Chemical vapor deposition (CVD) of TiSi2 from TIC14, H2, and substrate silicon has been investigated thermodynamically. From a critical evaluation of the thermochemical data, an assessment of the Ti-Si binary phase diagram has been performed. This is the basis of a new set of thermodynamic values for the titanium silicides, which have been used in the calculations. As a comparison, two other common data sets have also been used. The results from the calculations showed that the trends in selectivity as well as substrate etching were not affected by the choice of the silicide data. However, in the calculated CVD phase diagrams the stability regions for the various equilibria were strongly affected. The selectivity of the process was found to be very high and was favored by a low temperature and a low H2/TiC14 molar ratio. Moreover, improved selectivity can be expected for hot-wall reactor conditions. It was also shown that thermodynamics can be used for prediction of trends in substrate etching. The lowest etching yield was obtained at low pressures, at high temperatures, and at high H2/TiC14 molar ratios.With the decreasing feature sizes of the integrated circuits there is a need for new metallization schemes. Metals like W, Cu, and AI and disilicides of Ti, Mo, and W are here attractive candidates for various metallizatien applications. I Among the disilicides TiSi2 has the lowest resistivity and a low contact resistance to silicon.TiSi2 can be prepared by techniques like evaporation and sputtering. ~ However, chemical vapor deposition (CVD) offers several advantages like selectivity, excellent uniformity, and good step coverage. TiSi2 can be deposited from an H2-TiCI4 vapor and using substrate silicon 2-6 or from H~-TiCI4 vapor with a gaseous silicon-carrying precursor (SiHI4 or SIC14). s-17 The latter case has the advantage of less consumption of the substrate silicon. Cold-wall ~47 as well as hot-wall reactors are used for TiSi~ CVD. 2-4 Concerning the deposition pathways, the basic difference between these two reactor types is that the homogeneous reactions in the vapor are favored in the hot-wall reactor, while these reactions are suppressed in a cold-wall reactor.As mentioned above, TiSi2 can be deposited selectively onto silicon on a patterned Si/SiO2 substrate from a TIC14 carrying vapor. The selectivity is based on the difference in reactivity between the different substrate materials Si and SiO2. The Si is much more reactive towards the vapor than SiO2 and hence the Ti deposition with the subsequent TiSi2 formation is localized to the Si windows according to a reaction TiCl4(g) + 3St(s) --) TiSi~(s) + SiCl4(g)[I]With He in the reaction gas mixture, competing reactions involving HCI also occur. Thermodynamic calculations can be used for prediction of trends in selectivity as well as substrate etching when changing the experimental parameters. Calculated CVD phase diagrams are often used in order to select appropriate deposition parameters, such as temperature, total pressure and molar ratio between the ...