Zeptomolar detection of 4-aminothiophenol by SERS using silver nanodendrites decorated with gold nanoparticles

In the present work, we report a simple, fast, reproducible and cheap methodology for SERS substrate fabrication of silver dendritic nanostructures (prepared by electrodeposition) decorated with gold nanospheres by electrophoretic deposition. This is the first report where a metal dendritic nanostructure has been decorated with another type of metal nanoparticles by this technique. The decorated nanostructures were used directly as SERS substrate using 4-aminothiophenol (4-ATP) as analyte. The objective of the decoration is to create more hot-spots in order to detect the analyte in a lower concentration. Decorated nanodendrites had a detection limit one million times lower than bare silver nanodendrites and all the substrates showed an increase in the Raman intensity at concentrations below 1 nM; because this concentration corresponds to the threshold for the formation of a monolayer resulting in a triple mechanism of intensity increase, namely electric field, chemical factor and hot-spots. 4-ATP was detected in zeptomolar concentration, which is below 1 ppq, corresponding to an analytical enhancement factor in the order of 10¹⁵.