Leveraging coffee‐ring effect on plasmonic paper substrate for sensitive analyte detection using Raman spectroscopy

Abstract

Raman spectroscopy has demonstrated immense promise as a molecular fingerprinting tool in biomedical diagnostics. However, the utility of conventional Raman scattering for ultrasensitive measurements of biofluids is limited by intrinsically weak signals and has spurred advances in and wider applications of plasmon‐enhanced measurements. Here, we propose a label‐free methodology that leverages drop coating deposition on a silver ink‐based plasmonic paper substrate with tunable hydrophobic attributes to combine two distinct sources of enhancement, namely, solute preconcentration and excitation of localized surface plasmons. The facile modulation of the hydrophobicity of the plasmonic silver paper facilitates investigations into the coffee‐ring effect that results from the interplay of contact line pinning, solvent evaporation, and capillary flow. We show that the Raman spectra acquired from the hydrated ring deposits show clear enhancement beyond that obtained from surface‐enhancement owing to the presence of the silver nanofilm. In light of the superior sensitivity and lack of substantive sample preparation requirements, our findings open the door for a complementary low‐cost paper‐based analytical device for molecular sensing.We propose a label‐free analytical tool that leverages drop coating deposition on a silver ink‐based plasmonic paper substrate to combine two distinct sources of enhancement for Raman scattering signals. The facile modulation of the hydrophobicity of the plasmonic silver paper facilitates investigations into the coffee‐ring effect that results from the interplay of contact line pinning, solvent evaporation, and capillary flow. Raman spectra acquired show clear enhancement beyond that obtained from surface‐enhancement owing to the presence of the silver nanofilm.