Cu-Assisted Corrosion Conquers Irregularities in Mesoporous Si

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.