f64b5d8bb075
Barnett, Stephen M.
138bdd7f-b0ec-4d93-b113-7bb5be7faabd
Baumberg, Jeremy J.
51423b5f-bdb8-4851-8d50-472253ceb12c

Mahajan, Sumeet, Cole, Robin M., Speed, Jonathon, Pelfrey, Suzanne H., Russell, Andrea E., Bartlett, Philip N., Barnett, Stephen M. and Baumberg, Jeremy J. (2009) Understanding the surface-enhanced Raman spectroscopy “background”. The Journal of Physical Chemistry C, 114 (16), 7242-7250. (doi:10.1021/jp907197b).

Record type: Article

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.

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More information

e-pub ahead of print date: 16 December 2009
Published date: 16 December 2009
Additional Information: Funded by EPSRC: Soft NanoPhotonics Programme Grant (sNaP) (EP/G060649/1)
Keywords: optical, electron, mass spectroscopy, other related properties
Organisations: Chemistry, Physics & Astronomy, Electronics & Computer Science, Electrochemistry, Molecular Diagnostics & Thereputics

Identifiers

Local EPrints ID: 175197
URI: http://eprints.soton.ac.uk/id/eprint/175197
ISSN: 1932-7447
PURE UUID: c31cab3f-b791-4544-a77c-65ee5ecad493
ORCID for Sumeet Mahajan: ORCID iD orcid.org/0000-0001-8923-6666
ORCID for Andrea E. Russell: ORCID iD orcid.org/0000-0002-8382-6443
ORCID for Philip N. Bartlett: ORCID iD orcid.org/0000-0002-7300-6900

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Date deposited: 09 Mar 2011 15:03
Last modified: 15 Mar 2024 02:44

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Contributors

Author: Sumeet Mahajan ORCID iD
Author: Robin M. Cole
Author: Jonathon Speed
Author: Suzanne H. Pelfrey
Author: Stephen M. Barnett
Author: Jeremy J. Baumberg

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