P-type (100) oriented silicon wafers were etched with vapors of concentrated Hydrofluoric acid in a reaction chamber under continuous vapor-flow at standard temperature and pressure. The surface morphology of the etched samples was examined by scanning electron microscope and pore size analyzer. The radius of the pores and quantum dots were found to be 6 nm and 4 nm respectively. Etched samples emitted red luminescence when exposed to ultra violet (UV) light. The red luminescence emitted by the etched surface has been assigned to energy states induced by quantum confinement of holes.