Superoxidation and electrochemical reactions during switching in Pb(Zr,Ti)O₃ ceramics

Under ferroelectric switching in Pb(Zr,Ti)O₃ (PZT) ceramics, we demonstrate that oxygen gas is emitted and degrades electrode microstructure. The oxygen is a direct result of the defect chemistry associated with superoxidation which is established during the processing of the ceramics. Under high alternating electric fields, electron injection into the ceramic surface induces a reduction process, and surface layers are believed to change from a p-type electronic compensation to an ionic compensation of oxygen vacancies and A-site lead vacancies. During this process, we noticed progressive changes in capacitance, loss, remnant polarization, and coercive field. The wider implications of this observation for PZT thin film nonvolatile memories are discussed in brief.