Gap-tunable Ag-nanorod arrays on alumina nanotip arrays as effective SERS substrates

Abstract

Large area arrays of length-tunable alumina nanotips on the joints of hexagonally patterned conical-pores in an anodic aluminum oxide (AAO) template are achieved via a repeated process of anodizing Al foil for pore growth downwards and phosphoric acid etching for pore-widening. By top-view sputtering Ag on the alumina nanotip arrays, hexagonally patterned arrays of Ag-nanorods (Ag-NRs) on the alumina nanotips and uniformly distributed Ag-nanoparticles (Ag-NPs) on the upper rim of the inner surface of the conical-pores are obtained and they exhibit strong surface-enhanced Raman scattering (SERS) activity due to the high density of sub-10 nm gaps between the nearest neighboring Ag-NRs and between the adjacent Ag-NPs. The resultant nanostructures are tailored to attain an optimal SERS enhancement factor of ∼3.2 × 10⁷ by tuning the Ag-sputtering duration. SERS measurements demonstrate that the as-fabricated large-scale Ag-nanostructures can serve as highly sensitive and reproducible SERS substrates. Finite element method calculation also confirms that the fabricated substrates possess excellent SERS activity. By modifying the Ag-NR arrays with mono-6-thio-β-cyclodextrin, the SERS detection limit of PCB-77 (a congener of polychlorinated biphenyls (PCBs)) reaches 10⁻⁶ M, showing potential in SERS-based rapid detection of trace PCBs, a kind of global environmental hazardous material.