Evidence for pressure induced polarization rotation, octahedral tilting and reentrant ferroelectric phase in tetragonal (Pb0.5Bi0.5)(Ti0.5Fe0.5)O3

TL;DR

This study investigates pressure-induced phase transitions in a modified tetragonal PbTiO3-based material, providing experimental evidence for antiferrodistortive transitions and reentrant ferroelectric phases, clarifying previous controversies.

Contribution

First experimental confirmation of antiferrodistortive transition and reentrant ferroelectric phase in pressure-induced phase behavior of BiFeO3-modified PbTiO3.

Findings

AFD transition observed at ~2.15 GPa with superlattice reflections.

Reentrant ferroelectric phase Cc-II stabilizes above ~7 GPa.

Octahedral tilting aids in volume reduction and phase stabilization.

Abstract

Despite the technological significance of the tetragonal PbTiO3 for the piezoelectric transducer industry, its high pressure behaviour is quite controversial as two entirely different scenarios, involving pressure induced (1) morphotropic phase boundary (MPB) like structural transition with concomitant rotation of the ferroelectric polarization vector and (2) antiferrodistortive (AFD) phase transition followed by emergence of a reentrant ferroelectric phase, have been proposed in recent theoretical and experimental studies. We have attempted to address these controversies through a high resolution synchrotron x-ray diffraction study of pressure induced phase transitions in the tetragonal phase of a modified PbTiO3 composition containing 50% BiFeO3, where BiFeO3 was added to enhance the AFD instability of PbTiO3. We present here the first experimental evidence for the presence of the characteristic superlattice reflections due to an AFD transition at a moderate pressure pc1 ~2.15 GPa in broad agreement with scenario (2), but the high pressure ferroelectric phase belongs to the monoclinic space group Cc, and not the tetragonal space group I4cm predicted under scenario (2), which permits the rotation of the ferroelectric polarization vector as per scenario (1). We show that the monoclinic distortion angle and ferroelectric polarization of the Cc phase initially decrease with increasing pressure for p < 7 GPa, but start increasing above pc2 ~ 7 GPa due to an isostructural Cc-I to Cc-II transition reminiscent of MA(apc > bpc ~ cpc) to MB(apc< bpc ~ cpc) transition predicted for MPB systems. We also show that octahedral tilting provides an efficient mechanism for accommodating pressure induced volume reduction for the stabilisation of the reentrant ferroelectric phase Cc-II.