The phase formation during rapid thermal annealing of a Ti/Mo bilayer sequentially deposited on Si substrates has been studied. The Mo layer varied from 0.5 to 2 nm and the Ti layer was always 60 nm thick. The presence of the Mo interposing layer enhances the formation of the C54 of TiSi2by first forming a Mo‐bearing silicide phase of hexagonal structure. The desired C54 phase then nucleates and grows on top of this Mo‐bearing silicide phase at a temperature as low as 650 °C via Si diffusion through the growing silicide layers. This is about 100 °C lower than what is usually needed for the C49–C54 transformation. The significance of this finding is that the usual route for the formation of TiSi2, i.e., the C49 phase forms as a result of the Ti–Si interaction and the C54 phase forms as the product of phase transformation, is altered by the interposition of a thin refractory metal (here Mo) layer between Ti and Si. ©1996 American Institute of Physics.