Nanogap-Engineered Core–Shell-Like Nanostructures for Comprehensive SERS Analysis

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Abstract
Development of fabrication protocols for large-area plasmonic nanostructures with sub-10 nm gaps with a spatially controlled distribution is critical for their real-world applications. In this work, we develop a simple, cleanroom-free protocol for the fabrication of macroscopic-sized plasmonic substrates (>6 cm2), featuring a tunable multiresonance optical response and light concentration in sub-10 nm gaps. Critically, these gaps are free to interact with the surrounding medium. This architecture consists of nonperiodically distributed dielectric nanospheres coated with a metal multilayer, forming semispherical core-shell-like nanostructures (CSLNs) surrounded by a planar film. The sub-10 nm gaps formed between metal caps and the planar film are easily tuned by adjusting fabrication parameters, such as multimetal layer thickness, composition, or nanosphere size and density. The excellent structural homogeneity, wide optical tunability, and extreme light confinement in the spatially controlled subwavelength nanogaps make CSLN-based substrates an ideal platform for comprehensive surface-enhanced Raman scattering (SERS) spectroscopy. This is proven through a combination of numerical modeling and iterative fabrication/characterization, leading to the optimized substrates showing cutting-edge spatial uniformity down to 1.9% determined as the relative standard deviation (RSD) of the SERS signal of p-mercaptobenzoic acid for 225 spectra over the 3600 μm2 area. High sensitivity is evidenced by an enhancement factor of ∼10.6 The proposed substrates also meet all other demanding criteria, including sufficient signal temporal stability (RSD <4%), high substrate-to-substrate reproducibility (<15%), and SERS activity toward three various analytes. The unique geometry and wide spectral tunability of the CSLN substrates will also be of great value for other plasmon-driven applications.
Funding Information
  • Narodowe Centrum Nauki (2019/35/B/ST5/02477)
  • Uniwersytet Warszawski (BOB-IDUB-622-228/2022 PSP 501-D111-20-2004310, BOB-IDUB-622-228/2022 PSP 501-D112-20-1004310)

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