TEM and DFT investigation of CVD TiN/κ–Al2O3 multilayer coatings

Artikel i vetenskaplig tidskrift, 2007

This paper investigates the interfacial structure in hot-wall CVD TiN/kappa-Al2O3 multilayer coatings using both HREM and DFT modeling. Two multilayers with different thicknesses of the TiN layers (50 and 600 nm) separating the kappa-Al2O3 layers are analyzed. The general microstructure of the two multilayers is relatively similar. The TiN layer in the thicker TiN/kappa-Al2O3 coating is thick enough to be several TiN grains high. This means that epitaxial columns, which are often found in the thinner TiN/kappa-Al2O3 coatings, are not present. However, the orientation relationships at the TiN/kappa-Al2O3 interfaces are the same in both multilayers. The HREM investigations show that kappa-Al2O3 (001) planes can grow directly on flat (111) TiN faces, without any other phases or detectable amounts of impurities, such as sulphur, present. Where the TiN layers are more curved, gamma-Al2O3 can be grown, at least partly stabilized by the cube-on-cube orientation relationship between gamma-Al2O3 and the underlying TiN. The DFT calculations show very similar adsorption strengths for an 0 monolayer positioned on Ti-terminated TiC(111) and TiN(111) surfaces, with preferred adsorption in the fee site. 0 adsorption on N-terminated TiN(111) is much weaker, with preferred adsorption in the top site. Calculated elastic-energy contributions yield a higher stability for kappa-Al2O3 on TiN(111) than on TiC(111) and a higher stability for kappa-Al2O3 than for alpha-Al2O3 on both TiC and TiN. This indicates that the observed higher stability Of kappa-Al2O3 on TiC(111) than on TiN(111) is not due to the lattice mismatch, while the preferred epitaxial growth of kappa-Al2O3 over alpha-Al2O3 can be partly attributed to the mismatch.