Umbrella-frame silicon nanorod arrays decorated with Au nanoparticles as recyclable SERS substrates.

Surface-enhanced Raman scattering (SERS) is a powerful technique for detection and identification of trace amounts of molecules with high specificity. A variety of two- and three-dimensional (3D) SERS substrates have been developed. Among these SERS substrates, to further develop new morphology of 3D SERS-active substrate with robust SERS functionality is still desired and necessary. In this paper, what we believe to be a novel and effective SERS-active substrate based on large-scale 3D Si hierarchical nanoarrays in conjunction with homogeneous Au nanoparticles (AuNPs) was proposed. Its building block shaped like the umbrella-frame structure was fabricated by a simple and cost-effective top-down nanofabrication method. Such umbrella-frame structure achieved excellent SERS performance with high sensitivity and spatial uniformity. For R6G molecules, the detection limit can be as low as 10-14 M, with an enhancement factor of up to 107. The relative standard deviation can reach about 11% above 30 positions across an area of 100×100 µm2. This is mainly attributed to much more active-sites provided by the umbrella-frame structure for adsorption of target molecules and AuNPs, and sufficient 3D hotspots generated by the coupling between the SiNRs guided mode and AuNPs localized surface plasmon resonance (LSPR), as well as that between AuNPs LSPR. Especially by introducing the umbrella-ribs SiNRs and AuNPs, the light field can be greatly confined to the structure surface, creating strongly enhanced and even zero-gap fields in 3D space. Moreover, the proposed SERS-active substrate can be erased and reused multiple times by plasma cleaning and exhibits typically excellent recyclability and stability for robust SERS activity. The experimental results demonstrate the proposed substrate may serve as a promising SERS platform for trace detection of chemical and biological molecules.