We demonstrate that, at low reagent pressures (<10(-4) Torr), the prevalent TiN film deposition mechanism operates exclusively on the reactions between tetrakis(dimethylamido)titanium (TDMAT) and NH3 at the growth surface. Our surface spectroscopic analyses indicate that film deposition in the low-pressure regime is also capable of delivering TiN with very low residual carbon levels. Spectroscopic evidence supporting this surface-reaction pathway. to TiN films is presented in this report. The kinetics of the reactions between TDMAT and NH3 on TiN surfaces are also explored. In addition, we also discuss a proposed mechanistic framework for this low-pressure deposition process.