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Over the last 30 years, the study of ferroelectric oxides has been revolutionized by the implementation of epitaxial‐thin‐film‐based studies, which have driven many advances in the understanding of ferroelectric physics and the realization of novel polar structures and functionalities. New questions have motivated the development of advanced synthesis, characterization, and simulations of epitaxial thin films and, in turn, have provided new insights and applications across the micro‐, meso‐, and macroscopic length scales. This review traces the evolution of ferroelectric thin‐film research through the early days developing understanding of the roles of size and strain on ferroelectrics to the present day, where such understanding is used to create complex hierarchical domain structures, novel polar topologies, and controlled chemical and defect profiles. The extension of epitaxial techniques, coupled with advances in high‐throughput simulations, now stands to accelerate the discovery and study of new ferroelectric materials. Coming hand‐in‐hand with these new materials is new understanding and control of ferroelectric functionalities. Today, researchers are actively working to apply these lessons in a number of applications, including novel memory and logic architectures, as well as a host of energy conversion devices.

Ferroelectric materials exhibit spontaneous polarization that can be switched by electric field. Beyond traditional applications as nonvolatile capacitive elements, the interplay between polarization and electronic transport in ferroelectric thin films has enabled a path to neuromorphic device applications involving resistive switching. A fundamental challenge, however, is that finite electronic conductivity may introduce considerable power dissipation and perhaps destabilize ferroelectricity itself. Here, tunable microwave frequency electronic response of domain walls injected into ferroelectric lead zirconate titanate (PbZr_0.2Ti_0.8O₃) on the level of a single nanodomain is revealed. Tunable microwave response is detected through first‐order reversal curve spectroscopy combined with scanning microwave impedance microscopy measurements taken near 3 GHz. Contributions of film interfaces to the measured AC conduction through subtractive milling, where the film exhibited improved conduction properties after removal of surface layers, are investigated. Using statistical analysis and finite element modeling, we inferred that the mechanism of tunable microwave conductance is the variable area of the domain wall in the switching volume. These observations open the possibilities for ferroelectric memristors or volatile resistive switches, localized to several tens of nanometers and operating according to well‐defined dynamics under an applied field.

Epitaxial strain has been shown to produce dramatic changes to the orbital structure in transition metal perovskite oxides and, in turn, the rate of oxygen electrocatalysis therein. Here, epitaxial strain is used to investigate the relationship between surface electronic structure and oxygen electrocatalysis in prototypical fuel cell cathode systems. Combining high‐temperature electrical‐conductivity‐relaxation studies and synchrotron‐based X‐ray absorption spectroscopy studies of La_0.5Sr_0.5CoO₃and La_0.8Sr_0.2Co_0.2Fe_0.8O₃thin films under varying degrees of epitaxial strain reveals a strong correlation between orbital structure and catalysis rates. In both systems, films under biaxial tensile strain simultaneously exhibit the fastest reaction kinetics and lowest electron occupation in thed_z²orbitals. These results are discussed in the context of broader chemical trends and electronic descriptors are proposed for oxygen electrocatalysis in transition metal perovskite oxides.

The rapid development of computing applications demands novel low‐energy consumption devices for information processing. Among various candidates, magnetoelectric heterostructures hold promise for meeting the required voltage and power goals. Here, a route to low‐voltage control of magnetism in 30 nm Fe_0.5Rh_0.5/100 nm 0.68PbMg_1/3Nb_2/3O₃‐0.32PbTiO₃(PMN‐PT) heterostructures is demonstrated wherein the magnetoelectric coupling is achieved via strain‐induced changes in the Fe_0.5Rh_0.5mediated by voltages applied to the PMN‐PT. We describe approaches to achieve high‐quality, epitaxial growth of Fe_0.5Rh_0.5on the PMN‐PT films and, a methodology to probe and quantify magnetoelectric coupling in small thin‐film devices via studies of the anomalous Hall effect. By comparing the spin‐flop field change induced by temperature and external voltage, the magnetoelectric coupling coefficient is estimated to reach ≈7 × 10⁻⁸ s m⁻¹at 325 K while applying a −0.75 V bias.

The hafnate perovskites PbHfO₃(antiferroelectric) and SrHfO₃(“potential” ferroelectric) are studied as epitaxial thin films on SrTiO₃(001) substrates with the added opportunity of observing a morphotropic phase boundary (MPB) in the Pb_1−xSr_xHfO₃system. The resulting (240)‐oriented PbHfO₃(Pba2) films exhibited antiferroelectric switching with a saturation polarization ≈53 µC cm⁻²at 1.6 MV cm⁻¹, weak‐field dielectric constant ≈186 at 298 K, and an antiferroelectric‐to‐paraelectric phase transition at ≈518 K. (002)‐oriented SrHfO₃films exhibited neither ferroelectric behavior nor evidence of a polarP4mmphase . Instead, the SrHfO₃films exhibited a weak‐field dielectric constant ≈25 at 298 K and no signs of a structural transition to a polar phase as a function of temperature (77–623 K) and electric field (–3 to 3 MV cm⁻¹). While the lack of ferroelectric order in SrHfO₃removes the potential for MPB, structural and property evolution of the Pb_1−xSr_xHfO₃(0 ≤x < 1) system is explored. Strontium alloying increased the electric‐breakdown strength (E_B) and decreased hysteresis loss, thus enhancing the capacitive energy storage density (U_r) and efficiency (η). The composition, Pb_0.5Sr_0.5HfO₃produced the best combination ofE_B = 5.12 ± 0.5 MV cm⁻¹,U_r = 77 ± 5 J cm⁻³, and η = 97 ± 2%, well out‐performing PbHfO₃and other antiferroelectric oxides.

