Evolution of Ferroelectricity in Sr0.6Ba0.4Nb2O6-BaTiO3 Solid Solution with a Strong Electrocaloric Effect.

In conventional knowledge, ferroelectric solid solutions were formed between members belonging to the same crystal structure family. Since both tungsten bronze and perovskite structures are constructed by connecting the corner-sharing oxygen octahedra, it offers a possibility for formatting an unusual solid solution between these two families. Herein, (1 - x)Sr0.6Ba0.4Nb2O6-xBaTiO3, (1 - x)SBN-xBT, solid solutions were synthesized and the solution mechanism was resolved from a structure viewpoint. With increasing BT content, the solid solution persists of tetragonal tungsten bronze structure, but the lattice parameter a (= b) decreases whereas c increases, resulting in the significant reduction of grains anisotropy. The ferroelectric-relaxor phase transition temperature shows a monotonic increase as x increases. However, the ferroelectricity evolution is not monotonous as a function of BT content because of the competitive effects of Ba and Ti on the property. As a result, the x = 0.10 ceramic shows the strongest ferroelectricity and a remarkable electrocaloric effect of 1.4 K near room temperature. This work challenges the traditional view of solid solution formation and provides an alternative way to modulate the structure and properties of ferroelectrics.

Synergy of Oxygen Octahedra Distortion and Polar Nanodomains Induced Emergent Electrocaloric Effect in NaNbO3-Based Ceramics.

High-performance electrocaloric materials are essential for the development of solid-state cooling technologies; however, the contradiction of the electrocaloric effect (ECE) and temperature span in ferroelectrics frustrates practical applications. In this work, through modulating oxygen octahedra distortion and short-range polar nanodomains with moderate coupling strength, an EC value of ΔT ∼ 0.30 K with an ultrawide temperature span of 85 K is obtained in the x = 0.04 composition [(0.88 - x)NaNbO3-0.12BaTiO3-xLiSbO3 (x = 0-0.06)]. The LiSbO3 dopant induces a P4bm-to-R3cH phase transition and intensifies the oxygen octahedra distortion degree, accompanied by the ferroelectric domain smashing into polar nanodomains. Also, LiSbO3 addition enhances the relaxation degree with a downshift of Tfd (ferroelectric-to-diffuse phase transition temperature) and TJ (temperature of the maximal current density value), and Tfd is shifted to near room temperature with an absence of TJ in x = 0.04. Local energy barriers induced by oxygen octahedra distortion inhibit the phase transition in conjunction with activation of short-range polar order switching under thermal stimuli, which is the underlying mechanism for an excellent EC performance for x = 0.04. This work not only clarifies that ferroelectrics with oxygen octahedra distortion and short-range polar order are expected to achieve remarkable EC performances but also provides a design strategy to seek emergent EC behaviors in complex oxygen-octahedra-distortion materials.

The Influence of Measurement Conditions on the Electrocaloric Effect in Ferroelectric Ceramics of Modified Barium Titanate.

In this work, the electrocaloric effect (ECE) and electrocaloric strength (ΔT/E) were measured and thermal and dielectric studies were performed on Pb-modified BaTiO3 (BPT). The saturated hysteresis loops and normal ferroelectric behavior of the ferroelectric ceramics allow the utilization of the indirect method to estimate the electrocaloric properties. The electrocaloric measurements were performed under high (18 kV/cm) versus low (8 kV/cm) electric field conditions. These conditions were chosen to notice and then eliminate an artificial negative electrocaloric effect in the tested ceramics. At the same time, relatively high values of positive electrocaloric temperature change ΔT (~ 2.19 K) and electrocaloric strength ΔT/E (~0.27-0.11 K·cm/kV) were obtained.

Achieving Ultrahigh Electrocaloric Response in (Bi0.5Na0.5)TiO3-Based Ceramics through B-Site Defect Engineering.

