Large-scale high-quality 2D silica crystals: dip-drawing formation and decoration with gold nanorods and nanospheres for SERS analysis

High-quality colloidal crystals (CCs) are important for use in photonic research and as templates for large-scale plasmonic SERS substrates. We investigated how variations in temperature, colloid concentration, and dip-drawing parameters (rate, incubation time, etc) affect the structure of 2D CCs formed by highly monodisperse silica nanoparticles (SiNPs) synthesized in an l-arginine solution and regrown by a modified Stöber method. The best quality 2D CCs were obtained with aqueous 12 wt% colloids at a temperature of 25 °C, an incubation time of 1 min, and a drawing rate of 50 mm min−1. Assembling of gold nanorods (GNRs) on 2D CCs resulted in the formation of ring-like chains with a preferential tail-to-tail orientation along the hexagonal boundaries. To the best of our knowledge, this is the first time that such nanostructures have been prepared. Owing to the preferential tail-to-tail packing of GNRs, 2D SiNP CC + GNR substrates demonstrated an analytical SERS enhancement of about 8000, which was 10 to 15 times higher than that for self-assembled GNRs on a silicon wafer. In addition, the analytical SERS enhancement was almost 60 times lower after replacing the nanorods in 2D SiNP CC + GNR substrates with 25 nm gold nanospheres.