Raman
spectroscopy is a technique that measures the energy of photons generated by
the inelastic scattering of monochromatic excitation photons. A specialized
version of Raman spectroscopy is surface enhanced Raman spectroscopy (SERS). SERS utilizes the unique optical properties
of nanostructured metallic substrates to enhance the intensity of the native
Raman signal of an adsorbed analyte by several orders of magnitude.
Nanostructured substrates composed of noble metals (primarily silver and gold)
are capable of supporting localized surface plasmon resonance (LSPR). LSPR is a
condition induced by the resonant excitation of surface-bound substrate
electrons which generates a highly enhanced localized electromagnetic field.
Raman scattering intensity is governed by the polarizability of the analyte
being interrogated as well as the localized electromagnetic field experienced
by the analyte as a result of laser excitation. LSPR results in a significant
increase in magnitude of the local electromagnetic field near the surface of a
nanostructured substrate. Adsorption of an analyte onto a LSPR-supporting
nanostructured substrate followed by excitation with a laser of appropriate
wavelength leads to an increase in Raman signal intensity by several orders of
magnitude and a significant increase in sensitivity compared to traditional
Raman spectroscopy.
SERS utilizes a
conventional Raman spectrometer and a SERS substrate for sample
preparation. The success of a SERS
measurement is critically dependent on the ability of the nanostructured
substrate to support LSPR. Therefore, the development of robust, reproducible,
and highly-active SERS substrates is an active research topic in the academic
and commercial communities. There are several commercially available SERS
substrates, mostly utilizing a chip-based array of metallic nano-features
fabricated using lithographic techniques common to the semi-conductor
processing industry. There are several other SERS substrate configurations in
use including metallic nanoparticles in solution and thin, nanostructured
metallic films supported on dielectric substrates. Substrate suitability is
dependent upon several application-specific criteria including wavelength of
the Raman excitation source used and adsorption affinity of the analyte for the
substrate. Customized substrates can be fabricated to induce
analyte-specificity by including a molecular recognition moiety such as an
antibody/antigen or an analyte-specific aptamer. While SERS has been reported for decades, it
is an emerging commercial area. A number
of commercial substrates are available and cost is dependent upon substrate
configuration.