Influence of long-range cation order on relaxor properties of doped Pb (Mg1/3 Nb2/3) O3 ceramics

The 1:1 B -site cation order in Pb (Mg1/3 Nb2/3) O3 relaxor ferroelectric ceramics was significantly enhanced by doping of minor amounts of La3+, Sc3+, or W6+ (less than 3 at.%) combined with a slow cooling procedure. Transmission electron microscopy examination confirmed the size increase of the cation-ordered regions embedded in a disordered matrix in the samples that were slowly cooled after sintering. The average cation ordering parameter (S) determined from x-ray diffraction data in these partially ordered samples was about 0.3-0.4. The ferroelectric properties and dielectric relaxation were compared in partially ordered and disordered (S=0) samples with the same composition. It was found that typical relaxor behavior was preserved in partially ordered ceramics. Furthermore, the temperature and diffuseness of the characteristic relaxor permittivity peak and the parameters of dielectric relaxation (in particular, the distribution of relaxation times and the Vogel-Fulcher freezing temperature) were practically independent of S. In contrast, the diffuseness of the phase transition from the ferroelectric phase (induced by external electric field) to the ergodic relaxor phase appeared to be much larger in the disordered samples than in the partially ordered ones (this diffuseness was assessed using pyroelectric current and ferroelectric hysteresis loops). These results suggest that cation ordering did not influence the behavior of polar nanoregions which are responsible for the dielectric response in the ergodic relaxor phase but significantly influenced the ferroelectric phase transition. The results are interpreted in terms of different types of polar regions in the disordered matrix and cation-ordered domains.