Harvesting waste heat for useful purposes is an essential component of improving the efficiency of primary energy utilization. Today, approaches such as pyroelectric energy conversion are receiving renewed interest for their ability to turn wasted energy back into useful energy. From this perspective, the need for these approaches, the basic mechanisms and processes underlying their operation, and the material and device requirements behind pyroelectric energy conversion are reviewed, and the potential for advances in this area is also discussed.

Deterministic control of the intrinsic polarization state of ferroelectric thin films is essential for device applications. Independently of the well‐established role of electrostatic boundary conditions and epitaxial strain, the importance of growth temperature as a tool to stabilize a target polarization state during thin film growth is shown here. Full control of the intrinsic polarization orientation of PbTiO₃thin films is demonstrated—from monodomain up, through polydomain, to monodomain down as imaged by piezoresponse force microscopy—using changes in the film growth temperature. X‐ray diffraction and scanning transmission electron microscopy reveal a variation ofc‐axis related to out‐of‐plane strain gradients. These measurements, supported by Ginzburg–Landau–Devonshire free energy calculations and Rutherford backscattering spectroscopy, point to a defect mediated polarization gradient initiated by a temperature dependent effective built‐in field during growth, allowing polarization control not only under specific growth conditions, but ex‐situ, for subsequent processing and device applications.

We report the pulsed‐laser deposition of epitaxial double‐perovskite Bi₂FeCrO₆(BFCO) films on the (001)‐, (110), and (111)‐oriented single‐crystal SrTiO₃substrates. All of the BFCO films with various orientations show theandsuperlattice‐diffraction peaks. The intensity ratios between the‐superlattice and the main 111‐diffraction peak can be tailored by simply adjusting the laser repetition rate and substrate temperature, reaching up to 4.4%. However, both optical absorption spectra and magnetic measurements evidence that the strong superlattice peaks are not correlated with theB‐site Fe³⁺/Cr³⁺cation ordering. Instead, the epitaxial (111)‐oriented Bi₂FeCrO₆films show an enhanced remanent polarization of 92 μC/cm²at 10 K, much larger than the predicted values by density‐functional theory calculations. Positive‐up‐negative‐down (PUND) measurements with a time interval of 10 μs further support these observations. Therefore, our experimental results reveal that the strong superlattice peaks may come fromA‐ orB‐site cation shifts along the pseudo‐cubic [111] direction, which further enhance the ferroelectric polarization of the BFCO thin films.

Topological spin/polarization structures in ferroic materials continue to draw great attention as a result of their fascinating physical behaviors and promising applications in the field of high‐density nonvolatile memories as well as future energy‐efficient nanoelectronic and spintronic devices. Such developments have been made, in part, based on recent advances in theoretical calculations, the synthesis of high‐quality thin films, and the characterization of their emergent phenomena and exotic phases. Herein, progress over the last decade in the study of topological structures in ferroic thin films and heterostructures is explored, including the observation of topological structures and control of their structures and emergent physical phenomena through epitaxial strain, layer thickness, electric, magnetic fields, etc. First, the evolution of topological spin structures (e.g., magnetic skyrmions) and associated functionalities (e.g., topological Hall effect) in magnetic thin films and heterostructures is discussed. Then, the exotic polar topologies (e.g., domain walls, closure domains, polar vortices, bubble domains, and polar skyrmions) and their emergent physical properties in ferroelectric oxide films and heterostructures are explored. Finally, a brief overview and prospectus of how the field may evolve in the coming years is provided.

Memristors with excellent scalability have the potential to revolutionize not only the field of information storage but also neuromorphic computing. Conventional metal oxides are widely used as resistive switching materials in memristors. Interface‐type memristors based on ferroelectric materials are emerging as alternatives in the development of high‐performance memory devices. A clear understanding of the switching mechanisms in this type of memristors, however, is still in its early stages. By comparing the bipolar switching in different systems, it is found that the switchable diode effect in ferroelectric memristors is controlled by polarization modulated Schottky barrier height and polarization coupled interfacial deep states trapping/detrapping. Using semiconductor theories with consideration of polarization effects, a phenomenological theory is developed to explain the current–voltage behavior at the metal/ferroelectric interface. These findings reveal the critical role of the interaction among polarization charges, interfacial defects, and Schottky interface in controlling ferroelectric resistive switching and offer the guidance to design ferroelectric memristors with enhanced performance.