Mobile Domain Walls as a Bridge between Nanoscale Conductivity and Macroscopic Electromechanical Response

The interfaces in complex oxides present unique properties exploitable in nanoscale devices. Recent studies on ferroelectric BiFeO₃, BaTiO₃, and Pb(Zr,Ti)O₃ have revealed an unusually high electric conductivity of the domain walls (DWs), adding another degree of freedom for controlling the local properties of these materials. While most of the investigations are focused on thin films for nanoscale applications, many practical devices, including piezoelectric sensors, actuators, and transducers, rely on the macroscopic properties of bulk polycrystalline materials where the average effect of local properties should be small. It is shown that in polycrystalline BiFeO₃ the local domain‐wall conductivity interferes with the dynamics of the DWs within the grains, resulting in an unexpectedly large effect on the macroscopic piezoelectric response. The results thus bridge the local conductivity and the macroscopic piezoelectricity via domain‐wall dynamics, revealing that the domain‐wall conductivity must be considered when interpreting and controlling macroscopic electromechanical properties.     

Origin of Grain Size Effects on Voltage‐Driven Ferroelastic Domain Evolution in Polycrystalline Tetragonal Lead Zirconate Titanate Thin Film

Grain size effects on electromechanical properties and voltage‐driven ferroelastic domain wall motion are a well‐known phenomenon in polycrystalline ferroelectrics. Here, the origin of the grain size effects on voltage‐driven ferroelastic domain wall motion is presented with the direct observation of ferroelastic domain evolution with applied DC voltage by piezoelectric force microscopy and polarization hysteresis loop. It is demonstrated that the microstructure parameter for controlling the voltage‐driven ferroelastic domain wall motion is the number of colonies of stripe domains in a grain rather than the grain size. Single colony grains do not show considerable out‐of‐plane (001) domain width change whereas multiple colony grains exhibit significant domain width increase with an applied DC voltage. No independent grain size effect on ferroelastic domain wall motion is observed in the grain size range 0.6–1.6 µm.     

Constructing Polymorphic Nanodomains in BaTiO3 Films via Epitaxial Symmetry Engineering

Ferroelectric materials owning a polymorphic nanodomain structure usually exhibit colossal susceptibilities to external mechanical, electrical, and thermal stimuli, thus holding huge potential for relevant applications. Despite the success of traditional strategies by means of complex composition design, alternative simple methods such as strain engineering have been intensively sought to achieve a polymorphic nanodomain state in lead‐free, simple‐composition ferroelectric oxides in recent years. Here, a nanodomain configuration with morphed structural phases is realized in an epitaxial BaTiO₃ film grown on a (111)‐oriented SrTiO₃ substrate. Using a combination of experimental and theoretical approaches, it is revealed that a threefold rotational symmetry element enforced by the epitaxial constraint along the [111] direction of BaTiO₃ introduces considerable instability among intrinsic tetragonal, orthorhombic, and rhombohedral phases. Such phase degeneracy induces ultrafine ferroelectric nanodomains (1–10 nm) with low‐angle domain walls, which exhibit significantly enhanced dielectric and piezoelectric responses compared to the (001)‐oriented BaTiO₃ film with uniaxial ferroelectricity. Therefore, the finding highlights the important role of epitaxial symmetry in domain engineering of oxide ferroelectrics and facilitates the development of dielectric capacitors and piezoelectric devices.     

