Silicon nanowires (SiNWs) were fabricated in a metal-assisted chemical etching method with two steps including dipping silicon wafers in AgNO3/HF solutions and then in H2O2/HF solutions. Grazing incidence X-ray diffraction measurements with a set of incidence angles were carried out on the resulting samples to detect characteristics of silver nanoparticles in the etched silicon. Compared with the uniform size of silver nanoparticles on the surface, the silver nanoparticles in etched silicon were found with size increasing and content decreasing corresponding to the depths. Based on the silver size increasing phenomenon, a detailed supplementary hypothesis about SiNWs formation was proposed about silver disintegration and redeposition in the later stage of silicon etching. For 2, 3, 4, and 8 mM AgNO3 solutions used to study their effect on the SiNWs, it was found that a higher quantity of Ag+ concentration such as 8 mM were not beneficial for producing good quality SiNWs.

Herein, we report an efficient method to produce silver (Ag) nanoparticle-decorated silicon (Si) nanowire (NW) arrays on a pyramidal Si (P-Si) substrate by using a pure chemical method and rapid thermal annealing in different atmospheres. A metal-assisted chemical etching technique was used to produce vertical Si NW arrays on pyramidal Si. The etching was observed to be heavily dependent on the substrate type. On planar Si (100), the etching was observed to occur in a uniform manner. However, the etching rate was observed to increase from the top to the base of the Si pyramid. The Si NWs produced from P-Si have zig-zag sidewalls as observed from high-resolution transmission electron microscopy images. However, for the same oxidant concentration, Si NWs produced from planar Si (100) consist of straight and amorphous sidewalls. Local variation of oxidant concentration is responsible for the formation of different sidewalls. The substrates are both surface-enhanced Raman scattering (SERS) active and hydrophobic. The hydrophobicity is due to the dual scale of roughness contributed to by both pyramidal and NW structures. Finite-difference time-domain simulation shows that the gap between two Ag spheres and also the gap between Si NWs and Ag spheres contributed to SERS enhancement.