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Antiferroelectric materials exhibit electric field-induced phase transitions between antiferroelectric and ferroelectric states, which enable their use in energy storage and other applications. However, the mechanisms of these transitions are insufficiently understood. Here, we considered the electric field-induced phase transition in the lead-free antiferroelectric NaNbO$_3$. Macroscopic measurements of polarization and longitudinal, transverse, and volumetric strain were complemented with simultaneous structural investigations using high-energy x-ray radiation, yielding crystallographic strain and unit cell volume changes. The field-induced behavior can be divided into the structural antiferroelectric–ferroelectric phase transition at about 8 kV/mm and the clearly decoupled polarization switching process at about 12 kV/mm, which is associated with a large increase in polarization and strain. Decoupling of the field-induced phase transition and polarization switching is related to the randomly oriented grains and mechanical stress present at the phase boundary.

The correlation between dielectric permittivity and electrocaloric (EC) temperature change (ΔTEC) has been investigated in (1 − x)Pb(Mg1/3Nb2/3)O3−xPbTiO3 (PMN–100xPT, with x = 0, 0.05, and 0.10) relaxor ferroelectric ceramics. At a given electric field, both peak temperatures, including the temperature of the permittivity peak (Tm) and the temperature of the maximum of the ΔTEC (TEC max) increase with increasing PT content. The peak of the dielectric permittivity is, regardless of the applied electric field, always at a higher temperature than is the TEC max, and the temperature gap between both maxima progressively increases with increasing applied DC bias. This is particularly true above the threshold field, which induces the long-range ordered ferroelectric state. The results, which are explained in terms of the electric field–temperature phase diagram of relaxor systems, thus reveal that Tm can only roughly mark the temperature of the upper boundary of the temperature–electric field window, where the EC responsivity (ΔTEC/ΔE) is the highest.

Mechanical confinement or restricted degrees of freedom have been explored for its potential to enhance the performance of ferroelectric devices. It presents an easy and reversible method to tune the response for specific applications. However, such studies have been mainly limited to uni- or bi-axial stress. This study investigates the effect of hydrostatic pressure on the ferroelectric behavior of bulk polycrystalline Pb0.99Nb0.02(Zr0.95Ti0.05)0.98O3. Polarization versus electric field hysteresis plots were generated as a function of hydrostatic pressure for a range of operating temperatures (298–398 K). The application of hydrostatic pressure was observed to induce anti-ferroelectric like double hysteresis loops. This in turn enhances the piezoelectric, energy storage, energy harvesting, and electrocaloric effects. The hydrostatic piezoelectric coefficient (dh) was increased from 50 pCN−1 (0 MPa) to ∼900 pC N−1 (265 MPa) and ∼3200 pCN−1 (330 MPa) at 298 K. Energy storage density was observed to improve...

We present a critical review that encompasses the fundamentals and state-of-the-art knowledge of barium titanate-based piezoelectrics. First, the essential crystallography, thermodynamic relations, and concepts necessary to understand piezoelectricity and ferroelectricity in barium titanate are discussed. Strategies to optimize piezoelectric properties through microstructure control and chemical modification are also introduced. Thereafter, we systematically review the synthesis, microstructure, and phase diagrams of barium titanate-based piezoelectrics and provide a detailed compilation of their functional and mechanical properties. The most salient materials treated include the (Ba,Ca)(Zr,Ti)O3, (Ba,Ca)(Sn,Ti)O3, and (Ba,Ca)(Hf,Ti)O3 solid solution systems. The technological relevance of barium titanate-based piezoelectrics is also discussed and some potential market indicators are outlined. Finally, perspectives on productive lines of future research and promising areas for the applications of these ma...

Application of a negative field on a positively poled ferroelectric sample can enhance the electrocaloric cooling and appears as a promising method to optimize the electrocaloric cycle. Experimental measurements show that the maximal cooling does not appear at the zero-polarization point, but around the shoulder of the P-E loop. This phenomenon cannot be explained by the theory based on the constant total entropy assumption under adiabatic condition. In fact, adiabatic condition does not imply constant total entropy when irreversibility is involved. A direct entropy analysis approach based on work loss is proposed in this work, which takes the entropy contribution of the irreversible process into account. The optimal reversed field determined by this approach agrees with the experimental observations. This study signifies the importance of considering the irreversible process in the electrocaloric cycles.

Electric-field- and stress-induced phase transformations were investigated in polycrystalline 0.5 mol. % Mn-doped (1−x)(Bi1/2Na1/2)TiO3-x(Bi1/2K1/2)TiO3 (x = 0.1, 0.2). To characterize the effect of electric field and stress on the stability of the ferroelectric and relaxor states, polarization- and current density-electric field curves, as well as the stress-strain response as a function of temperature were characterized. Analogous to the observed electrical behavior, the macroscopic mechanical constitutive behavior showed a closed hysteresis at elevated temperatures, indicating a reversible stress-induced relaxor-to-ferroelectric transformation. The electrical and mechanical measurements were used to construct electric field–temperature and stress-temperature phase diagrams, which show similar characteristics. These data show that a mechanical compressive stress, similarly to an electric field, can induce long-range ferroelectric order in a relaxor ferroelectric.

