This study reveals a significant improvement in surface-enhanced Raman scattering (SERS) activity of Ag/ZrO₂ substrates covered with a few-layer graphene preliminary exposed to ultraviolet (UV) light. The SERS-active substrates are formed by the “silver mirror” deposition of Ag nanoparticles on annealed zirconia blocks. The film composed of ~3 graphene layers is grown on copper foil by a chemical vapor deposition and then wet-transferred to the SERS-active substrates. The graphene-free Ag/ZrO₂ samples are found to provide an enhancement of the Raman scattering from rhodamine 6G (R6G) at a micromolar concentration, which is associated with combined effects from the surface plasmon resonance in the Ag nanoparticles and a charge transfer facilitated by zirconium dioxide. It is revealed that the SERS signal from the analyte molecules can be suppressed by a UV exposure of the Ag/ZrO₂ samples due to photocatalytic activity of the wide band gap semiconductor. However, if the samples are covered with a few-layer graphene (Gr/Ag/ZrO₂) it prevents the dye molecule decomposition upon the UV treatment and improves SERS activity of the substrates. The 365 nm treatment leads to a 40% increase in the 10^–6 M R6G SERS spectrum intensity, while the 254 nm irradiation causes it to rise by 47%, which is explained by different responses from the surface and bulk zirconia crystals to the short and long UV wavelengths. This enhancement is attributed to the distinct responses of surface and in-depth zirconia crystals to varied UV wavelengths and underscores the pivotal role of graphene as a protective and enhancing layer.

Metal-coated mesoporous PSi (mesoPSi) opens up disruptive perspectives for biosensing, which is primarily enabled by surface-enhanced Raman scattering (SERS). Although the unique performance of SERS-active substrates based on metal-coated mesoPSi has already been praised, influence of defects in silicon wafer on its morphology has not been revealed. Defects lead to formation of spiral regions in mesoPSi with varying porosity, which affects SERS activity of the overlying metallic nanostructures. It limits the reliability of SERS analysis. Here, we investigate repeatability of morphology and SERS activity of silver particles on mesoPSi as a function of defects in parent silicon, which are induced by irregular dopant levels. We propose an original corrosion approach that has not yet been applied to control the morphology of silicon nanostructures in general and mesoPSi in particular. By replacing silicon nanocrystallites with sacrificial copper nanoparticles, we were able to eliminate the surface irreproducibility of mesoPSi. The copper-corrosion-modified porous silicon surface was shown to be a suitable substrate for reliable SERS-active substrates. In more detail, SERS-active substrate based on mesoPSi without a defective surface layer allowed for a more than 40% increase in the SERS-active surface area with a signal deviation of only 10 % compared to that with a defective layer.