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Pyroelectric materials have been widely studied because of their important role in infrared detectors, sensors, thermal imaging, and other applications, among which, lead-based ceramics are extensively adopted. However, the environmental problems caused by lead-based compounds in production and processing are becoming increasingly serious. Meanwhile, the surface mounting technology is extensively employed in the electronics industry for device miniaturization and integration. However, due to its high processing temperature (∼260 °C), it makes most pyroelectric ceramic materials unsuitable for this process. Therefore, it is of great significance to develop novel high-performance lead-free pyroelectric ceramics with high depolarization temperature (>260 °C). In this work, we report the Na0.995Ag0.005NbO3-0.1%Mn (NANM) pyroelectric ceramics. The antiferroelectric–ferroelectric phase transition field and coercive field of NaNbO3 ceramics were reduced by the introduction of AgNbO3 and Mn, making it easier to induce the ferroelectric phase and realize poling in NANM ceramics. The NANM ceramics exhibited an excellent pyroelectric coefficient of 2.55 × 10−4 C m−2 K−1 and figures of merit as Fi = 0.93 × 10−10 m/V, Fv = 6.46 × 10−2 m2/C, and Fd = 2.92 × 10−5 Pa−1/2 at room temperature. More importantly, a high depolarization temperature of 280 °C was achieved, ensuring the ability to withstand high temperature during production and operation. The NANM ceramics with excellent pyroelectric properties and high depolarization temperature are expected to be a promising lead-free candidate for uncooled infrared detector applications. [ABSTRACT FROM AUTHOR]

Recently, Bi0.5Na0.5TiO3-based ceramics have drawn widespread attention due to their excellent energy storage properties. Here, a comprehensive analysis of the composition- and temperature-driven transition processes in (1 − x)Bi0.5Na0.5TiO3-xSm2Ti2O7 (BNST-x) polycrystals have been presented using Raman scattering and spectroscopic ellipsometry. With increasing Sm2Ti2O7 content, BNST-x ceramic gradually becomes disordered and belongs to the superparaelectric state at x = 0.12 near room temperature. Moreover, the thermal evolution of the lattice kinetic behaviors shows two crucial temperatures: the depolarization temperature Td and the temperature at the maximum dielectric permittivity Tm, which suggest the transitions from nonergodic relaxor ferroelectric—ergodic relaxor (ER) ferroelectric and ER ferroelectric—superparaelectric, respectively. It is noteworthy that the series of changes is closely related to the ordering degree of the B-site ion affected by the doping and the temperature. This work gives an insight into the connection among the phonon behavior, electronic transition, and lattice structure of BNST-x ceramics, which can further understand the phase transition mechanisms under the doping and thermal field. [ABSTRACT FROM AUTHOR]

High polarization of ferroelectric materials has profound research significance and is the decisive factor in the application of energy storage, pyroelectricity, and explosive energy conversion. Herein, in force-electric conversion field, an ultrahigh remanent polarization (51.43 μC/cm2) and record-breaking energy density (4.59 J/cm3) after poling were achieved with a lead-free (1 − x)Bi0.5Na0.5TiO3 − xAgNbO3 [(1 − x)BNT – xAN] relaxor ceramics. The enhancement effect of AgNbO3 on polarization is attributed to the increase in lattice distortion and orientation after poling. Additionally, a significant force-electric conversion effect under hydrostatic pressure (depolarization rate ∼44.8%, 400 MPa) and shock pressure (depolarization rate ∼54.4%, 6.3 GPa) in (1 − x)BNT – xAN was attributed to the pressure-driven ferroelectric/relaxor (FE/RE) phase transition. This work is expected to enlighten the further design of ferroelectric materials with high polarization for pulse power energy conversion application. [ABSTRACT FROM AUTHOR]

The pressure‐driven explosive energy‐conversion (EEC) effect of ferroelectric (FE) materials has been extensively studied in scientific research and high‐tech applications owing to its high pulse‐power output capability. The fundamental principle of this effect is pressure‐driven phase transition and depolarization in FE materials, accompanied by discharging behavior from the charge release upon pressure loading. Pb(Zr,Ti)O3 has been an excellent example of a materials exhibiting these properties. However, recent investigations have been focused on developing other lead‐based or lead‐free materials with a higher energy‐storage ability and better temperature stability. In this article, we review the recent progress achieved in the past decades on different types of lead‐based and lead‐free ceramics, single crystals, and multilayer films, based on their unique pressure‐driven phase transition and energy‐conversion properties. Their pulse power discharging performance under actual shock‐wave compression is also summarized, followed by a detailed discussion of the failure mechanism under shock‐wave compression. Finally, several issues and perspectives are proposed for future investigation in this area. All these not only assist in the design of new materials for high‐performance EEC but are also helpful for the practical application of these promising materials in pulse‐power technologies. [ABSTRACT FROM AUTHOR]

