Effect of off-center ion substitution in morphotropic lead zirconate titanate composition

Abstract

A detailed study of the effect of off-center donor ion (Sc3+) substitution on structural, microstructural, optical, dielectric, electrical, and ferroelectric properties of morphotropic composition of lead zirconate titanate electroceramics with the stoichiometric formula Pb0.85Sc0.10Zr0.53Ti0.47O3 (PSZT) and synthesized using a high energy solid-state reaction technique was carried out. Powder x-ray diffractometry was used to identify the stabilized tetragonal phase (space group P4mm) with considerably reduced tetragonal strain, c/a= 1.005. An analysis of the thermal dependence of the Raman results indicated a smooth displacive (ferroelectric-paraelectric) phase transition as revealed by the observed disappearance of the soft modes A1 (1TO) and A1 (2TO) above 460 K. The dielectric response of Pt/PSZT/Pt metal-ferroelectric-metal capacitors was probed over a wide range of thermal excursions (85–600 K) and ac signal frequencies (102–106 Hz). Thermally activated dynamic and static conduction processes indicate hopping conduction mechanism (Eact ≤ 0.015 eV) and the formation of small polarons caused by the electron and/or hole-lattice (phonon) interaction (Eact ≥ 0.1 eV) at low (100–300 K) and high temperatures (300–600 K), respectively. The reduction in remnant polarization obtained is in good agreement with the largely reduced tetragonal strain observed in this sample, (Pr ∝c/a−1). DC conduction is dominated by Poole-Frenkel mechanism that assumes a Coulombic attraction between detrapped electrons and positively charged stationary defect species in the polycrystalline matrix.