We investigate Co silicide phase formation when extra Si is added within an as deposited 50 nm Co film. The addition of Si is investigated for both the Co/SiO2 and Co/Si(1 0 0) system. A series of 10 Co-Si mixed films with a Si content varying from 21 to 59 at.% was prepared and investigated during annealing with in situ X-ray diffraction. The oxide system is used as reference system to identify phases that initially crystallize in an amorphous mixture of a given composition. Multiple phases can nucleate, and the temperature of crystallization depends on the Co-Si atomic ratio. Upon heating of the Co(Si)/Si system, the first reaction is a similar crystallization reaction of the Co(Si) mixture. Once the first phase is formed, one has the normal system of a silicide phase in contact with an unlimited amount of Si from the substrate, and the sequential phase formation towards CoSi2 is established. For deposited layers of composition ranging from 48%Si to 52%Si, the CoSi is the first phase to form and increasing the amount of Si leads to a remarkable improvement of the thermal stability of CoSi on Si(1 0 0). CoSi2 nucleation was extensively delayed by 150 °C compared to the reaction observed from a pure Co film on Si(1 0 0). Electron backscatter diffraction measurements reveal that in this range, the gradual Si increase systematically leads to bigger CoSi grains (up to 20 μm). This shows that the grain size of the CoSi precursor strongly affects the nucleation of the following CoSi2 phase. Laser-light scattering measurements suggest that adding more than 42%Si reduces the roughness of the CoSi2 layer. © 2009 Elsevier B.V. All rights reserved.