Ultrahighly Sensitive Surface-Enhanced Raman Spectroscopy Film of Silver Nanoparticles Dispersed in Three Dimensions...

To develop highly sensitive surface-enhanced Raman spectroscopy (SERS) films, various types of aggregated Ag nanowire (NW) and nanoparticle (NP) complex structures were fabricated using anodic aluminum oxide (AAO) templates and thermal evaporation. Aggregated AgNW structures with numerous tapered nanogaps were fabricated via Ag deposition on aggregated thin alumina nanowires of different lengths. AgNP complex structures were obtained by collapsing vertically aligned thin alumina nanowires 1 μm in length and depositing AgNPs on their tops and sides using surface tension during ethanol drying after functionalization. The Raman signal enhancement factors (EFs) of the samples were evaluated by comparing the SERS signal of the thiophenol (TP) self-assembled monolayer (SAM) on the nanostructures with the Raman signal of neat TP. EFs as high as ~2.3 × 10⁷ were obtained for the optimized aggregated AgNW structure (NW length of 1 μm) and ~3.5 × 10⁷ for the optimized AgNP complex structure. The large EF of the AgNP complex film is attributed mainly to the AgNPs dispersed in three dimensions on the sides of the thin alumina nanowires, strongly implying some important, relevant physics yet to be discovered and also a very promising nanostructure scheme for developing ultrahighly sensitive SERS films with EF > 10⁸.