Antiferroelectrics are essential ingredients for the widely applied piezoelectric and ferroelectric materials: the most common ferroelectric, lead zirconate titanate is an alloy of the ferroelectric lead titanate and the antiferroelectric lead zirconate. Antiferroelectrics themselves are useful in large digital displacement transducers and energy-storage capacitors. Despite their technological importance, the reason why materials become antiferroelectric has remained allusive since their first discovery. Here we report the results of a study on the lattice dynamics of the antiferroelectric lead zirconate using inelastic and diffuse X-ray scattering techniques and the Brillouin light scattering. The analysis of the results reveals that the antiferroelectric state is a ‘missed’ incommensurate phase, and that the paraelectric to antiferroelectric phase transition is driven by the softening of a single lattice mode via flexoelectric coupling. These findings resolve the mystery of the origin of antiferroelectricity in lead zirconate and suggest an approach to the treatment of complex phase transitions in ferroics.

Antiferroelectric lead zirconate is the key ingredient in modern ferroelectric and piezoelectric functional solid solutions. By itself it offers opportunities in new-type non-volatile memory and energy storage applications. A highly useful and scientifically puzzling feature of this material is the competition between the ferro- and antiferroelectric phases due to their energetic proximity, which leads to a challenge in understanding of the critical phenomena driving the formation of the antiferroelectric structure. We show that application of hydrostatic pressure drastically changes the character of critical lattice dynamics and enables the soft-mode-driven incommensurate phase transition sequence in lead zirconate. In addition to the long known cubic and antiferroelectric phases we identify the new non-modulated phase serving as a bridge between the cubic and the incommensurate phases. The pressure effect on ferroelectric and incommensurate critical dynamics shows that lead zirconate is not a single-instability-driven system.

We report the results of a comprehensive study of the critical dynamics of the classical perovskite antiferroelectric ${\mathrm{PbZrO}}_3$. The combination of inelastic x-ray and diffuse x-ray scattering techniques and Brillouin light scattering was used. It is found that the dispersion of the transverse acoustic (TA) phonons is strongly anisotropic. The dispersion curve of the in-plane polarized TA phonons propagating in [1 1 0] direction demonstrates pronounced softening. Slowing down of the excitations at $R$ point is found, it is manifested in growing of the central peak. This slowing down is too weak to be considered as a primary origin of the corresponding order parameter. Obtained results are treated in terms of TA-transverse optic (TO) flexoelectric mode coupling. It is demonstrated that the structural phase transformation in ${\mathrm{PbZrO}}_3$ can be considered as the result of the only intrinsic instability associated with the ferroelectric soft mode.

Complementary diffuse and inelastic synchrotron x-ray scattering measurements of lead zirconate-titanate single crystals with composition near the morphotropic phase boundary ($x=0.475$) are reported. In the temperature range $293\mathrm{K}<T<400\mathrm{K}$ a highly anisotropic quasielastic diffuse scattering is observed. Above 400 K this scattering disappears. Its main features can be reproduced by the model of inhomogeneous lattice deformations caused by inclusions of a tetragonal phase into a rhombohedral or monoclinic phase. This observation supports the idea that PZT at its morphotropic phase boundary is essentially structurally inhomogeneous.

We report a type of structural phase transitions in dielectric materials: the triggered incommensurate (IC) transition. We demonstrate evidence for such a transition in the perovskite antiferroelectric ${\mathrm{PbHfO}}_3$ by means of single-crystal x-ray diffraction, diffuse, and inelastic-scattering experiments, which we interpret using the Landau theory of phase transitions. This transition is not driven by an IC soft mode, as is the case for the majority of IC dielectrics, but by the soft mode associated with a different, coexisting order parameter related to antiferrodistortive (AFD) tilts of the oxygen octahedra. When cooling from the high-temperature cubic phase these two order parameters are established simultaneously and discontinuously at $T_{\text{IC}}\approx 468$ K. Two lattice instabilities are present in the cubic phase: AFD instability with critical temperature $T_0\approx 441$ K and ferroelectric instability with $T_0\approx 408$ K. The IC instability is absent. The analysis of the transition mechanism within the Landau theory of coupled order parameters indicates that the transition is of triggered character, conditioned upon the attractive biquadratic coupling between the IC modulation and the AFD octahedral tilts, and is driven by the AFD soft mode.

Applications of epitaxial antiferroelectrics face scientific challenges, such as limited understanding of degraded (in comparison to bulk) switching behavior and its relation to nanoscale structural organization. We report on an unusual structural response of ${\mathrm{PbZrO}}_3/{\mathrm{SrRuO}}_3/{\mathrm{SrTiO}}_3$ (001) heterostructures to precritical (lower than required for switching) electric fields. In situ x-ray diffraction shows a ferrielectric-like structure, which forms gradually upon increasing the applied field and makes up a heterophase state with the host antiferroelectric phase. The field-induced structure is similar to the antiferroelectric parent phase in the octahedral-tilt pattern, but differs from it in the lead-ion displacement pattern. The latter can be encoded as $\uparrow \uparrow \uparrow \uparrow \downarrow \uparrow \uparrow \downarrow$ provided that the antiferroelectric structure is encoded as $\downarrow \downarrow \uparrow \uparrow$. We propose that the unusual commensurateness (as opposed to the more ubiquitous incommensuration in similar materials) between the modulation periods of host and guest phases can be explained by accounting for the energy of heterophase boundaries, which is important in dense nanostructures due to the high surface-to-bulk ratio of nanodomains. An analysis using the ab-initio-correlated, but empirical (parametrized) energy model suggests that the observed field-induced structure is likely to be selected in ${\mathrm{PbZrO}}_3$ instead of the others in the case when the above commensuration effect is at play. The results point to the mechanism leading to the smearing of polarization-field loops in such heterostructures and suggest a perspective for the controlled creation of delicate dipolar orderings for ferroic-based memory.