Different aspects of the reaction between Ti and single‐crystal (100) Si are reported when the reaction is thermally activated by rapid thermal annealing. The sheet resistance variation of the
TiSix
film was measured for a wide range of annealing temperatures, from 400° to 1100°C, in two different atmospheres of high purity Ar and
N2
gas, for bare and As‐implanted Si. At temperatures ⩾800°C, the only silicide formed was
TiSi2
. Both cross‐sectional TEM and RBS results indicate that the amount of titanium consumed in the reaction depends strongly on the atmosphere used for silicidation. Argon makes possible the reaction of almost the whole Ti layer with silicon, while nitrogen leaves an unreacted layer of about 15 nm, independent of the thickness of the original film. A two‐step anneal is necessary to eliminate bridging in a patterned oxide structure. No difference was observed in the roughness of the external surface whether the samples were annealed in Ar or in
N2
. No significant enhanced diffusion of As into Si was observed near the
normalSi/TiSi2
interface after RTA in an Ar ambient, while a redistribution of As into the silicide takes place. The As piles up at the
TiSi2
surface, from which it evaporates at high temperatures. Results of furnace‐annealed samples in
N2
atmosphere show a pile‐up of As at the
normalSi/TiSi2
and the
TiSi2/normalambient
atmosphere interfaces, where it evaporates from the latter, at high temperatures.