Inkjet Printing of Ag and Polystyrene Nanoparticle Emulsions for the One-Step Fabrication of Hydrophobic Paper-Based Surface-Enhanced Raman Scattering Substrates

Hydrophobic substrates for surface-enhanced Raman scattering (SERS) of adsorbate species are of great interest in chemical analysis because they can concentrate the analyte molecules in a small area of the surface, thereby improving the SERS sensitivity. Here, we propose a general strategy to fabricate hydrophobic paper-based substrates for SERS applications. The paper substrates have been manufactured by inkjet printing of aqueous emulsions containing Ag and polystyrene (PS) colloidal nanoparticles. In a first stage, the SERS performance of the substrates was optimized by varying the relative amounts of polymer/metal colloidal nanoparticles, the number of printing layers, and the degree of hydrophobicity of the substrates, using crystal violet as a molecular probe, which is well known for its strong SERS activity. In these conditions, the strongest surface Raman enhancement was observed for the highest water contact angle (146°) achieved. The selected Ag/PS-coated paper substrates showed wide applicability for several analytes, but in this study, a detailed analysis is provided for the pesticide thiram as a proof of concept. Several samples spiked with thiram have been analyzed by SERS, giving a detection limit of 0.024 ppm thiram in mineral water and apple juice, while in apple peel, the detection limit achieved for the same pesticide was 600 ng/cm2. We suggest that this one-step fabrication method produces a hydrophobic coating whose nanoscale features improve the SERS performance of the paper substrates.