It is proposed that direct formation of epitaxialCoSi2andNiSi2as the first phase, is due to the interlayer between the metal and silicon acting as a diffusion barrier, which decreases the metal concentration at the growth interface. Such concentration controlled phase selection (CCPS) is explained thermodynamically by utilizing the effective heat of formation (EHF) model. This approach is also used to explain silicide formation with metal alloys. Concentration controlled phase selection (CCPS) is not only applicable to silicide formation but should in general enable materials scientists to form phases with desirable properties, by controlling the concentrations of the reactants at the growth interface. ©1997 American Institute of Physics.