The mechanism and evolution from the early stages of the Ti/Si reaction by rapid thermal processing (RTP) at 650°C in the presence of Mo doping was studied and compared to the case without Mo doping; for amorphous, polycrystalline and single crystal (100) Si substrates. It was found that for Mo doped polycrystalline Si or Mo doped amorphous Si, the low resitivity C54 TiSi2 phase nucleates at the Ti/Si interface and grows following diffusion limited kinetics, bypassing the nucleation of the high resistivity C49 TiSi2 phase. The conventional phase sequence, with C49 TiSi 2 nucleation and growth, was observed on Mo doped (100) Si and all samples without Mo. The mechanism of early C54 nucleation was identified by high resolution transmission electron microscopy (HRTEM): at early stages of the reaction, precursor silicide phases lattice matched to C54 TiSi2 nucleate at the Ti/Mo doped Si interface, and act as templates for epitaxial nucleation of C54 TiSi2. Two such phases were observed, MoSi2 and a phase with spacings of 2.26 Å and 4.2 Å. Image simulations suggest that the structure of the second template phase is based on Mo5Si3. Similar kinetics were observed on large structures and narrow lines for Mo doped Si (except for the case of (100) Si), indicating that this growth mechanism eliminates the linewidth dependence. Implementation on a 0.10 μm CMOS technology of a process combining Mo doping with pre-amorphization (PAI) achieves low source/drain (S/D) sheet resistance, and the first Ti salicide process with low gate sheet resistance down to 0.06 μm.