Using alternating exposures of Si2H6and Si2Cl6, very thin Si layers have been grown on the Si(100) surface at temperatures (T) as low as 475 °C. Although this growth method is not truly self‐limiting, some of the desired features for Si atomic layer epitaxy (ALE) are retained, as discussed here. The growth rate of new Si on Si(100) using this method is limited by the thermal desorption of H2and HCl. Doping the surface with boron atoms can lower the growth temperature, due to a weakening of the Si—H and Si—Cl bonds on the surface as observed in the temperature programmed desorption results from H2, HCl, and SiCl2desorption from the clean and the boron‐doped Si(100) surfaces.