Journal of the Electrochemical Society, Vol.147, No.6, 2206-2209, 2000
Retarding effect of HCl on rate of chemical vapor deposition of TiN from TiCl4-H-2-N-2
The deposition rate of TiN was measured in a hot-wall chemical vapor deposition reactor using TiCl4-H-2-N-2(-HCL) gas mixtures at 1 bar total pressure and 950-1470 K. With respect to HCl, the reaction order was found to be -3. From the experimental results, a reaction model was derived that assumes (Reaction I) TiCl4(g) + 1/2H(2)-->TiCl3(g) + HCl to be the rate-determining reaction in the homogeneous gas phase, and (Reaction III) Ti(ad) + 1/2N(2)-->TiN(s) to be the slow heterogeneous step. The heterogeneous reaction preceding Reaction III, which may be described as (Reaction II) TiCl3(g) + 3/2H(2) = Ti(ad) + 3HCl, was assumed to be sufficiently fast to attain equilibrium. Reaction II accounts for the strongly retarding effect of HCl on the rate of TiN deposition. By proper adaptation of the rate constants and the activation energies of Reactions I and III, the numerical simulation led to deposition rates in good agreement with the measured values.