An investigation of the formation of refractory metal (tungsten, molybdenum and tantalum) silicides by reaction of the metal with crystalline and polycrystalline silicon at temperatures above 900°C indicates that WSi2 formation can be inhibited by certain processing techniques. These techniques utilize the growth of an SiO2 diffusion barrier about 20 Å thick on crystalline silicon and the deposition of tungsten films in vacuum ambients that will ensure oxygen incorporation (P ≥ 2 × 10−7 Torr). The reactivity of vacuum-deposited tungsten films results in the formation of an isolating oxide between the deposited silicon and tungsten films and the maintenance of the stability of the SiO2 diffusion barrier between tungsten films and a crystalline silicon substrate. This barrier is effective up to 1050°C in hydrogen ambients containing 15–20 ppm H2O. These procedures, however, are ineffective in preventing the formation of MoSi2 or TaSi2 at or above 900°C. A possible explanation for these results is that the tungsten film contains some level of oxygen due to the gettering of residual oxygen in the vacuum. In addition, the outgassing of the silicon source may enhance the level of oxygen at the evaporated W-Si interface. When the composite layer is annealed at high temperatures in a hydrogen ambient, the oxygen diffuses readily out of the bulk of the tungsten film to the interface, probably forming Sio2 which is more stable than WO3.The resulting thin SiO2 film has sufficient integrity to prevent silicon diffusion into the tungsten, thereby preventing WSi2 formation. This property of tungsten makes it inherently useful for buried-metal films in silicon devices.