An Intriguing Polarization Configuration of Mixed Ising- and Néel-Type Model in the Prototype PbZrO₃-Based...

Antiferroelectrics are of great academic and technological interest due to their excellent strain and energy storage properties, while the incommensurate modulation-related complex configuration of polarization remains unclear. In this study, an intriguing polarization configuration of mixed Ising- and Néel-type has been established in the prototype PbZrO₃-based antiferroelectric materials via the combination of high-resolution synchrotron X-ray and neutron diffraction investigations. Such unusual polarization configuration of antiferroelectrics shows the internal coupling, which mainly contributes from the displacement of the A-site and the distortion of the AO₁₂ and BO₆ polyhedra. The electric dipole oscillates in the (001)_P plane, and its magnitude and direction show obvious modulation characteristics resulting in a neither antiparallel nor fully compensated polarization configuration, which is completely different from the traditional view of antiferroelectricity. There is an antiferroelectric feature along the [110]_P direction, while there is a ferrielectric one along the [1̅10]_P direction in which the net polarization can reach 12 μC/cm². The maximum local polarization can reach 4.3 μC/cm² in the [110]_P direction and 27.6 μC/cm² in the [1̅10]_P direction. This work will be very helpful for the development of antiferroelectric theories and the design of novel energy storage materials.