Epitaxial Ferroelectric Heterostructures with Nanocolumn‐Enhanced Dynamic Properties

The possibility to tailor ferroelectricity by controlling epitaxial strain in thin films and heterostructures of complex metal oxides is well established. Here it is demonstrated that apart from this mechanism, 3D film growth during heteroepitaxy can be used to favor specific domain configurations that lead to step‐like polarization switching and a giant nonlinear dielectric response in sub‐switching ac electric fields. A combination of cube‐on‐cube epitaxial growth and the formation of columnar structures during pulsed laser deposition of Pb_0.5Sr_0.5TiO₃ films on La_0.5Sr_0.5CoO₃ bottom electrode layers and MgO (001) substrates stabilizes ferroelectric nanodomains with enhanced dynamic properties. In the Pb_0.5Sr_0.5TiO₃ films, a‐ and c‐oriented epitaxial columns grow from the bottom to the top of the film leading to random polydomain architectures with strong associations between the ferroelectric domains and the nanocolumns. Polarization switching in the two domain populations is initiated at distinctive fields due to domain wall pinning on column boundaries. Moreover, piezoelectric coupling between ferroelectric domains leads to strong interdomain elastic interactions, which result in an enhanced Rayleigh‐type dielectric nonlinearity. The growth of epitaxial films with 3D columnar structures opens up new routes towards the engineering of enhanced ferroelectric and electromechanical functions in a broad class of complex oxide materials.     

A Ferroelectric Ferromagnetic Composite Material with Significant Permeability and Permittivity

Composite materials containing both ferroelectric and ferromagnetic phases have been synthesized from nanometer‐sized powders of BaTiO₃ (ferroelectric phase) and NiCuZn ferrite (ferromagnetic phase) by a standard ceramic method. The coexistence of magnetic and electric hysteresis in the composite material has been observed at room temperature. Upon the application of magnetic and electric fields, the magnetization and electric polarization of the composite material can easily be tuned based on the changing BaTiO₃ content of the materials studied. These composite materials exhibit both excellent dielectric and soft‐magnetic properties with a variation of the frequency. Our results strongly suggest that this composite material may be the best candidate for the development of truly integrated passive filters. Due to the combination of both inductance and capacitance in one material, the adoption of an integrated passive filter could greatly reduce the size of printed circuit boards and could efficiently suppress electromagnetic interference, thereby enabling significant miniaturization of electronic elements and devices.     

Mechanical Confinement: An Effective Way of Tuning Properties of Piezoelectric Crystals

Using <001>‐oriented Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ ferroelectric single crystals as a model material, the impact of mechanical confinements on polarization hysteresis, coercive field, and remanent polarization of relaxor‐based piezocrystals is investigated. Comparative studies are made among rhombohedral and tetragonal single crystals, as well as a polycrystalline ceramic, under uniaxial and radial compressive pre‐stresses. The dramatic changes observed are interpreted in terms of the piezoelectric effect and possible phase transitions for rhombohedral crystals, and ferroelastic domain switching and the piezoelectric effect for tetragonal crystals. Under radial compressive stresses, the coercive field for the rhombohedral crystal is observed to increase to 0.67 kV/mm and that for the tetragonal crystal is increased to 0.78 kV/mm. This is a 200% increase relative to the unstressed condition. The results demonstrate a general and effective approach to overcome the drawback of low coercive fields in these relaxor‐based ferroelectric crystals, which could help facilitate widespread implementation of these piezocrystals in engineering devices.     

Mobile Ferroelastic Domain Walls in Nanocrystalline PZT Films: the Direct Piezoelectric Effect

Ferroelastic (90°) domain wall motion occurs readily in bulk samples of displacive ferroelectrics such as Pb(Zr,Ti)O₃ (PZT), dictating critical piezoelectric, dielectric, and polarization switching properties. Many prior studies have used converse piezoelectric measurements to probe the dynamics of ferroelastic domains in thin films; however, such experiments are strongly influenced by the mechanical clamping effect of the substrate, which inhibits electric field‐induced 90° domain wall motion. Nevertheless, these observations raise a tantalizing question: Does the application of mechanical stress, rather than electric field, result in an entirely different response in thin films? Here we report biaxial stress‐driven crystallographic reorientation of (100)/(001) textured, 70 nm thick Pb(Zr_0.25Ti_0.75)O₃ films via 90° domain wall motion, measured in situ by both x‐ray diffraction and piezoforce microscopy. Visual evidence of nanoscale mechanisms that underlie the direct piezoelectric effect is shown. Mobile 90° domain walls effect complete orientation switching in the grains in which they operate, without apparent wall pinning, indicating that bulk‐like ferroelastic behavior can extend to nanocrystalline films in the absence of substrate clamping.     