Lead-free electrocaloric (EC) ferroelectrics are considered ideal for the next generation of environmentally friendly solid-state refrigeration materials. However, their inferior performance compared to lead-based materials significantly restricts their potential application. According to phase-field simulations, it is predicted that the pinning effect of a moderate number of defects can effectively enhance the reversible polarization response associated with the entropy change. Herein, sodium-bismuth titanate (BNT) ceramics with high spontaneous polarization are selected to construct B-site defects by introducing Li+ and Nb5+. Under an electric field of 6 kV mm-1, ultrahigh EC temperature changes of ΔTpos = 1.77 and ΔTneg = 1.49 K are achieved at 65 °C by direct measurement (ΔTneg > 1 K over 55-120 °C). Furthermore, ΔTneg remains above 0.70 K in the temperature range from 25 to 130 °C, exhibiting immense potential for practical applications. This study offers a promising direction for optimizing the EC response in defect systems.

Realization of the Giant Pyroelectric Response via Modulated Polar Structures.

Among pyroelectric materials, Bi0.5Na0.5TiO3 (BNT)-based relaxors are particularly noteworthy due to their significant polarization fluctuation near the depolarization temperature (Td), resulting in a large pyroelectric response. What has been overlooked is the dynamic behavior of inherent polar structures, particularly the temperature-dependent evolution of polar nanoregions (PNRs), which significantly impacts the pyroelectric behavior. Herein, based on the large pyroelectric response origination (the ferroelectric-relaxor phase transition), the mixed nonergodic and ergodic relaxor (NR+ER) critical state is constructed, which is believed to trigger the easily fluctuating polarization state with excellent pyroelectric response. Composition engineering (with Li+, Sr2+, and Ta5+) strategically controls the relaxor process and modulates the dynamic behavior of inherent polar structures by the random field effect. The pyroelectric coefficient of more than 1441 µCm-2K-1 at room temperature (RT), more than 9221 µCm-2K-1 (RT), and ≈107911 µCm-2K-1 (Td) are achieved in the Li+-doped sample, the Sr2+-doped sample, and the (Li++Ta5+) co-doped sample, respectively. This work earns the highest RT pyroelectric coefficient in BNT-based relaxors, which is suitable for pyroelectric applications. Furthermore, it provides a strategy for modulating the pyroelectric performance of BNT-based relaxors.

Multifunctional Flexible Ferroelectric Thin Films with Large Electrocaloric Effect and High Energy Storage Performance.

Flexible ferroelectric films with high polarization hold great promise for energy storage and electrocaloric (EC) refrigeration. Herein, we fabricate a lead-free Mn-modified 0.75 Bi(Mg0.5Ti0.5)O3-0.25 BaTiO3 (BMT-BTO) thin film based on a flexible mica substrate. Excellent EC performance with maximum adiabatic temperature change (ΔT ∼23.5 K) and isothermal entropy change (ΔS ∼33.1 J K-1 kg-1) is achieved in the flexible BMT-BTO film, which is attributed to the local structural transition and lattice disorder near 90 °C. Meanwhile, a good energy storage density of ∼70.6 J cm-3 and a quite high efficiency of ∼82% are realized in the same ferroelectric film, accompanied by excellent stability of frequency and electric fatigue (500-10 kHz and 108 cycles). Furthermore, there is no apparent variation in performance under different bending strains. These prominent properties indicate that the multifunctional BMT-BTO ferroelectric film is a promising candidate for applications of flexible energy storage and EC refrigeration.

Enhanced Electrocaloric Effect of Lead Scandium Tantalate by Zirconium Doping.

The electrocaloric effect (ECE) is a novel technology that offers high efficiency and environmental friendliness, making it suitable for solid-state refrigeration applications. Among the extensively studied ECE materials, lead scandium tantalate (PST) stands out for its excellent performance. However, its applications are restricted by its narrow working temperature range. To overcome this limitation, we explore the enhancement of the ECE through zirconium ion doping. We synthesized PbSc0.5-0.5xTa0.5-0.5xZrxO3 samples (x = 0, 0.025, 0.05, 0.075). The introduction of zirconium ions led to an increase in the Curie temperature from 28.9 °C (x = 0) to 55.5 °C (x = 0.075). Additionally, the relaxation factor γ of the ceramics increased from 1.40 (x = 0) to 1.59 (x = 0.075). The temperature span (Tspan) exhibited a rising trend with increasing x, reaching 10.9 K at x = 0.075. The maximum temperature change (ΔTmax) was observed at x = 0.025, with a value of 1.94 K. X-ray diffraction (XRD) patterns revealed that zirconium ion doping influenced the B-site ordering degree, thereby regulating the ECE. To further validate the results, we employed direct measurements and thermodynamic calculations. Overall, the regulation of ionic ordering through zirconium doping effectively enhances the ECE performance. These findings contribute to the development of advanced materials for solid-state refrigeration technologies.

