Mg–Ti–spinel formation at the TiN/MgO interface by solid state reaction: Confirmation by high-resolution electron microscopy

Abstract

Mg–Ti–spinel formation along the interface of epitaxial TiN(100) films to MgO(100) substrates has recently been investigated by transmission electron microscopy (TEM) in the diffraction-contrast mode in samples grown at substrate temperatures higher than 800 °C and in such post-annealed at 850 °C. This phenomenon has now been investigated by high resolution electron microscopy of cross-sectional samples, at an acceleration voltage of 300 kV. Emphasis is given to the TiN/spinel and the spinel/MgO interfaces with respect to their structure and morphology. The results obtained confirm the previously drawn conclusions on the atomic mechanism of the solid state reaction during the spinel-forming process: The spinel, which most likely is of the composition Mg₂TiO₄, forms by counterdiffusion of the cations Ti⁴⁺and Mg²⁺in the rigid oxygen frame provided by the fcc oxygen sublattice of MgO. The latter is completely taken over by the spinel lattice. This “host” character of the MgO substrate lattice for the topotaxial growth of the spinel lattice and the coherency of the solid state reaction with respect to the lattices of all the phases involved are demonstrated. Misfit dislocations at the TiN/MgO, TiN/spinel, and the spinel/MgO interfaces, as well as antiphase boundaries of the cation sublattice of the spinel phase, have also been observed.