High‐Performance [001]c‐Textured PNN‐PZT Relaxor Ferroelectric Ceramics for Electromechanical Coupling Devices

[001]_C‐Textured 0.55Pb(Ni_1/3Nb_2/3)O₃–0.15PbZrO₃–0.3PbTiO₃ (PNN‐PZT) ceramics are prepared by the templated grain‐growth method using BaTiO₃ (BT) platelet templates. Samples with different template contents are fabricated and compared in terms of texture fraction, microstructure, and piezoelectric, ferroelectric and dielectric properties. High piezoelectric performance (d₃₃ = 1210 pC N^?1, d₃₃* = 1773 pm V^?1 at 5 kV cm^?1) and high figure of merit g₃₃?d₃₃ (21.92 × 10^?12 m² N^?1) are achieved in the [001]_C‐textured PNN‐PZT ceramic with 2 vol% BaTiO₃ template, for which the texture fraction is 82%. In addition, domain structures of textured PNN‐PZT ceramics are observed and analyzed, which provide clues to the origin of the giant piezoelectric and electromechanical coupling properties of PNN‐PZT ceramics.     

Effects of Annealing Temperature on the Electric Properties of 0.94(Na0.5Bi0.5)TiO3–0.06BaTiO3 Ferroelectric Thin Film

0.94(Na_0.5Bi_0.5)TiO₃–0.06BaTiO₃ (NBT–BT6) ferroelectric thin films have been fabricated on Pt–Ti–SiO₂–Si(100) substrate by metal–organic decomposition. The effects of annealing temperature (650–800°C) on the microstructure, and the piezoelectric, ferroelectric, and dielectric properties of the thin films were studied in detail. The residual stress was evaluated by the orientation average method to clarify its dependence on annealing temperature and grain size, and it was correlated with the electric properties to understand the mechanism of piezoelectric enhancement. Among the thin films, NBT–BT6 thin film annealed at 750°C has the largest effective piezoelectric coefficient, 95.1 pm/V, remnant polarization, 49.7 μC/cm², spontaneous polarization, 105.2 μC/cm², and dielectric constant, 504, and the lowest dielectric loss, 0.05, and tensile residual stress, 24.5 MPa. For the NBT–BT6 thin film annealed at 750°C, a wide temperature range, 183–210°C, around the phase transition temperature (T _m) was observed in the dielectric temperature plots, and the diffusion coefficients (γ) were quantitatively assessed as 1.6, 1.78, and 1.6. Piezoelectric performance is discussed on the basis of the dispersion phase transition and residual stress.     

Nanofragmentation of Ferroelectric Domains During Polarization Fatigue

The microscopic mechanism for polarization fatigue in ferroelectric oxides has remained an open issue for several decades in the condensed matter physics community. Even though numerous models are proposed, a consensus has yet to be reached. Since polarization reversal is realized through ferroelectric domains, their behavior during electric cycling is critical to elucidating the microstructural origin for the deteriorating performance. In this study, electric field in situ transmission electron microscopy is employed for the first time to reveal the domain dynamics at the nanoscale through more than 10³ cycles of bipolar fields. A novel mechanism of domain fragmentation is directly visualized in polycrystalline [(Bi_1/2Na_1/2)_0.95Ba_0.05]_0.98La_0.02TiO₃. Fragmented domains break the long‐range polar order and, together with domain wall pinning, contribute to the reduction of switchable polarization. Complimentary investigations into crystal structure and properties of this material corroborate our microscopic findings.     

