Wafer-Scale Hierarchical Nanopillar Arrays Based on Au Masks and Reactive Ion Etching for Effective 3D SERS Substrate

Two-dimensional (2D) periodic micro/nanostructured arrays as SERS substrates have attracted intense attention due to their excellent uniformity and good stability. In this work, periodic hierarchical SiO2 nanopillar arrays decorated with Ag nanoparticles (NPs) with clean surface were prepared on a wafer-scale using monolayer Au NP arrays as masks, followed by reactive ion etching (RIE), depositing Ag layer and annealing. For the prepared SiO2 nanopillar arrays decorated with Ag NPs, the size of Ag NPs was tuned from ca. 24 to 126 nanometers by controlling the deposition thickness of Ag film. Importantly, the SiO2 nanopillar arrays decorated with Ag NPs could be used as highly sensitive SERS substrate for the detection of 4-aminothiophenol (4-ATP) and rhodamine 6G (R6G) due to the high loading of Ag NPs and a very uniform morphology. With a deposition thickness of Ag layer of 30 nm, the SiO2 nanopillar arrays decorated with Ag NPs exhibited the best sensitive SERS activity. The excellent SERS performance of this substrate is mainly attributed to high-density hotspots derived from nanogaps between Ag NPs. Furthermore, this strategy might be extended to synthesize other nanostructured arrays with a large area, which are difficult to be prepared only via conventional wet-chemical or physical methods.