New Soft Actuating Way by Rapidly Temperature Change of Electrocaloric Effect.

Compared to traditional temperature control methods, the electrocaloric (EC) effect offers several advantages such as small size, rapid response, and environmental friendliness. However, current EC effects are generally used for the cooling area rather than heating. Here, poly(vinylidenefluorideter-trifluoroethylene-ter-chlorofluoroethylene) [P(VDF-TrFE-CFE)] film is combined with an electrothermal actuator (ETA) composed of polyethylene (PE) film and carbon nanotube (CNT) film. The heating and cooling process of the EC effect is used to help drive the ETA. The P(VDF-TrFE-CFE) film can produce a temperature change (ΔT) of 3.7 °C at 90 MV/m, and this process occurs within 0.1 s. With this ΔT, the composite film actuator can produce a deflection of 10°. In addition, due to the electrostrictive effect of P(VDF-TrFE-CFE), the composite film can also be used as an actuator. At 90 MV/m, the composite film actuator can produce a deflection over 240° within 0.05 s. Apart from other current driving modes for thermally responsive actuators, in this paper, a new type of soft actuating composite film by the temperature change of the EC effect is proposed. Except from ETAs, the EC effect can also have a wide application prospect in other thermally responsive actuators, including shape memory polymer actuators, shape memory alloy actuators, and so on.

Substantially Enhanced Electrocaloric Effect in Ba(Zr0.2Ti0.8)O3 Lead-Free Ferroelectric Ceramics via Lattice Stress Engineering.

As an alternative to conventional vapor-compression refrigeration, cooling devices based on electrocaloric (EC) materials are environmentally friendly and highly efficient, which are promising in realizing solid-state cooling. Lead-free ferroelectric ceramics with competitive EC performance are urgently desirable for EC cooling devices. In the past few decades, constructing phase coexistence and high polarizability have been two crucial factors in optimizing the EC performance. Different from the external stress generated through heavy equipment and inner interface stress caused by complex interface structures, the internal lattice stress induced by ion substitution engineering is a relatively simple and efficient means to tune the phase structure and polarizability. In this work, we introduce low-radius Li+ into BaZr0.2Ti0.8O3 (BZT) to form a particular A-site substituted cell structure, leading to a change of the internal lattice stress. With the increase of lattice stress, the fraction of the rhombohedral phase in the rhombohedral-cubic (R-C) coexisting system and ferroelectricity are all pronouncedly enhanced for the Li2CO3-doped sample, resulting in the significant enhancement of saturated polarization (Ps) as well as EC performance [e.g., adiabatic temperature change (ΔT) and isothermal entropy change (ΔS)]. Under the same conditions (i.e., 333 K and 70 kV cm-1), the ΔT of 5.7 mol % Li2CO3-doped BZT is 1.37 K, which is larger than that of the pure BZT ceramics (0.61 K). Consequently, in cooperation with the great improvement of electric field breakdown strength (Eb) from 70 to 150 kV cm-1, 5.7 mol % Li2CO3-doped BZT achieved a large ΔT of 2.26 K at a temperature of 333 K, which is a competitive performance in the field of electrocaloric effect (ECE). This work provides a simple but effective approach to designing high-performance electrocaloric materials for next-generation refrigeration.

Composition-Related Dielectric, Ferroelectric and Electrocaloric Properties of Pb5Ge3O11 Single Crystals Modified by Ba Ions.

