Under electrical bias, mixed ionic conductors such as SrTiO₃ are characterized by oxygen vacancy migration which leads to resistance degradation. The defect chemistry to describe the relationship between conductivity and oxygen vacancies is usually obtained by high temperature conductivity data or quenching experiments. These techniques can investigate the equilibrated state only. Here, we introduce a new approach using in-situ impedance studies with applied dc voltage to analyze the temperature dependent electrical properties of degraded SrTiO₃ single crystals. This procedure is most beneficial since it includes electric field driven effects. The benefits of the approach are highlighted by comparing acceptor doped and undoped SrTiO₃. This approach allows the determination of the temperature activation of both anodic and cathodic conductivity of Fe-doped SrTiO₃ in the degraded state. The anodic activation energy matches well with the published results, while the activation energy of the degraded cathode region reported here is not in agreement with earlier assumptions. The specific discrepancies of the experimental data and the published defect chemistry are discussed, and a defect chemistry model that includes the strong temperature dependence of the electron conductivity in the cathode region is proposed.

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