Stoichiometric shifts in the refractory metal silicides due to subsequent thermal processing have been an important consideration in VLSI processing. Optimal stoichiometry for interconnect application has been controversial. Shift in silicon‐to‐metal atomic ratio of the metal silicide films, due to heat treatment under inert and oxidizing ambients, have been studied. Existence of a thermodynamical equilibrium stoichiometry has been investigated by studying films on both silicon and silicon dioxide. The silicide films were deposited by planar magnetron cosputtering and Rutherford backscattering was the primary technique used for monitoring the stoichiometry.