The formation and structure of a thin film deposited using tetrakis-(dimethylamino)-titanium [Ti(N(CH3)(2))(4), TDMAT] as a precursor onto a Si(100)-2 x 1 substrate at ultrahigh vacuum (UHV) conditions was investigated by a combination of surface analytical techniques. The effects of surface temperature and pressure of the precursor molecules on the deposition rate are correlated with the monolayer chemistry of the precursor. The titanium carbonitride (TiCxNy) thin films produced by thermal deposition of TDMAT onto Si(100)-2 x 1 at 593 K are continuous and smooth with a root-mean-square (RMS) roughness of < 2 nm, having a thickness with a lower limit of 4.7 +/- 0.4 nm, and a stoichiometry of approximately x=y=1. In addition, it was determined that the lower limit of the sputtering rate for TiCxNy was similar to0.016 nm s(-1) under the conditions used here. These films hold great promise as barrier materials in next-generation microelectronic devices. (C) 2004 Elsevier B.V. All rights reserved.