Stable, Flexible, and High-Performance SERS Chip Enabled by a Ternary Film-Packaged Plasmonic Nanoparticle Array

The high sensitivity and long-term storage stability of a plasmonic substrate are vital for practical applications of the surface-enhanced Raman scattering (SERS) technique in real-world analysis. In this study, a rationally designed, ternary film-packaged, silver-coated gold-nanoparticle (Au@Ag NP) plasmonic array was fabricated and applied as a stable and high-performance SERS chip for highly sensitive sensing of thiabendazole (TBZ) residues in fruit juices. The ternary films played different roles in the plasmonic chip: a newborn poly(methyl methacrylate) (PMMA) film serving as a template for fixing the self-assembled closely packed monolayer Au@Ag NP array that provided an intensive hot spot, a fluorescent quantitative polymerase chain reaction adhesive film (qPCR film) acting as a carrier to retrieve the Au@Ag/PMMA film that was used to improve the robustness of the plasmonic array, and a polyethylene terephthalate (PET) film covered over the Au@Ag/PMMA/qPCR film performing as a barrier to improve the stability of the chip. The Au@Ag/PMMA/qPCR-PET film chip showed high sensitivity with an enhancement factor of 3.14 × 106, long-term storage stability without changing SERS signals for more than 2 months at room temperatures, and a low limit of detection for sensing TBZ in pear juice (21 ppb), orange juice (43 ppb), and grape juice (69 ppb). In addition, the procedure for fabricating the Au@Ag/PMMA/qPCR-PET film SERS chip was easy to handle, offering a new strategy to develop flexible and wearable sensors for on-site monitoring of chemical contaminants with a portable Raman spectrometer in the future.