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 degrees) 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/cm(2). We suggest that this one-step fabrication method produces a hydrophobic coating whose nanoscale features improve the SERS performance of the paper substrates.

Automated summary

This study introduces a general method to fabricate hydrophobic paper-based SERS substrates and optimizes their performance by controlling factors such as the ratio of nanoparticles and the number of printing layers. The selected substrates showed good SERS performance for various analytes, with specific analysis conducted on the pesticide thiram. The one-step fabrication method is suggested to enhance the SERS performance of the paper substrates through nanoscale features of the hydrophobic coating.