Abstract: An atomic layer deposition (ALD) method employing Si2Cl6 and NH3, or Si2Cl6 and activated NH3 as reactants. In one embodiment, the invention includes the steps of (a) placing a substrate into a chamber, (b) injecting a first reactant containing Si2Cl6 into the chamber, (c) chemisorbing a first portion of the first reactant onto the substrate and physisorbing a second portion of the first reactant onto the substrate, d) removing the non-chemically absorbed portion of the first reactant from the chamber, (e) injecting a second reactant including NH3 into the chamber, (f) chemically reacting a first portion of the second reactant with the chemisorbed first portion of the first reactant to form a silicon-containing solid on the substrate, and (g) removing the unreacted portion of the second reactant from the chamber. In other embodiments, the first reactant can contain two or more compounds containing Si and Cl, such as Si2Cl6 and SiCl4.