An electric field–temperature (E-T) phase diagram for a lead-free 0.5 mol. % Mn-doped Bi(Na0.1K0.9)TiO3 ceramics was investigated. The x-ray diffraction, dielectric and polarization measurements revealed relaxor behavior and were used to characterize the stability regions of the non-ergodic relaxor, ergodic relaxor and electric field induced ferroelectric states. As indicated by the polarization–current density profiles, transformation between two electric fields, induced ferroelectric states with opposite polarization direction arise via a two-step process through an intermediate relaxor state. Interplay between the ferroelectric state conversion and intermediate relaxor state is governed by the dynamics of polarization relaxation. The presented E-T phase diagram revealed the effects of the applied electric field and temperature on stability regions. This is of special interest since the Bi0.5(Na0.1K0.9)0.5TiO3 ceramics were proposed as a potential piezoceramic material.

Contributions to the piezoelectric response of (1 − x)Ba(Zr0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3 ceramics are quantified by small signal measurements made as functions of bias field and temperature. The highest fraction of intrinsic contributions is observed far from phase boundaries, of extrinsic contributions around phase boundaries, and of irreversible switching in the orthorhombic phase. The largest piezoelectric response, d33 = 475 ± 85 pC/N, is found near the orthorhombic to tetragonal phase boundary due to both reversible and irreversible switching. A peak in reversible switching above the Curie temperature for all compositions suggests a line of critical points associated with first order phase transitions, indicating that concurrence of triple and tricritical points in the zero-field phase diagram is not the responsible mechanism of enhanced piezoelectricity.

The piezoelectric effect of ZnO has been investigated recently with the goal to modify metal/semiconductor Schottky-barriers and p-n-junctions by application of mechanical stress. This research area called “piezotronics” is so far focused on nano structured ZnO wires. At the same time, ZnO varistor materials are already widely utilized and may benefit from a piezotronic approach. In this instance, the grain boundary potential barriers in the ceramic can be tuned by mechanical stress. Polycrystalline varistors exhibit huge changes of resistivity upon applied electrical and mechanical fields and therefore offer descriptive model systems to study the piezotronic effect. If the influence of temperature is contemplated, our current mechanistic understanding can be interrogated and corroborated. In this paper, we present a physical model based on parallel conducting pathways. This affords qualitative and semi-quantitative rationalization of temperature dependent electrical properties. The investigations demonstrate that narrow conductive pathways contribute to the overall current, which becomes increasingly conductive with application of mechanical stress due to lowering of the barrier height. Rising temperature increases the thermionic current through the rest of the material with higher average potential barriers, which are hardly affected by the piezoelectric effect. Hence, relative changes in resistance due to application of stress are higher at low temperature.

The impact of uniaxial compressive mechanical stress on the electrical properties of a ZnO varistor ceramic was studied with respect to a potential use in pressure sensor applications. Current-voltage measurements as a function of temperature are strongly affected by the applied stress. The modulation of charge transport properties with uniaxial stress causes large changes in resistance. Hence, a gauge factor of ∼800 is attained, which significantly exceeds the value of conventional sensors. The effect is attributed to the piezotronic effect, i.e., the altering of the potential barrier at grain boundaries due to the piezoelectricity of ZnO. This change in grain boundary potential barriers via mechanical deformation represents a promising physical concept for the development of better materials for sensor applications.

The electric-field–temperature phase diagram for the lead-free relaxor material (1 − x)(Bi1/2Na1/2)TiO3 − xBaTiO3 (x = 0.03, 0.06, and 0.09) doped with 0.5 mol% Mn (BNT-100xBT:Mn) was established. Transition lines between ergodic or nonergodic relaxor states and the field-induced ferroelectric state were determined at constant temperatures with electric-field-dependent measurements of the polarization as well as of the piezoelectric coefficient and permittivity. Near the depolarization temperature T d, the switching between two ferroelectric poling directions occurs in two steps via an intermediate relaxor state. This effect is closely related to the pinching of the ferroelectric hysteresis loop.

Transport properties are studied in the MoS2 selective morphology system. Fluctuation-induced tunneling dominates in pressed pellets at temperatures up to about 90 K. At higher temperatures, variable range hopping (VRH) transport mechanism prevails, with diverse dimensionality and temperature range. In Mo6S2I8 nanowires, 1D VRH is shown, in MoS2 plate-like crystals 2D VRH and in MoS2 coaxial nanotubes and MoS2 size-controlled nanotubes 3D VRH is found. Decreasing of dimensionality is accompanied by an increase of the conductivity in MoS2 nanotubes, compared to the plate-like crystals. Transport properties are discussed in relation to the nature and density of defects, giving rise to changes in the electronic structure and influencing the scattering mechanism governing the charge transport.