Long-range enhancement for fluorescence and Raman spectroscopy using Ag nanoislands protected with column-structured silica overlayer

Abstract

We demonstrate long-range enhancement of fluorescence and Raman scattering using a dense random array of Ag nanoislands (AgNIs) coated with column-structured silica (CSS) overlayer of over 100 nm thickness, namely, remote plasmonic-like enhancement (RPE). The CSS layer provides physical and chemical protection, reducing the impact between analyte molecules and metal nanostructures. RPE plates are fabricated with high productivity using sputtering and chemical immersion in gold(I)/halide solution. The RPE plate significantly enhances Raman scattering and fluorescence, even without proximity between analyte molecules and metal nanostructures. The maximum enhancement factors are 10⁷-fold for Raman scattering and 10²-fold for fluorescence. RPE is successfully applied to enhance fluorescence biosensing of intracellular signalling dynamics in HeLa cells and Raman histological imaging of oesophagus tissues. Our findings present an interesting deviation from the conventional near-field enhancement theory, as they cannot be readily explained within its framework. However, based on the phenomenological aspects we have demonstrated, the observed enhancement is likely associated with the remote resonant coupling between the localised surface plasmon of AgNIs and the molecular transition dipole of the analyte, facilitated through the CSS structure. Although further investigation is warranted to fully understand the underlying mechanisms, the RPE plate offers practical advantages, such as high productivity and biocompatibility, making it a valuable tool for biosensing and biomolecular analysis in chemistry, biology, and medicine. We anticipate that RPE will advance as a versatile analytical tool for enhanced biosensing using Raman and fluorescence analysis in various biological contexts.