Engineering Silicon to Porous Silicon and Silicon Nanowires by Metal-Assisted Chemical Etching: Role of Ag Size and Electron-Scavenging Rate on Morphology Control and Mechanism

We demonstrate controlled fabrication of porous Si (PS) and vertically aligned silicon nanowires array starting from bulk silicon wafer by simple chemical etching method, and the underlying mechanism of nanostructure formation is presented. Silicon-oxidation rate and the electron-scavenging rate from metal catalysis play a vital role in determining the morphology of Si nanostructures. The size of Ag catalyst is found to influence the Si oxidation rate. Tunable morphologies from irregular porous to regular nanowire structure could be tailored by controlling the size of Ag nanoparticles and H₂O₂ concentration. Ag nanoparticles of size around 30 nm resulted in irregular porous structures, whereas discontinuous Ag film yielded nanowire structures. The depth of the porous Si structures and the aspect ratio of Si nanowires depend on H₂O₂ concentration. For a fixed etching time, the depth of the porous structures increases on increasing the H₂O₂ concentration. By varying the H₂O₂ concentration, the surface porosity and aspect ratio of the nanowires were controlled. Controlling the Ag catalyst size critically affects the morphology of the etched Si nanostructures. H₂O₂ concentration decides the degree of porosity of porous silicon, dimensions and surface porosity of silicon nanowires, and etch depth. The mechanisms of the size- and H₂O₂-concentration-dependent dissociation of Ag and the formation of porous silicon and silicon nanowire are described in detail.