Impedance spectroscopy of PZT ceramics- measuring diffusion coefficients, mixed conduction, and Pb loss

Sintering of lead zirconate titanate (PZT) at high temperatures results in loss of Pb unless an ambient Pb activity is maintained. The tell-tale sign of Pb loss is an increased conductivity, usually manifested in unacceptably high values of tan ¿. The conductivity is caused by oxygen vacancies and/or electron holes which are a byproduct of Pb evaporation. In the first part of this paper, it is shown how impedance spectroscopy can be used to separate ionic and electronic conductivity in a properly designed sample by selection of appropriate boundary conditions. Subsequently, impedance is used to probe defect concentrations in PZT during prolonged annealing at 700°C. It is found that oxygen vacancies are generated during annealing in air but the rate of generation actually decreases upon lowering the ambient pO₂. These results are explained by a model of Pb evaporation which, in this case, leads predominantly to oxygen vacancy generation. In principle, this effect could be used to generate a specific vacancy concentration in similar Pb-based oxides.