Nucleation and growth processes of water deposited onto Si(100) and (111) substrates were investigated in terms of the influences of hydrogenation and hydroxylation of the surface, as well as high-energy electron-beam irradiation. On the hydrogenated Si(100) substrate, randomly oriented ice Ic crystallites grow by heating a monolayer of amorphous solid water (ASW) to ca. 150 K after agglomeration into droplets at T > 80 K. In contrast, nucleation of the ASW monolayer is strongly prohibited on the hydroxylated Si(100) substrates; crystallites are formed in the multilayer regime out-of-registry with the substrate as a result of spontaneous nucleation. The epitaxial growth is quenched on the hydroxylated Si(100) surface (bare Si(100)-(2 × 1) surface) because water molecules bound tightly to the substrate via hydrogen bonds (weak chemical bonds) control the ice nucleation in contrast to the physisorbed water species. On the other hand, the epitaxial growth (nonepitaxial growth) of ice is observed even at 100 ...