A process of doping a silicon layer with dopant atoms generally includes reacting a vapor of a dopant precursor with oxide and/or hydroxide reactive sites present on the silicon layer to form a self assembled monolayer of dopant precursor; hydrolyzing the self assembled monolayer of the dopant precursor with water vapor to form pendant hydroxyl groups on the dopant precursor; capping the self assembled monolayer with an oxide layer; and annealing the silicon layer at a temperature effective to diffuse dopant atoms from the dopant precursor into the silicon layer. Additional monolayers can be formed in a similar manner, thereby providing controlled layer-by-layer vapor phase deposition of the dopant precursor compounds for controlled doping of silicon.