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 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.

Perovskite solid solutions ${\mathrm{PbHfO}}_3\text{−}{\mathrm{PbSnO}}_3$ offer valuable opportunities for studying the formation mechanisms of incommensurate phases, owing to the presence of an intermediate (between cubic and incommensurate) phase, which is stabilized in ${\mathrm{PbHfO}}_3$ upon ${\mathrm{PbSnO}}_3$ admixture. Here, an x-ray diffuse scattering signal is used to quantify the evolution of susceptibilities related to different modes of distortion (ferroelectric, incommensurate, antiferrodistortive) as a function of temperature and the results are critically compared to the predictions of a minimal symmetry-based Landau-like model with two coupled order parameters (ferroelectric and antiferrodistortive) and an incommensurate order parameter being interpreted as inhomogeneous polarization. Experimentally, we observe a Curie-Weiss-like linear dependence of ferroelectric stiffness (inverse of susceptibility related to homogeneous polarization fluctuations) in the cubic phase down to about 50 K above the transition to the intermediate phase, where this dependence nearly saturates. Upon cooling down to the intermediate phase, the maximum of susceptibility shifts gradually to the nonzero wave vector, where another Curie-Weiss-like linear stiffness trend is established, but with respect to the incommensurate order parameter. Symmetry of diffuse scattering distributions indicates an orthorhombic symmetry of the intermediate phase. A notable temperature dependence of the constant that describes the energy of polarization inhomogeneities is observed experimentally, which is in disagreement with the model expectations. The specifics of this dependence suggest the presence of a nearly temperature-independent characteristic length scale for inhomogeneities across several phases. Other differences with the model suggest that the incommensurate order parameter cannot be straightforwardly identified with weakly inhomogeneous ferroelectric polarization.

Control and analysis of the crystal phase in semiconductor nanowires are of high importance due to the new possibilities for strain and band gap engineering for advanced nanoelectronic and nanophotonic devices. In this letter, we report the growth of the self-catalyzed GaP nanowires with a high concentration of wurtzite phase by molecular beam epitaxy on Si (111) and investigate their crystallinity. Varying the growth temperature and V/III flux ratio, we obtained wurtzite polytype segments with thicknesses in the range from several tens to 500 nm, which demonstrates the high potential of the phase bandgap engineering with highly crystalline self-catalyzed phosphide nanowires. The formation of rotational twins and wurtzite polymorph in vertical nanowires was observed through complex approach based on transmission electron microscopy, powder X-ray diffraction, and reciprocal space mapping. The phase composition, volume fraction of the crystalline phases, and wurtzite GaP lattice parameters were analyzed for the nanowires detached from the substrate. It is shown that the wurtzite phase formation occurs only in the vertically-oriented nanowires during vapor-liquid-solid growth, while the wurtzite phase is absent in GaP islands parasitically grown via the vapor-solid mechanism. The proposed approach can be used for the quantitative evaluation of the mean volume fraction of polytypic phase segments in heterostructured nanowires that are highly desirable for the optimization of growth technologies.