Journal
JOURNAL OF RAMAN SPECTROSCOPY
Volume 43, Issue 2, Pages 173-180Publisher
WILEY
DOI: 10.1002/jrs.3021
Keywords
tip-enhanced Raman spectroscopy; tip fabrication; mechanism of enhancement; top illumination; hematin
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Funding
- Australian Research Council [DP0664012, DP0878464]
- Monash University
- Engineering and Physical Sciences Research Council [EP/E500145/1] Funding Source: researchfish
- Australian Research Council [DP0664012, DP0878464] Funding Source: Australian Research Council
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Tip-enhanced Raman scattering (TERS) spectroscopy is a promising technique for nanoscale chemical analysis. However, there are several challenges preventing widespread application of this technology, including reproducible fabrication of efficient TERS probes. These problems reflect a lack of clear understanding of the origins of, and the parameters influencing TERS. It is believed that the coating characteristics at the apex of the tip have a major effect on the near-field optical enhancement and thus the TERS activity of a metalized probe. Here we show that the aspect ratio of the tip can play a significant role in the efficiency of TERS probes. We argue that the electrostatic field arising from the lightning-rod effect has a substantial role in the observed TERS effect. This argument is supported by edge-enhanced Raman scattering which is shown for a noble metal film. Furthermore, it is reported that an associated tip-surface-enhanced Raman scattering effect can be achieved by using a TERS-inactive metalized probe on a surface-enhanced Raman spectroscopy-inactive roughened surface. This observation can be explained by an interparticle enhancement of the electromagnetic field. Copyright (C) 2011 John Wiley & Sons, Ltd.
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