The Contributions of Polar Nanoregions to the Dielectric and Piezoelectric Responses in Domain‐Engineered Relaxor‐PbTiO3 Crystals

The existence of polar nanoregions is the most important characteristic of relaxor‐based ferroelectric materials. Recently, the contributions of polar nanoregions to the shear piezoelectric property of relaxor‐PbTiO₃ (PT) crystals are confirmed in a single domain state, accounting for 50%–80% of room temperature values. For electromechanical applications, however, the outstanding longitudinal piezoelectricity in domain‐engineered relaxor‐PT crystals is of the most significance. In this paper, the contributions of polar nanoregions to the longitudinal properties in [001]‐poled Pb(Mg_1/3Nb_2/3)O₃‐0.30PbTiO₃ and [110]‐poled Pb(Zn_1/3Nb_2/3)O₃‐0.15PbTiO₃ (PZN‐0.15PT) domain‐engineered crystals are studied. Taking the [110]‐poled tetragonal PZN‐0.15PT crystal as an example, phase‐field simulations of the domain structures and the longitudinal dielectric/piezoelectric responses are performed. According to the experimental results and phase‐field simulations, the contributions of polar nanoregions (PNRs) to the longitudinal properties of relaxor‐PT crystals are successfully explained on the mesoscale, where the PNRs behave as “seeds” to facilitate macroscopic polarization rotation and enhance electric‐field‐induced strain. The results reveal the importance of local structures to the macroscopic properties, where a modest structural variation on the nanoscale greatly impacts the macroscopic properties.     

Piezoelectric applications of ferroelectrics

The utility of ferroelectrics for piezoelectric devices rests on two characteristics, asymmetry and high dielectric constant. In one type of ferroelectric crystal, including Rochelle salt, asymmetry is intrinsic in the structure. Substances which owe their piezoelectric effect to ferroelectric polarity are of particular utility because domain orientation by electric field imparts piezoelectric response to polycrystalline bodies. Once this orientation has been achieved one usually desires to have a minimum of the nonlinearity, hysteresis losses, and high temperature coefficients connected with ferroelectricity. This has been achieved with modified barium titanate and especially lead titanate zirconate ceramics. Use of piezoelectric transducers in electroacoustics and ultrasonics has kept pace with the general growth in these fields, especially in phonograph pickups, industrial ultrasonics, and underwater acoustics. Piezoelectric spark sources for gas lighting are becoming a substantial consumer item. Piezoelectric ceramic IF filters both for 455 kHz and 10.7 MHz are of increasing interest due to their ruggedness and small size compatible with transistor and integrated circuitry.     

Giant Piezoelectric Coefficients in Relaxor Piezoelectric Ceramic PNN‐PZT for Vibration Energy Harvesting

It is well known that the piezoelectric performance of ferroelectric Pb(Zr,Ti)O₃ (PZT) based ceramics is far inferior to that of ferroelectric single crystals due to ceramics' polycrystalline nature. Herein, it is reported that piezoelectric stress coefficient e₃₃ = 39.24 C m^?2 (induced electric displacement under applied strain) in the relaxor piezoelectric ceramic 0.55Pb(Ni_1/3Nb_2/3)O₃–0.135PbZrO₃–0.315PbTiO₃ (PNN‐PZT) prepared by the solid state reaction method exhibits the highest value among various reported ferroelectric ceramic and single crystal materials. In addition, its piezoelectric coefficient d₃₃* = 1753 pm V^?1 is also comparable with that of the commercial Pb(Mg_1/3Nb_2/3)O₃‐PbTiO₃ (PMN‐PT) piezoelectric single crystal. The PNN‐PZT ceramic is then assembled into a cymbal energy harvester. Notably, its maximum output current at the acceleration of 3.5 g is 2.5 mA_pp, which is four times of the PMN‐PT single crystal due to the large piezoelectric e₃₃ constants; while the maximum output power is 14.0 mW, which is almost the same as the PMN‐PT single crystal harvester. The theoretical analysis on force‐induced power output is also presented, which indicates PNN‐PZT ceramic has great potential for energy device application.     

