2014 Volume 40 Issue 5 Pages 425-431
The growth rate of titanium nitride (TiN) film by thermal chemical vapor deposition (CVD) in horizontal tubular reactor was investigated experimentally and numerically. Titanium tetrachloride (TiCl4) was selected as a raw material, and TiCl4 vapor was mixed with nitrogen and hydrogen in the reactor. The initial molar fraction of TiCl4 was about 0.0003, and the pressure at the exit of the reactor was about 50700 Pa. There were two regions for the growth rate distribution along the axis in the tubular reactor. In the first region, the growth rate could be controlled by the surface reaction of TiCl4 because it increased with temperature at the inner wall, TIW, of the reactor. In this region, analysis of reaction kinetics for a differential reactor showed that the rate constant for the surface reaction increased with the temperature at TIW<1163 K and did not change at TIW>1163 K. In the second region, the growth rate was found to decrease exponentially with axial position in the reactor and could be controlled by the diffusion rate of remaining TiCl4. The growth rates of the TiN film calculated by combining heat and mass transfer analysis with the nonlinear least-squares method agreed well with the experimental ones. The activation energy for the rate constant of the surface reaction was 201.9 kJ/mol.
