Aerosol Direct Writing and Thermal Tuning of Copper Nanoparticle Patterns as Surface-Enhanced Raman Scattering Sensors

Surface-enhanced Raman scattering (SERS) substrates are of great interest for detecting low-concentrated analytes. However, issues such as multistep processing, cost, and possible presence of hazardous substances in the fabrication still represent a significant drawback. In this paper, an innovative direct writing method is introduced for solvent-free and spatially selective deposition of fine metal copper nanoparticles (CuNPs), with size distribution below 20 nm, generated in-line through a spark ablation method (SAM). The deposited CuNPs' morphology and composition were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), and energy-dispersive X-ray spectroscopy (EDS). The resulting CuNP patterns feature porous 3D microdomains with nanometric structures serving as hot spots for Raman signal enhancement. Low-temperature post-treatment (below 200 °C) of the deposited CuNPs significantly evolves its morphology and leads to sintering of NPs into a semicrystalline structure with sharp geometric features, which resulted in a more than 10-fold increase of the enhancement factor (up to 2.1 × 105) compared to non-heat-treated samples. The proposed method allows creating SERS substrates constituted by sharp 3D metallic nanopatterns selectively deposited onto specific regions, which paves the way for new printed, highly sensitive SERS-based sensors.