Ti3SiC2 thin films were synthesized by magnetron sputtering from Ti3SiC2 and Ti targets. Sputtering from a Ti3SiC2 target alone resulted in films with a C content of similar to 50 at. % or more, due to gas-phase scattering processes and differences in angular and energy distributions between species ejected from the target. Addition of Ti to the deposition flux from a Ti3SiC2 target is shown to bind the excess C in TiCx intergrown with Ti3SiC2 and Ti4SiC2. Additionally, a substoichiometric TiC, buffer layer is shown to serve as a C sink and enable the growth of Ti3SiC2. (c) 2007 American Vacuum Society.