The adsorption and pyrolysis of tetrakis-͑dimethylamido͒-titanium ͑TDMAT͒, Ti͓NMe 2 ͔ 4 , on several metal substrates, were studied using x-ray photoelectron spectroscopy, Auger electron spectroscopy, infrared reflection absorption spectroscopy and thermal desorption mass spectrometry. TDMAT was found to decompose readily above ϳ480 K on metallic substrates, producing TiC x N y films exhibiting a carbon-rich interface. However, in the presence of NH 3 , well below the threshold of gas-phase reactions ͑Ͻ10 Ϫ4 Torr͒, the growth of low-carbon-content ͑р8 at. %͒ titanium nitride films proceeds readily, via surface mediated reaction͑s͒ of TDMAT and NH 3 between 550 and 750 K. The effects of surface temperature and reagent pressures are reported and discussed.