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Science. 2008 Jul 18;321(5887):388-92. doi: 10.1126/science.1159499. Epub 2008 Jun 26.

Measurement of the distribution of site enhancements in surface-enhanced Raman scattering.

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  • 1School of Chemical Sciences, University of Illinois at Urbana-Champaign, Urbana, IL 61801, USA.


On nanotextured noble-metal surfaces, surface-enhanced Raman scattering (SERS) is observed, where Raman scattering is enhanced by a factor, G, that is frequently about one million, but underlying the factor G is a broad distribution of local enhancement factors, eta. We have measured this distribution for benzenethiolate molecules on a 330-nanometer silver-coated nanosphere lattice using incident light of wavelength 532 nanometers. A series of laser pulses with increasing electric fields burned away molecules at sites with progressively decreasing electromagnetic enhancement factors. The enhancement distribution P(eta)deta was found to be a power law proportional to (eta)(-1.75), with minimum and maximum values of 2.8 x 10(4) and 4.1 x 10(10), respectively. The hottest sites (eta >10(9)) account for just 63 in 1,000,000 of the total but contribute 24% to the overall SERS intensity.

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