Dielectric Properties of Pure (BaSr)TiO3 and Composites with Different Grain Sizes Ranging from the Nanometer to the Micrometer

Starting with a BST (Ba_0.6Sr_0.4TiO₃) nanopowder with a mean diameter of about 50 nm, the average grain size increases from the nanometer to the micrometer range (from 70 nm to 1–2 μm) by thermal annealing between 700 and 1400 °C. The dielectric properties of these pressed powders has been determined, showing that the temperature of transition decreases with grain size. In order to check this evolution in dense ceramics in which the grain size is conserved, composite materials based on ferroelectric nanograins and a non‐ferroelectric matrix have been prepared. Core–shell composites with different core sizes (150 and 50 nm) were synthesized in this way and the results obtained confirmed the decrease of the transition temperature with grain size, from 290 to 230 K respectively. Furthermore, dielectric losses are very weak in these core–shell composites—at between 0.1 and 1 % in the temperature range 150–450 K and the frequency range 1 × 10³–1 × 10⁵ Hz. Ferroelectric nanograins of BST were also incorporated into silica gel for comparison with the core–shell materials. Even for a high fraction of BST (approx. 75 %), the properties of the grains are masked by the presence of silica, which possesses a very low dielectric constant. This study has allowed the possible determination of the macroscopic dielectric properties in nanostructured ceramics.     

Conformational Domain Wall Switch

Domain walls in ferroelectric materials have tantalizing potential in disruptive memory and reconfigurable nanoelectronics technologies. Here, a ferroelectric domain wall switch with three distinct addressable resistance states is demonstrated. The device operation hinges on fully controllable and reversible conformational changes of the domain wall. As validated by atomistic simulations consistent with the experiments, using electric field, the shape—and hence the charge state—of the domain wall and ultimately its conduction are altered. Sequential nanoscale transitions of the walls are visualized directly using stroboscopic‐piezoresponse force microscopy and Kelvin probe microscopy. Anisotropic head‐to‐head domain wall injection, stabilized by the majority carrier type of the ferroelectric, BiFeO₃, is identified as the key factor that enables conformational control.     

Criticality: Concept to Enhance the Piezoelectric and Electrocaloric Properties of Ferroelectrics

Compositional engineering with a focus on structural phase transitions has been considered as the most important approach for enhancement of the functional properties of ferroelectric materials due to the critical fluctuation of physical properties. Of special interest are electric‐field‐induced phase transitions, which can terminate in a liquid–vapor‐type critical point with a strong enhancement of functional properties. Whereas the critical point in liquid–vapor space considers changes in temperature and pressure, the critical point in this study is placed in electric field–temperature diagrams. In single crystals, temperature and electric field of a critical point are sharply defined and therefore not appealing for practical applications. However, in ceramics, it is demonstrated that the orientational dependence of the critical point leads to a broadened temperature and electric field range. The presence of a diffuse critical point in ceramics provides a conceptually novel approach for the enhancement of functional properties, such as piezoelectric and electrocaloric (EC) responses, as validated here on the example of the 0.75Bi_1/2Na_1/2TiO₃‐0.25SrTiO₃ lead‐free relaxor ferroelectric ceramics. The realization of a broad criticality range will further facilitate the development of the piezoelectric and EC materials and provide an alternative concept to manipulate the functional properties by application of an electric field.     