In this paper, we studied some ferroelectric properties of archetypal oxide uniaxial ferroelectric single crystals of Pb5Ge3O11 modified by Ba ions. They include dielectric, DSC, ferroelectric polarization, and electrocaloric effect (ECE) measurements. The measurements show that increasing Ba doping considerably influences all the measured parameters, mainly by lowering the Curie temperature, gradually diffusing the phase transition, and decreasing values of polarization as well as the coercive field. The decrease in overall ECE is influenced by decreasing polarization. Compared with the pure PGO single crystals, this decrease is from 1.2 K to 0.2 K. However, the effect of diffusing the phase transition increases the range of its occurrence (up to 30 K), which might be beneficial in applications.

An Active Pixel-Matrix Electrocaloric Device for Targeted and Differential Thermal Management.

More than 55% of electronic failures are caused by damage from localized overheating. Up to now, there is still no efficient method for targeted temperature control against localized overheating. Although some existing thermal management devices handle this issue by full coverage cooling, it generates a lot of useless energy consumption. Here, a highly efficient pixel-matrix electrocaloric (EC) cooling device is reported, which can realize a targeted and differential thermal management. The modified poly(vinylidene fluoride-tertrifluoroethylene-chlorofluoroethylene) reaches a large adiabatic temperature change of 7.8 K and is more suitable for thermal transfer and electrostatic actuation at high frequencies. All active pixels in the EC cooling device exhibit a stable temperature span of 4.6 K and a heat flux of 62 mW cm-2 , which is more than twice that of the one-layer EC device. Each refrigeration pixel can be independently controlled and effectively cooled down the localized overheating site(s) in situ. The surface temperature of the simulated central processing unit decreases by 33.2 K at 120 s after applying this EC device. Such a compact, embeddable, low cost, and active solid-state pixel-matrix cooling device has great potential for localized overheating protection in microelectronics.

Optimization of Processing Steps for Superior Functional Properties of (Ba, Ca)(Zr, Ti)O3 Ceramics.

Lead-free piezoelectric ceramics with nominal composition at morphotropic phase boundary Ba0.85Ca0.15Ti0.9Zr0.1O3 (BCTZ) prepared by different processing routes and sintered either by conventional solid-state reaction or by spark plasma sintering (SPS) techniques were comparatively investigated to observe the role of structural modifications and of microstructures on the dielectric, ferroelectric, piezoelectric and electrocaloric responses. The ceramics presented relative densities from 75% to 97% and showed variations in their phase composition as a result of variable mixing and different synthesis and sintering parameters providing local compositional heterogeneity. As result, all of the ceramics showed diffuse phase transition and ferroelectric switching responses, with parameters affected mostly by density (Pr between 3.6 to 10.1 µC/cm2). High values for the electrocaloric response in the Curie range were found for the ceramics with predominantly orthorhombic character. Field-induced structural modifications were probed by tunability anomalies and by XRD experiments in remanence conditions. Piezoelectric effects with notably high figure of merit values were assigned to the better densification and poling efficiency of BCTZ ceramics.

Giant Negative Electrocaloric Effect over an Ultra-Wide Temperature Region in Relaxation Frozen State Ferroelectrics.

A giant negative electrocaloric effect with the electrocaloric temperature change range from -27.3 to -9.8 K over an ultra-wide temperature region of 260 K (-180 to 80 °C) is obtained in a relaxation frozen state ferroelectric film of Bi5Ti3AlO15. A strategy is proposed to extend the temperature region of the electrocaloric effect by gradually slowing and locally freezing the relaxation dynamics. The slow and frozen nanodomains below freezing temperature Tf of ∼80 °C do not yield to the applied electric field but are noncolinear to the field, which results in an inverse configuration entropy change and negative electrocaloric effect over an ultra-wide temperature region in frozen relaxor state ferroelectric films. A semiphenomenological model based on modified Ginzburg-Landau-Devonshire theory is presented to reveal the evolution of the slowing and freezing of the nanodomains. The breakthroughs in the operating temperature region and cooling temperature change make relaxation frozen state ferroelectrics excellent electrocaloric refrigeration materials.