Bi0.5Na0.5TiO3‐based ceramics with high remnant polarization Pr have shown outstanding potential in the application of high‐power ferroelectric transducers. However, low depolarization temperature Td is an obstacle for their application. Here, a composition design strategy was proposed to simultaneously improve the Td and Pr in BNT‐based materials. Ultrahigh Pr of 40.56 µC/cm2 and relative high Td of 184°C were synergistically achieved in (Bi0.5Na0.5)(Ti0.995Mn0.005)O3 (BNMT) ceramics by adding 1.0 mol% BiGaO3 (BG), which is superior to other reported lead‐free systems. The excellent ferroelectric properties were attributed to strengthen ferroelectric order as evidenced by increased rhombohedral distortion. Meanwhile, the enhanced depolarization temperature, increasing from 168°C for x = 0% to 184°C for x = 1.0%, can be ascribed to the suppression of the thermal‐induced ferroelectric‐relaxor phase transition by adding BG. Those results enable the BNMT‐BG systems ceramics to be an attractive candidate for application in high‐power supplies. [ABSTRACT FROM AUTHOR]

The pressure‐driven force‐electric conversion materials with extremely rapid response time have been widely used in mining, defense, and energy areas. The discharge process by the force‐electric conversion effect in ferroelectrics is dominated by polar‐nonpolar phase transformation. In this work, (Pb0.985La0.01)(ZrxTi1‐x)O3 (PLZT, x = 0.85–0.94) ceramics is designed by tunning Zr4+/Ti4+ ratio and aliovalent La doping to achieve high remnant polarization (Pr) and excellent temperature stability. We focus on the pressure‐driven depolarization in PLZT ceramics, and their corresponding phase structure, ferroelectric properties, dielectric properties, and thermal depolarization. In PLZT (x = 0.93) ceramics, the original polarization P0 increases to 43.42 μC/cm2. The pressure‐driven depolarization releases 37.66 μC/cm2 with the depolarization proportion of 86.73%, which is attributed to irreversible ferroelectric‐antiferroelectric phase transition. It also exhibits excellent temperature stability up to 120°C (> 36 μC/cm2). This work provides a high‐performance alternative to Pb(Zr0.95Ti0.05)O3 and guidance for the development of pulse power energy conversion devices. [ABSTRACT FROM AUTHOR]

As one of the classic antiferroelectrics, high complexity of a NaNbO3 structure sequence attracts great attention in the ferroelectric physics field. Here, temperature-pressure phase diagrams as a function of a CaSnO3 content for antiferroelectric (1-x)NaNbO3-xCaSnO3 ceramics have been improved by Raman spectroscopy. We clarify structural order of phase transitions on CaSnO3-modified NaNbO3 ceramics within the temperature range of 80–840 K by discussing the anomalies of lattice and phonon dynamics. The doping effect of CaSnO3 on the P-R phase transition has been summarized from the decreased critical temperature from 660 to 580 K. The intermediate phase at 480 K was recognized as an incommensurate phase. In addition, the anomalous pressure with respect to phonon frequency at the stress field of 0–25 GPa also provides the evidence of structural transformations at 6.55 and 10.05 GPa. Upon increasing the CaSnO3 content, phase transition moves to a lower pressure range. This work would provide the powerful supplement of phase transitions for the broad NaNbO3-based crystalline family with Raman scattering. [ABSTRACT FROM AUTHOR]

(Bi0.5Na0.5)TiO3 (BNT)‐based ferroelectric ceramics have drawn extensive attention because of their excellent electrical properties and interesting depolarization behavior. However, the poor thermal stability of electrical properties limits their practical application. In this work, the effect of sintering temperature (Ts) on the depolarization behavior of BNT‐based ceramics was systematically investigated. It is found that the depolarization temperature Td determined from pyroelectric measurement tends to decrease with increasing Ts, which indicates that lower Ts defers the ferroelectric‐relaxor (FE‐RE) phase transition. However, for the samples sintered at higher Ts (such as 1180°C), although the Td is reduced, the thermal stability is better compared with the sample sintered at lower Ts (1100°C) because the diffuse behavior of the FE‐RE phase transition is suppressed. According to these results, we propose that the thermal stability of electrical properties for BNT‐based ceramics is not only related to high Td, but also to the diffuse degree of phase transition. [ABSTRACT FROM AUTHOR]

Ferroelectric materials under shock compression can generate current and power by a drastic change of the remnant polarizations and surface bound charge. This behavior has been employed in applications involving nuclear fusion trigger, energy storage devices, and high pulse power sources. Despite the large power output in lead‐containing ferroelectrics, lead‐free materials are highly desirable owing to the environmental concerns. Herein, the phase transition behaviors and current outputs of 0.92Bi0.5Na0.5TiO3‐0.08BiAlO3 (BNT‐8BA) materials are studied under high pressure. The BNT‐8BA ferroelectric ceramics can be completely depolarized from polar to the nonpolar state under shock compression, resulting in a current output in the external circuit. The phase‐transition‐induced depolarization pressures of BNT‐8BA are lower than those of the pure Bi0.5Na0.5TiO3 under both dynamic and static high‐pressure loads. These results can allow the understanding of the high‐pressure behavior of BNT‐8BA for application as ferroelectric pulsed power supply. [ABSTRACT FROM AUTHOR]

