We demonstrate the use of a synchrotron radiation source for in situ x-ray diffraction analysis during rapid thermal annealing (RTA) of 0.35 μm Salicide (self-aligned silicide) and 0.4 μm Polycide (silicided polysilicon) TiSi2 Complementary Metal Oxide Semiconductor (CMOS) gate structures. It is shown that the transformation from the C49 to C54 phase of TiSi2 occurs at higher temperatures in submicron gate structures than in unpatterned blanket films. In addition, the C54 that forms in submicron structures is (040) oriented, while the C54 that forms in unpatterned Salicide films is randomly oriented. Although the preferred oreintation of the initial C49 phase was different in the Salicide and Polycide gate structures, the final orientation of the C54 phase formed was the same. An incomplete conversion of C49 into C54-TiSi2 during the RTA of Polycide gate structures was observed and is attributed to the retarding effects of phosphorus on the transition.