Kinetics and mechanism of the thermal decomposition of tetrakis(dimethylamino)titanium

Tetrakis(dimethylamino)titanium (TDMAT) is ail important precursor for TiN and TiSiN thin films in chemical vapor deposition. In order to better understand how the gas phase chemistry influences tile formation of these films, the decomposition of TDMAT has been studied between 300 and 600K. The Arrhenius plot clearly shows two kinetic regimes, with a transition occurring 530K. The activation energies calculated were 16 +/- 2 kJ mol(-1) (333 - 530K) and 166 +/- 16 kJ mol(-1) (530 - 583K). The mechanistic implications of the kinetic and species data ale discussed. No measurable pressure dependence was found. The kinetics of the decomposition of silane was also measured from 823 - 1023K. Tile calculated Arrhenius parameters indicate that the process probably involves a surface reaction as well. The reaction between TDMAT and silane at 450degreesC shows no reactivity without tile presence of ammonia, which is in agreement with the mechanistic insights from the TDMAT decomposition.