High-field/high-frequency EPR of paramagnetic functional centers in Cu2+- and Fe3+-modified polycrystalline Pb[ZrxTi1−x]O3 ferroelectrics

Copper(II)- and iron(III)-modified Pb[Zr(x)Ti(1-x)]O3 ferroelectrics were investigated by means of high-field/high-frequency EPR. The results obtained suggest that Cu2+ and Fe3+ both substitute as acceptor centers for [Zr,Ti]4+. Whereas for the iron-doped system the charge compensating oxygen vacancies (V(O)**) lead to the formation of charged (Fe'(Ti-)V(O)**)* defect associates, no such associates have been observed for the copper-modified system. As regards the morphotropic phase boundary, the model of a mesoscopic mixing of the pure-member phases has been refined to a picture in which a nanoscale composition distribution prevails.