The C54 phase formation process of titanium silicide was studied after selective chemical vapor despostion (CVD) onto very small silicon structures, to ascertain the efficacy of CVD to form low resistance contacts in sub-quarter micron technology. Because the selective CVD process forms silicide on any exposed silicon in a CMOS device, the process was studied on both polysilicon and Si (100) chips. The structures consisted of arrays of about 106 identical lines, 0.1 2.0 μm in width, depending on the chip. The CVD process employed TiCl4 and SiH4 for the most part as process gases and the depostion temperature ranged from 730–825°C. X-ray diffraction (XRD) was used to document the amount of C54 phase present after deposition. In some cases samples were annealed after deposition and the phase transformation behavior studied by in-situ XRD. The latter technique employed a synchrotron radiation source providng for rapid XRD spectra collection, so that the C49-C54 phase transformation could be examined with great precision in real time during rapid thermal annealing. The results of CVD depositions were compared to titanium silicide formed by sputter deposition of Ti on identical silicon chips, followed by a typical salicide protocol. Although the phase formation is affected by both film thickness and substrate temperature during CVD, the general result is that the C54 formation is more facile using the CVD process, especially for the smallest line dimensions. The findings are discussed with respect to nucleation processes occurring during growth and post-deposition thermal processing.