The potential for creating hierarchical domain structures, or mixtures of energetically degenerate phases with distinct patterns that can be modified continually, in ferroelectric thin films offers a pathway to control their mesoscale structure beyond lattice-mismatch strain with a substrate. Here, it is demonstrated that varying the strontium content provides deterministic strain-driven control of hierarchical domain structures in Pb_{1- x} Sr_x TiO₃  solid-solution thin films wherein two types, c/a and a₁ /a₂ , of nanodomains can coexist. Combining phase-field simulations, epitaxial thin-film growth, detailed structural, domain, and physical-property characterization, it is observed that the system undergoes a gradual transformation (with increasing strontium content) from droplet-like a₁ /a₂  domains in a c/a domain matrix, to a connected-labyrinth geometry of c/a domains, to a disconnected labyrinth structure of the same, and, finally, to droplet-like c/a domains in an a₁ /a₂  domain matrix. A relationship between the different mixed-phase modulation patterns and its topological nature is established. Annealing the connected-labyrinth structure leads to domain coarsening forming distinctive regions of parallel c/a and a₁ /a₂  domain stripes, offering additional design flexibility. Finally, it is found that the connected-labyrinth domain patterns exhibit the highest dielectric permittivity.

In a first-order phase transition, critical nucleus size governs nucleation kinetics, but the direct experimental test of the theory and determination of the critical nucleation size have been achieved only recently in the case of ice formation in supercooled water. The widely known metal-insulator phase transition (MIT) in strongly correlated VO_{2} is a first-order electronic phase transition coupled with a solid-solid structural transformation. It is unclear whether classical nucleation theory applies in such a complex case. In this Letter, we directly measure the critical nucleus size of the MIT by introducing size-controlled nanoscale nucleation seeds with focused ion irradiation at the surface of a deeply supercooled metal phase of VO_{2}. The results compare favorably with classical nucleation theory and are further explained by phase-field modeling. This Letter validates the application of classical nucleation theory as a parametrizable model to describe phase transitions of strongly correlated electron materials.

Controlling the domain formation in ferroelectric materials at the nanoscale is a fertile ground to explore emergent phenomena and their technological prospects. For example, charged ferroelectric domain walls in BiFeO₃ and ErMnO₃ exhibit significantly enhanced conductivity which could serve as the foundation for next-generation circuits (Estévez and Laurson, Phys. Rev. B 2015, 91, 054407). Here, we describe a concept in which polar vortices perform the same role as a ferroelectric domain wall in classical domain structures with the key difference being that the polar vortices can accommodate charged (i.e., head-to-head and tail-to-tail) domains, for example, in ferroelectric PbTiO₃/dielectric SrTiO₃ superlattices. Such a vortex domain wall structure can be manipulated in a reversible fashion under an external applied field.

Next-generation microelectronics and electrical power systems call for high-energy-density dielectric polymeric materials that can operate efficiently under elevated temperatures. However, the currently available polymer dielectrics are limited to relatively low working temperatures. Here, the solution-processable polymer nanocomposites consisting of readily prepared Al₂ O₃ fillers with systematically varied morphologies including nanoparticles, nanowires, and nanoplates are reported. The field-dependent electrical conduction of the polymer nanocomposites at elevated temperatures is investigated. A strong dependence of the conduction behavior and breakdown strength of the polymer composites on the filler morphology is revealed experimentally and is further rationalized via computations. The polymer composites containing Al₂ O₃ nanoplates display a record capacitive performance, e.g., a discharged energy density of 3.31 J cm^-3 and a charge-discharge efficiency of >90% measured at 450 MV m^-1 and 150 °C, significantly outperforming the state-of-the-art dielectric polymers and nanocomposites that are typically prepared via tedious, low-yield approaches.

Epitaxial strain is a powerful tool to induce functional properties such as ferroelectricity in thin films of materials that do not possess ferroelectricity in bulk form. In this work, a ferroelectric state was stabilized in thin films of the incipient ferroelectric, CaTiO3, through the careful control of the biaxial strain state and TiO6 octahedral rotations. Detailed structural characterization was carried out by synchrotron x-ray diffraction and scanning transmission electron microscopy. CaTiO3 films grown on La0.18Sr0.82Al0.59Ta0.41O3 (LSAT) and NdGaO3 (NGO) substrates experienced a 1.1% biaxial strain state but differed in their octahedral tilt structures. A suppression of the out-of-plane rotations of the TiO6 octahedral in films grown on LSAT substrates resulted in a robust ferroelectric I4?mm phase with remnant polarization ∼5?μC/cm2 at 10?K and Tc near 140?K. In contrast, films grown on NGO substrates with significant octahedral tilting showed reduced polarization and Tc. These results highlight the key role played by symmetry in controlling the ferroelectric properties of perovskite oxide thin films.

