Ag-Nanowire Bundles with Gap Hot Spots Synthesized in Track-Etched Membranes as Effective SERS-Substrates

This paper presents a cost-effective approach for the template-assisted electrodeposition fabrication of substrates for surface-enhanced Raman scattering (SERS) with metal nanowires (NWs) grown in pores of polymer track-etched membranes (TM). This technique allows the synthesis of NWs array with its certain surface density and diameter (from dozen to hundreds of nm). NWs length also may be varied (order of μm) by controlling deposition time. Here we grow vertical Ag-NWs which are leaning towards their nearest neighbors, forming self-assembled bundles whose parameters depend on the NW aspect ratio (length to diameter). We show that in such bundles there are “hot spots” in the nm-gaps between NWs tips. Computer simulations have demonstrated a strong enhancement of the electric field within these hot spots; thus, the Raman signal is markedly amplified for analyte molecules placed directly inside the gaps. We have experimentally proved the potential of this SERS-technique on the example of 4-Mercaptophenylboronic acid (4-MPBA). For 4-MPBA the maximal enhancement of Raman signal was found at NWs length of ~1.6 μm and diameter of ~100 nm. The effect is higher (up to twice) if “wet” substrate is used just immediately after the TM polymer removal so that the tips are brought to lean after analyte exposure. We suggest this new type of nanostructured SERS-substrates as a base of effective sensing of extremely low concentration of analytes.