High-Throughput Surface-Enhanced Raman Scattering for Screening Chemical Sensor Candidates Enabled by Bipolar Electrochemistry.

Abstract

A variety of hydrothermal or electrochemical methods have been explored to prepare noble metal nanostructures as surface-enhanced Raman scattering (SERS) substrates. However, most of those metallic nanoarrays are structurally homogeneous, which makes it laborious to select the high-performance substrates for particular Raman sensing purposes. Here, a high-throughput SERS imaging strategy is demonstrated for the first time for screening chemical sensors with sub-nanomolar sensitivities. Bipolar electrochemistry was applied to generate Au or Au-Ag gradient nanoarrays with diverse chemical compositions, morphologies, and particle dimensions ranging from several nanometers to micrometers. The selected "hot-spots" on the Au-Ag alloy nanoarray exhibited a 660-fold enhancement in SERS intensity compared to those on the pure Au gradient nanoarray. The SERS screening of 4-aminothiophenol, 4-nitrothiophenol, and 4-mercaptobenzoic acid was carried out that provided a limit of detection (LOD) between 1 and 5 pM. The distinctive LODs among three thiophenolic Raman probes are ascribed to the differences in the affinity of the probe to the alloy, orientation of the metal-ligand monolayer, or plasmonic environment of the nanoarray surface. As a continuous, rapid, and cost-effective manner to fabricate transitional nanostructures and screen out SERS responsive sites, this method not only facilitates controllable synthesis of noble metal nanoarrays but has the potential to provide an alternative tool for ultrasensitive chemical sensing on a wide range of bimetallic substrates.