Understanding the phase transitions and domain evolutions of mesoscale topological structures in ferroic materials is critical to realizing their potential applications in next-generation high-performance storage devices. Here, the behaviors of a mesoscale supercrystal are studied with 3D nanoscale periodicity and rotational topology phases in a PbTiO₃ /SrTiO₃ (PTO/STO) superlattice under thermal and electrical stimuli using a combination of phase-field simulations and X-ray diffraction experiments. A phase diagram of temperature versus polar state is constructed, showing the formation of the supercrystal from a mixed vortex and a-twin state and a temperature-dependent erasing process of a supercrystal returning to a classical a-twin structure. Under an in-plane electric field bias at room temperature, the vortex topology of the supercrystal irreversibly transforms to a new type of stripe-like supercrystal. Under an out-of-plane electric field, the vortices inside the supercrystal undergo a topological phase transition to polar skyrmions. These results demonstrate the potential for the on-demand manipulation of polar topology and transformations in supercrystals using electric fields. The findings provide a theoretical understanding that may be utilized to guide the design and control of mesoscale polar structures and to explore novel polar structures in other systems and their topological nature.

Order–disorder transitions are widely explored in various vortex structures in condensed matter physics, that is, in the type-II superconductors and Bose–Einstein condensates. In this study, the ordering of the polar vortex phase in [Pb(Zr0.4Ti0.6)O3]n/(SrTiO3)n (PZT/STO) superlattices is investigated through phase-field simulations. With a large tensile substrate strain, an antiorder vortex state (where the rotation direction of the vortex arrays in the neighboring ferroelectric layers are flipped) is discovered for short-period PZT/STO superlattice. The driving force is the induced in-plane polarization in the STO layers due to the large tensile epitaxial strain. Increasing the periodicity leads to antiorder to disorder transition, resulting from the high energy of the head-to-head/tail-to-tail domain structure in the STO layer. On the other hand, when the periodicity is kept constant in short-period superlattices, the order–disorder–antiorder transition can be engineered by mediating the substrate strain, due to the competition between the induction of out-of-plane (due to interfacial depolarization effect) and in-plane (due to strain) polarization in the STO layer. The 3D ordering of such polar vortices is still a topic of significant current interest and it is envisioned that this study will spur further interest toward the understanding of order–disorder transitions in ferroelectric topological structures.

In ferroelectric heterostructures, the interaction between intrinsic polarization and the electric field generates a rich set of localized electrical properties. The local electric field is determined by several connected factors, including the charge distribution of individual unit cells, the interfacial electromechanical boundary conditions, and chemical composition of the interfaces. However, especially in ferroelectric perovskites, a complete description of the local electric field across micro-, nano-, and atomic-length scales is missing. Here, by applying four-dimensional scanning transmission electron microscopy (4D STEM) with multiple probe sizes matching the size of structural features, we directly image the electric field of polarization vortices in (PbTiO3)16/(SrTiO3)16 superlattices and reveal different electric field configurations corresponding to the atomic scale electronic ordering and the nanoscale boundary conditions. The separability of two different fields probed by 4D STEM offers the possibility to reveal how each contributes to the electronic properties of the film.

Very sensitive responses to external forces are found near phase transitions. However, transition dynamics and preequilibrium phenomena are difficult to detect and control. We have observed that the equilibrium domain structure following a phase transition in ferroelectric and ferroelastic BaTiO_{3} is attained by halving of the domain periodicity multiple times. The process is reversible, with periodicity doubling as temperature is increased. This observation is reminiscent of the period-doubling cascades generally observed during bifurcation phenomena, and, thus, it conforms to the "spatial chaos" regime earlier proposed by Jensen and Bak [Phys. Scr. T 9, 64 (1985)PHSTER0281-184710.1088/0031-8949/1985/T9/009] for systems with competing spatial modulations.