Misfit-Strain Phase Diagram, Electromechanical and Electrocaloric Responses in Epitaxial PIN-PMN-PT Thin Films.

xPb(In1/2Nb1/2)O3-(1-x-y)Pb(Mg1/3Nb2/3)O3-yPbTiO3 (PIN-PMN-PT) bulks possess excellent electromechanical coupling and dielectric properties, but the corresponding epitaxial PIN-PMN-PT thin films have not yet been explored. This paper adopts a nonlinear thermodynamics analysis to investigate the influences of misfit strains on the phase structures, electromechanical properties, and electrocaloric responses in epitaxial PIN-PMN-PT thin films. The misfit strain-temperature phase diagram was constructed. The results reveal that the PIN-PMN-PT thin films may exist in tetragonal c-, orthorhombic aa-, monoclinic M-, and paraelectric PE phases. It is also found that the c-M and aa-PE phase boundaries exhibit a superior dielectric constant ε11 which reached 1.979 × 106 with um = -0.494%, as well as the c-M phase boundary showing a large piezoelectric response d15 which reached 1.64 × 105 pm/V. In comparison, the c-PE and M-aa phase boundaries exhibit a superior dielectric constant ε33 over 1 × 105 around um = 0.316% and the piezoelectric response d33 reached 7235 pm/V. The large electrocaloric responses appear near the paraelectric- ferroelectric phase boundary. These insights offer a guidance for experiments in epitaxial PIN-PMN-PT thin films.

Role of Density and Grain Size on the Electrocaloric Effect in Ba0.90Ca0.10TiO3 Ceramics.

Pure perovskite Ba0.90Ca0.10TiO3 ceramics, with a relative density of between 79 and 98% and grain sizes larger than 1 µm, were prepared by solid-state reaction. The dielectric and electrocaloric properties were investigated and discussed considering the density and grain size of the samples. Room temperature impedance measurements show good dielectric properties for all ceramics with relative permittivity between 800 and 1100 and losses of <5%. Polarization vs. E loops indicates regular variation with increasing sintering temperature (grain size and density), an increase in loop area, and remanent and saturation polarization (from Psat = 7.2 µC/cm2 to Psat = 16 µC/cm2). The largest electrocaloric effect was 1.67 K for ceramic with GS = 3 µm at 363 K and electrocaloric responsivity (ζ) was 0.56 K mm/kV. These values are larger than in the case of other similar materials; thus, Ba0.90Ca0.10TiO3 ceramics with a density larger than 90% and grain sizes of a few µms are suitable materials for electrocaloric devices.

Electrocaloric Effect in Different Oriented BaZr0.15Ti0.85O3 Single Crystals.

The electrocaloric effect of ferroelectrics is promising for new solid-state refrigeration. However, the current research on the electrocaloric effect of bulk ferroelectrics mainly focuses on (001) orientation. Thus, we studied the electrocaloric effect of BaZr0.15Ti0.85O3 single crystals with different orientations through the nonlinear thermodynamic approach and entropy analysis. The results show that the dipolar entropy of (111)-oriented BaZr0.15Ti0.85O3 single crystals exhibits a greater change after applying an external electric field, compared with (001)- and (110)-orientations, and the (001)-oriented electrocaloric responses are consistent with experimental observations. The (111)-oriented BaZr0.15Ti0.85O3 single crystals have a more significant electrocaloric response, resulting in a broader work temperature range with a large electrocaloric effect. These insights offer an alternative way to enhance the electrocaloric response of ferroelectric single crystals.

Giant Room-Temperature Electrocaloric Effect of Polymer-Ceramic Composites with Orientated BaSrTiO3 Nanofibers.

Cooling based on the electrocaloric effect (ECE) is a promising solution to environmental and energy efficiency problems of vapor-compression refrigeration. Ferroelectric polymer-ceramics nanocomposites, integrating high electric breakdown of organic ferroelectrics and large EC strength of ceramics, are attractive EC materials. Here, we tuned the orientation of Ba0.67Sr0.33TiO3 nanofibers (BST nfs) in the P(VDF-TrFE-CFE) polymer. When the nfs were aligned parallel to the field, a ΔT of 11.3 K with an EC strength of 0.16 K·m/MV was achieved in the blends. The EC strength not only surpasses advanced nanocomposites but also is comparable to ferroelectric ceramics. The simulation indicates that a significantly higher electric field is concentrated in polymer regions around the ends of the orientated nfs, contributing to easier flipping of polymer chains for large ECE. This work provides a new method to obtain large ECE in composites for next-generation refrigeration.

