Silver‐Assisted Chemical Etching on Silicon with Polyvinylpyrrolidone‐Mediated Formation of Silver Dendrites

Metal‐assisted chemical etching (MaCE) on silicon (Si)—mediated by polyvinylpyrrolidone (PVP)—is systematically investigated herein. It is found that the morphologies and crystallographic natures of the grown silver (Ag) dendrites can be significantly modulated, with the presence of PVP in the MaCE process leading to the formation of faceted Ag dendrites preferentially along the (111) crystallographic phase, rather than along the (200) phase. Further explorations of the PVP‐mediated effect on Si etching are also revealed. In contrast to the aligned Si nanowires formed by MaCE without PVP addition, only distributed nanopores with sizes of 200 to 400 nm appear on the Si surfaces in the presence of PVP. The origin of surface polishing on Si in the PVP‐mediated MaCE process can be attributed to the distinct transport pathway of holes supplied by the Ag⁺ ions, where the holes are injected directly into the primary Ag seeds, rather than through Ag dendrites, thus leading to the isotropic etching of the Si surface.