Oxygen nonstoichiometry and dielectric evolution of BaTiO3. Part I—improvement of insulation resistance with reoxidation

Abstract

Impedance spectroscopy, transmission electron microscopy, and electron energy-loss spectroscopy are used to correlate local electrical properties with the microstructure and microchemistry of BaTiO3 in Ni-electrode multilayer ceramic capacitors. High densities of linear defects and some grains with structural modulations are observed in BaTiO3 grains in the as-cofired capacitors. The modulated structure is formed on {111} planes of the BaTiO3. Both types of structural defects are associated with high concentrations of oxygen vacancies. In particular, the oxygen content in the BaTiO3 grains that are in direct contact with the internal Ni electrodes is less uniform with a systematic decrease in oxygen content towards the electrode. In the capacitors that are reoxidized in a higher oxygen partial pressure at lower temperature, the BaTiO3 grains are almost free of linear defects and structural modulations and the oxygen content is homogeneous throughout the BaTiO3 active layers. A concomitant improvement in the total insulation resistance is observed.