Bimodal-Structured 0.9KNbO3-0.1BaTiO3 Solid Solutions with Highly Enhanced Electrocaloric Effect at Room Temperature.

0.9KNbO3-0.1BaTiO3 ceramics, with a bimodal grain size distribution and typical tetragonal perovskite structure at room temperature, were prepared by using an induced abnormal grain growth (IAGG) method at a relatively low sintering temperature. In this bimodal grain size distribution structure, the extra-large grains (~10-50 µm) were evolved from the micron-sized filler powders, and the fine grains (~0.05-0.35 µm) were derived from the sol precursor matrix. The 0.9KNbO3-0.1BaTiO3 ceramics exhibit relaxor-like behavior with a diffused phase transition near room temperature, as confirmed by the presence of the polar nanodomain regions revealed through high resolution transmission electron microscope analyses. A large room-temperature electrocaloric effect (ECE) was observed, with an adiabatic temperature drop (ΔT) of 1.5 K, an isothermal entropy change (ΔS) of 2.48 J·kg-1·K-1, and high ECE strengths of |ΔT/ΔE| = 1.50 × 10-6 K·m·V-1 and ΔS/ΔE = 2.48 × 10-6 J·m·kg-1·K-1·V-1 (directly measured at E = 1.0 MV·m-1). These greatly enhanced ECEs demonstrate that our simple IAGG method is highly appreciated for synthesizing high-performance electrocaloric materials for efficient cooling devices.

An Overview of Some Nonpiezoelectric Properties of BaTiO3 Ceramics Doped by Eu Ions.

Ferroelectric ceramics BaTiO3:x%Eu (x = 0, 0.1, 1, 2, 3) were synthesized by a conventional method. Structural investigation confirmed that all ceramics possessed tetragonal (P4mm) symmetries at room temperature for the undoped ceramics as well as for the doped ceramics. Furthermore, a slight downshifting of the Curie temperature (TC) with an increasing Eu3+ doping amount has been noted. The Raman spectra unveiled the existence of new modes for higher-doped BaTiO3:x%Eu (BTEx) which are related to local disorders and defects. The ferroelectric properties were found to depend on both doping and the microstructure. The electrocaloric effect was also studied for those ceramics. It was observed that ΔT decreases with doping; however, the temperature range of its occurrence widens considerably.

Revisiting the Kittel's model of antiferroelectricity: phase diagrams, hysteresis loops and electrocaloric effect.

We revisit the Kittel's model of antiferroelectricity by extending the model to study the phase transitions, hysteresis loop behaviors and electrocaloric effect (ECE) of antiferroelectrics (AFEs). By considering both the first- and second-order AFEs, explicit expressions for the physical and staggered polarizations of AFEs in the stable states are derived. We also obtain the analytical solutions for describing the dielectric susceptibilities of AFEs in the AFE and paraelectric (PE) phases. Coercive fields in AFE are also derived and studied. To verify the usefulness of the Kittel's model of antiferroelectricity, we apply the model to systematically investigate the phase transitions, hysteresis loops and ECEs of PbZrO3(PZO). By adopting appropriate values of the Kittel's parameters for first-order transition, analytical and numerical results are obtained and discussed. Our results show that PZO exhibits a complex temperature (T)-electric field (E) phase diagram, consisting of the AFE, ferroelectrics, ferrielectric, PE and mixed phases. TheT-Ephase diagram is qualitatively agreed with the new AFE model that was derived based on symmetry by Tolédano and Khalyavin (2019Phys. Rev.B99024105). We found that the calculated zero-field dielectric susceptibility is qualitatively and quantitatively agreed with experimental results. We show that the polarizations and dielectric susceptibilities of PZO in heating and cooling deviate from each other, as expected for the first-order materials. Our calculated results also reveal that the ECE in PZO has an electro-heating of ΔT≈ +6.5 °C and an electro-cooling of ΔT≈ -4.0 °C, respectively, which are comparable to the experimental results.