Polymer Template Synthesis of Flexible BaTiO3 Crystal Nanofibers

BaTiO₃ crystals are attractive materials due to their high dielectric properties, but they are brittle and inelastic ceramics, which limits their broader applications in emerging fields, such as flexible electronics. A scalable strategy for the fabrication of ultra‐flexible crystalline BaTiO₃ nanofiber (NF) films by a sol–gel electrospinning method, followed by a brief calcination, is reported. It facilitates the formation of perovskite BaTiO₃ crystals with intricate grain boundaries at a low temperatures by growing them within polymer NF templates. The ceramic films have a polymer‐like softness of 50 mN, a large Young's modulus of 61 MPa, and an elastic strain of 0.9%. Moreover, they have a low density of 28 mg cm^?3 and demonstrate superior softness without fracture after deformation. Piezoelectric sensors fabricated based on these films exhibit a high sensitivity of 80 ms with an output voltage of 1.05 V at a pressure of 100 kPa. This approach allows for the large‐scale fabrication of flexible BaTiO₃ crystal NF films.     

铌镁酸铅-钛酸铅铁电体准同型相界附近的压电性能研究

采用固相合成法制备了准同型相界附近的PMN-PT铁电陶瓷,对其介电和压电性能进行了研究,并讨论了不同掺杂对陶瓷的晶粒尺寸,介电常数,压电系数和机电耦合系数的影响,分析了不同掺杂取代位置对陶瓷的介电和压电性能的影响。发现这一体系陶瓷材料的压电性能与其晶粒的大小有一定的对应关系,同时在这一体系的掺杂后的影响可以较好地用传统PZT系统中的软硬掺杂解释。     

Acoustic Gain in Solids due to Piezoelectricity,Flexoelectricity, and Electrostriction

A quantitative discussion of the combined influence of three electromechanical effects: piezoelectricity, flexoelectricity, and electrostriction in solids is provided for acoustic absorption and gain. While piezoelectricity occurs in non‐centrosymmetric materials only, flexoelectricity and electrostriction exist in all materials. Two important new results are demonstrated: 1) the possibility to realize acoustic gain in all materials (centrosymmetric and non‐centrosymmetric) when the acoustic Cherenkov condition is fulfilled, and 2) realization of acoustic gain in the presence of a strong dc electric field, even when the Cherenkov condition is not fulfilled, in the case of strong cross‐coupling between piezoelectricity, flexoelectricity, and electrostriction. A simple analytical expression for the acoustic dispersion relation is derived for the combined effect of piezoelectricity, flexoelectricity, and electrostriction. At lower frequencies, the piezoelectric effect dominates for inversion‐asymmetric materials. At high frequencies (≈>1 MHz) flexoelectricity becomes increasingly important and eventually provides a major mechanism for gain and absorption in barium titanate (BaTiO₃). In the presence of strong electric fields (≈>1 MV m^?1), electrostriction provides a dominant isolated contribution to absorption/gain in BaTiO₃. Strong coupling between the three electromechanical contributions determines the total absorption/gain coefficient.     

Local Structural Heterogeneity and Electromechanical Responses of Ferroelectrics: Learning from Relaxor Ferroelectrics

Long‐range ordering of dipoles is a key microscopic signature of ferroelectrics. These ordered dipoles form ferroelectric domains, which can be reoriented by electric fields. Relaxor ferroelectrics are a type of ferroelectric where the long‐range ordering of dipoles is disrupted by cation disorder, exhibiting complex polar states with a significant amount of local structural heterogeneity at the nanoscale. They are the materials of choice for numerous devices such as capacitors, nonlinear optical devices, and piezoelectric transducers, owing to their extraordinary dielectric, electro‐optic, and electromechanical properties. However, despite their extensive applications in these devices, the origins of their unique properties are yet to be fully understood, hindering the design and exploration of new relaxor ferroelectric‐based materials. Herein, the complex polar states and applications of relaxor ferroelectrics are first introduced. Attention is then focused on their electromechanical properties, where the relationship between local structural heterogeneity and the extraordinary electromechanical properties is discussed. Based on the understanding of relaxor ferroelectrics, potential strategies to exploit the local structural heterogeneity to design ferroelectrics for drastically enhancing their electromechanical performances are also discussed. It is expected that this article will stimulate future studies on the important roles of local structural heterogeneity in improving the properties of various functional materials.