Theoretical study on gas‐phase reactions during chemical vapor deposition of TixAl1–xN from TiCl4, AlCl3, and NH3

Fcc‐TixAl1–xN (TiAlN) coatings synthesized via chemical vapor deposition (CVD) reduce cutting tool wear. Although CVD conditions reportedly influence coating quality, no quantitative guidelines are yet available. To quantitatively study the film‐forming mechanism of TiAlN CVD, the gas composition over the surface must be known. Therefore, we developed a gas‐phase elementary reaction model for TiAlN CVD derived from TiCl4/AlCl3/NH3. First, we constructed a novel thermodynamic dataset including molecules that contained both Ti and Al, and calculated the equilibrium composition. Thermal equilibrium calculations in the gas phase showed that the most stable species were AlCl3 and TiCl3 rather than TiCl4. An elementary reaction model was constructed based on the kinetics of the gas‐phase species that were generated. Kinetic analysis revealed that gas‐phase reactions were largely absent under our reactor conditions. The thermal equilibrium calculations indicated that TiCl4 may have given rise to TiCl3. Thus, other reaction pathways of TiCl4 to TiCl3 were explored. We calculated the reaction rate constants of 12 reactions of Ti species and added them to the model, which revealed that TiCl4 decomposed to TiCl3 via TiCl3NH2. Under our conditions, TiCl4 and TiCl3NH2 are the major Ti species and AlCl3 and AlCl2NH2 are the major Al species, which suggests that some of these species may form films. Unlike in the earlier reaction model, NH2 and H radicals were produced, which may have contributed to the surface reactions. For reactors with large Surface/Volume ratio of reactor, the effects of gas‐phase reactions should be considered. Our reaction model enables estimation of the partial pressures of reactor gas species and will therefore aid study of the TiAlN deposition mechanism.