Local monoclinic polarization rotation promoting a different domain alignment in rhombohedral Pb(Zr,Ti)O3 ferroelectrics

Domain switching takes a substantial role in the macroscopic electrical properties of perovskite-type ferroelectric materials. However, the attainable domain alignment in polycrystalline states is often far away from the saturation due to the constraint of long-range crystallographic symmetry. Herein, we report a field-induced saturated polarization alignment, facilitated by local monoclinic polarization rotation in conventional rhombohedral $\mathrm{Pb}({\mathrm{Zr}}_{0.54}{\mathrm{Ti}}_{0.46}){\mathrm{O}}_{3}$ via advanced electrical basing in situ synchrotron x-ray diffraction and pair distribution function measurements. It is found that the polarization alignment can reach the upper limit of theoretically calculated value in rhombohedral ceramic during high electric-field poling, and such a state can be maintained upon removal of electric field. In situ pair distribution function analysis demonstrates the occurrence of monoclinic distortion at local length $(<10\phantom{\rule{0.16em}{0ex}}\AA{})$, where the electric-field driven polarization rotation emerges, and promoting the alignment of polarization variations. Concurrently, large local piezoelectric strain $(1000\phantom{\rule{0.16em}{0ex}}\mathrm{pm}/\mathrm{V})$ and intrinsic lattice piezoelectric response $(1400\phantom{\rule{0.16em}{0ex}}\mathrm{pm}/\mathrm{V})$ during poling are found to be generated, while large remanent strains are also observed. These results offer fresh insight into the role of local structure in domain switching behavior and have potential for the theoretical investigation of domain alignment in ferroelectrics.