Anionen- und Kationendiffusion in Barium- und Strontiumtitanat

Perovskite oxides show various interesting properties providing several technical applications. In many cases the defect chemistry is the key to understand and influence the material's properties. In this work the defect chemistry of barium titanate and strontium titanate is analysed by anion and cation diffusion experiments and subsequent time-of-flight secondary ion mass spectrometry (ToF-SIMS). The reoxidation equation for barium titanate used in multi-layer ceramic capacitors (MLCCs) is found out by a combination of different isotope exchange experiments and the analysis of the resulting tracer diffusion profiles. It is shown that the incorporation of oxygen from water vapour is faster by orders of magnitude than from molecular oxygen. Chemical analysis shows the samples contain various dopants leading to a complex defect chemistry. Dysprosium is the most important dopant, acting partially as a donor and partially as an acceptor in this effectively acceptor-doped material. TEM and EELS analysis show the inhomogeneous distribution of Dy in a core-shell microstructure. The oxygen partial pressure and temperature dependence of the oxygen tracer diffusion coefficients is analysed and explained by the complex defect chemistry of Dy-doped barium titanate. Additional fast diffusion profiles are attributed to fast diffusion along grain boundaries. In addition to the barium titanate ceramics from an important technical application, oxygen diffusion in cubic, nominally undoped BaTiO3 single crystals has been studied by means of 18O2/16O2 isotope exchange annealing and subsequent determination of the isotope profiles in the solid by ToF-SIMS. It is shown that a correct description of the diffusion profiles requires the analysis of the diffusion through the surface space-charge into the material’s bulk. Surface exchange coefficients, space-charge potentials and bulk diffusion coefficients are analysed as a function of oxygen partial pressure and temperature. The data suggests that oxygen vacancies and electron holes play the key role in the formation of the equilibrium surface space-charge layers. The oxygen vacancy diffusivities and the oxygen vacancy migration enthalpy are compared to other experimentally and theoretically derived data for barium titanate and a global expression for the temperature dependence of the oxygen vacancy diffusivity is determined. The latter was used for a comparison of the oxygen vacancy diffusivity and the oxygen vacancy migration enthalpy for BaTiO3 to other perovskite oxides. Furthermore, this work shows results from cation interdiffusion experiments between BaZrO3 and SrTiO3. Thin films of barium zirconate were deposited on strontium titanate single crystals and the cation interdiffusion investigated as a function of temperature. All four cations show a main diffusion profile and an additional fast diffusion profile. Each main diffusion profile can be described independently by the thick-film solution of the diffusion equation suggesting the diffusion coefficients to be concentration independent. The fast diffusion profiles are attributed to fast diffusion of Ba and Zr along dislocations of the SrTiO3 single crystals and fast diffusion of Sr and Ti along the grain boundaries of the polycrystalline thin-film BaZrO3. The migration enthalpies of the bulk profiles for all four cations are very similar. The results suggest a complex diffusion mechanism with coupled diffusion of the cation vacancies on the A and B sites of the perovskite lattice