Title

Correlating Molecular Surface Coverage and Solution-Phase Nanoparticle Concentration to Surface-Enhanced Raman Scattering Intensities

Document Type

Article

Publication Date

2011

Abstract

Control over the composition, shape, size, stability, and local dielectric environment of solution-phase metallic substrates is vital to consistent surface-enhanced Raman scattering (SERS) signals. Because of their inherent instability, solution-phase nanoparticles can undergo uncontrolled aggregation when target molecules are added. Here, we demonstrate that both molecular surface coverage of the Raman active molecule, 2-naphthalenethiol (2-NT), and nanoparticle concentration are critical parameters for obtaining reproducible SERS signals using solution-phase gold nanoparticles. Both gold nanoparticle and 2-naphthalenethiol concentrations are varied, and the extinction of the nanoparticle substrate and the SERS intensity of the target molecule are monitored as a function of time. These results indicate that extinction and SERS spectral intensities increase predictably below full monolayer surface coverage. When excess molecules are added, uncontrolled and irreproducible nanoparticle aggregation leads to optimal overlap between the plasmonic properties of the nanoparticles and the SERS excitation wavelength. Importantly, this is the first report which correlates solution-phase nanoparticle concentration and stability to molecular surface coverage for simultaneous localized surface plasmon resonance (LSPR) and SERS spectroscopic measurements. As a result, these data should facilitate the experimental design and use of solution-phase SERS substrates for more predictable molecular detection.

Published In

The Journal of Physical Chemistry C

Volume

115

Issue

38

Pages

18511-18517

DOI

10.1021/jp206243y

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