Sub-100 nm anisotropic gold nanoparticles as surface-enhanced Raman spectroscopy substrates

This study describes a reliable preparation of relatively small Ag/Au-based anisotropic nanostructures possessing tunable absorption bands and their use as surface-enhanced Raman spectroscopy (SERS) substrates. These Au nanostructures were prepared via the seed growth process of small Ag-core–Au-shell-type nanoparticles that were obtained by the subsequent reduction of Ag and Au ions by NaBH₄ and L-ascorbic acid at room temperature. The presence of Ag during the transformation process of the Ag–Au core–shell nanoparticles under light irradiation led to the formation of various small anisotropic Au nanoparticles which clearly exhibited different structural and optical properties from those of nanoparticles prepared from typical Ag–Au alloy or bare Ag or Au seeds. As the optimal size of Au-based substrates for SERS applications was reported to be below 100 nm in diameter under a constant concentration, we tested our moderately small anisotropic nanoparticles (∼55 nm in diameter) as a SERS substrate to examine the signal enhancement of 4-nitrobenzenethiol. These nanoparticles exhibited a greatly increased SERS response compared to those of similar sizes of uniform Ag and Au nanoparticles, presumably because of the increased surface area due to the nanoparticles' anisotropic nature (i.e., chemical effect) and partial overlap of their absorption bands with the SERS excitation wavelength (i.e., electromagnetic effect). In addition, these nanoparticles have shown a suitable stability to prevent significant SERS signal fluctuations caused by unpredictable aggregations. Due to our simple synthetic and modification approaches, relatively small Au-based anisotropic nanostructures can be easily designed to serve as attractive SERS templates. (paper)