Surface Plasmon Structures for Surface-Enhanced Raman Scattering

ABSTRACTSurface-enhanced Raman scattering (SERS) can enhance the intensity of Raman radiation by many orders of magnitude for molecules bound to metallic nanostructures. SERS is generally thought to have been a result of excitation of surface plasmons in nanostructured metal, which greatly enhances local electric field experienced by the molecule. Common SERS substrates fabricated using noble metal colloidal or electrochemically roughened thin films suffer from lack of homogeneity where only few hot spots yield high enhancement. We explore semiconducting nanowires and metallic nanorods as an economical, stable, and uniform SERS substrate for the detection of trace amount of chemicals and bio-species. We utilize bulk synthesized semiconducting nanowires as nano-scale structures that can be coated with noble metals or their colloidal forms to allow for excitation of surface plasmons over broad frequency range. The use of nanowires as SERS substrates has several advantages. The surface properties of these nanowires are highly reproducible and well defined as compared to other systems like colloidal aggregates, electrochemical roughening etc. The synthesized nanowires offer many unique features (sharp vertices, noncircular cross-sections, inter-wire coupling) that may lead to larger field enhancement factors. High density of nanowires means close interaction between adjacent nanowires, which enables SERS to manifest for a broad selection of excitation sources. We have synthesized germanium dioxide and zinc oxide nanowires using the vapor-liquid-solid growth mechanism utilizing a simple quartz tube furnace set up. The nanowires are grown either using thin gold film (5-15 nm) or colloidal gold (20 nm or 60 nm) as catalyst on substrates of silicon, quartz, and alumina. The resulting nanowires are dense (100-300 nm diameter, 10-40 μm long) and randomly distributed on the substrate. The nanowires are subsequently coated with thin films (10-15 nm) of gold that provide plasmons active surface. We have also investigated silver nanorods on glass formed by grazing angle deposition using e-beam evaporation. These nanorods have a diameter of ∼ 50-70 nm with lengths averaging 300-400 nm. These well aligned high aspect ratio and dense structures are ideal for excitation of surface plasmons. The synthesized structures have been characterized using SEM, TEM, and EDS. The SERS studies were conducted using EzRaman-L system from Enwave Optronics, Inc. Silver nanorods and gold-coated nanowires have been found to exhibit significant Raman enhancement for micro-molar concentrations of Rhodamine 6G and Nile blue, and are promising candidates for SERS applications.