Ultrahigh-Density Array of Silver Nanoclusters for SERS Substrate with High Sensitivity and Excellent Reproducibility

We introduce a simple but robust method to fabricate an ultrahigh-density array of silver nanoclusters for a surface-enhanced Raman spectroscopy (SERS) substrate with high sensitivity and excellent reproducibility at a very large area (wafer scale) based on polystyrene-<i>block</i>-poly(4-vinylpyridine) copolymer (PS-<i>b</i>-P4VP) micelles. After silver nitrates were incorporated into the micelle cores (P4VP) followed by the reduction to silver nanoclusters, we systematically controlled the gap distance between two neighboring silver nanoclusters ranging from 8 to 61 nm, while the diameter of each silver nanocluster was kept nearly constant (∼25 nm). To make a silver nanocluster array with a gap distance of 8 nm, the use of crew-cut-type micelles is required. Fabricated SERS substrate with a gap distance of 8 nm showed very high signal intensity with a SERS enhancement factor as high as 10⁸, which is enough to detect a single molecule, and excellent reproducibility (less than ±5%) of the signal intensity. This is because of the uniform size and gap distance of silver nanoclusters in a large area. The substrate could also be used for label-free immunoassays, biosensing, and nanoscale optical antennas and light sources