We propose a heterogeneous reaction mechanism which is consistent with
experimental observations of the kinetics of metal-organic chemically
vapor deposited TiN films from tetrakisdiethylaminotitanium (TDEAT) a
nd ammonia. The proposed mechanism includes the readsorption of diethy
lamino radicals, which are formed as a byproduct of the deposition rea
ction. We use film profiles in holes on patterned wafers, in addition
to available growth rate data from flat wafer experiments, to estimate
parameter values for a kinetic expression derived from the proposed m
echanism. EVOLVE, a low pressure deposition process simulator, is used
to estimate the value of the adsorption parameter for the adsorbing r
eaction byproduct. Reactant partial pressures at the wafer surface are
estimated simultaneously. Step coverage depends on both the spatially
dependent TDEAT sticking factor and the value of the adsorption param
eter for the inhibiting byproduct. The byproduct inhibition model can
explain the observed kinetics as well as the film conformality; howeve
r, film profiles calculated using a simple sticking factor model (firs
t order reaction model) matched experimental profiles almost as well.
In this simple model, the step coverage of TDEAT sourced films depends
on the sticking factor of the depositing species, which may be formed
by homogeneous reactions. The activation energy estimated using the b
yproduct inhibition model is about 2300 cal g(-1) mol(-1).