We report the electric-field-induced ferroelectric (FEIN) to antiferroelectric (AFE) phase transition that is tuned by the poling temperatures in 0.89Bi0.5Na0.5TiO3-0.06BaTiO3-0.05K0.5Na0.5NbO3 (0.89BNT-0.06BT-0.05KNN) ceramics. Phase transition and pyroelectric behaviors of the ceramics were investigated as functions of temperature and electric field. Pyroelectric coefficient peaks of (3 ∼ 6.5) × 10-8 C cm-2 K-1 are detected at about 10 °C above the poling temperatures for the samples poled at different temperatures. The poling temperature tuned pyroelectric behaviors are attributed to the FEIN to AFE phase transition when the temperature increases. [ABSTRACT FROM AUTHOR]

A magnetoelectric (ME) heterostructure was fabricated by depositing a Ni‐Mn‐Ga (NMG) magnetic film on an antiferroelectric (AFE) PLZST—(Pb, La)(Zr, Sn, Ti)O3—ceramic substrate. Significant and reversible electric field‐induced relative magnetization changes (∆M/M0) were firstly observed in this magnetic/AFE heterostructure, and the ∆M/M0 vs electric field loops have been found to correspond well with the strain‐electric field curve of PLZST ceramic. The maximum ∆M/M0 variation can reach 15%, indicating an obvious strain‐mediated converse magnetoelectric (CME) effect. A maximum CME coefficient of 1.14 × 10‐9 s/m was obtained at the switching electric fields of PLZST. The collected results suggest that AFE materials with a large electric‐field‐induced phase transition strain could be alternative candidates in ME coupling heterostructures. [ABSTRACT FROM AUTHOR]

Solid solutions of (1−x)PbZrO3‐xBa(Mg1/3Nb2/3)O3 (PZ‐xBMN, x = 0.02, 0.03, 0.04, and 0.05) were prepared, and their microstructures, electrical properties, and phase transition behaviors under hydrostatic pressure were investigated. It was found that the incorporation of BMN into PZ can provide improved ferroelectric properties, leading to the formation of antiferroelectric/ferroelectric phase boundaries in PZ‐xBMN ceramics when the value of x is between 0.02 and 0.03. It was also demonstrated that the ferroelectric phases exhibit excellent temperature stability in the remanent polarization. Importantly, complete depolarization was observed in the PZ‐xBMN solid solution due to the hydrostatic pressure‐induced ferroelectric‐antiferroelectric phase transition. The resultant properties and phase transition behaviors of PZ‐xBMN ceramics under pressure will benefit their application in pulsed power supplies. [ABSTRACT FROM AUTHOR]

In this work, the effects of composition, temperature, and poling on the phase transition behavior under hydrostatic pressure of lead‐free (1‐x)[(0.98Bi0.5Na0.5Ti0.995Mn0.005O3‐0.02BiAlO3)]‐xNaNbO3 (BNT‐BA‐xNN) ceramics were investigated. It was found that hydrostatic pressure can induce a phase transformation from ferroelectric (FE) to relaxor (RE). Meanwhile, the FE‐RE phase transition pressure (PFR) tends to decrease as the NN addition increases. Moreover, increasing temperature exhibits a similar effect that is, reducing PFR. The reduced PFR were considered to result from the reduced FE stability and increasing proportion of RE phase. However, PFR was obviously enhanced after poling, which can be attributed to the induced FE phase and the formation of macrodomains with application of an electric field. These results will aid in understanding the phase transition behavior of BNT‐based relaxor ferroelectrics for applications under hydrostatic pressure. [ABSTRACT FROM AUTHOR]

The temperature scaling relations of the dynamic hysteresis were investigated in Zr-rich lead zirconate titanate (PZT) bulk ceramics. At each relation curve, there is a discontinuous district corresponding to the low- and high-temperature phase transitions. The temperatures are divided into low-T region and high-T region. At each temperature region, three power-law scaling relations were obtained for hysteresis area , coercivity Ec, and remnant polarization Pr with T, respectively. The six temperature scaling relations are field dependent and the simplified forms are different from the results obtained from the soft and hard PZT ceramics. [ABSTRACT FROM AUTHOR]

Abstract: High pyroelectric performance and good thermal stability of pyroelectric materials are desirable for the application of infrared thermal detectors. In this work, enhanced pyroelectric properties were achieved in a new ternary (1−x)(0.98(Bi0.5Na0.5)(Ti0.995Mn0.005)O3–0.02BiAlO3)–xNaNbO3 (BNT–BA–xNN) lead‐free ceramics. The effect of NN addition on the microstructure, phase transition, ferroelectric, and pyroelectric properties of BNT–BA–xNN ceramics were investigated. It was found that the average grain size decreased as x increased to 0.03, whereas increased with further NN addition. The pyroelectric coefficient p at room temperature (RT) was significantly increased from 3.87 × 10−8Ccm−2K−1 at x = 0 to 8.45 × 10−8Ccm−2K−1 at x = 0.03. The figures of merit (FOMs), Fi, Fv and Fd, were also enhanced with addition of NN. Because of high p (7.48 × 10−8Ccm−2K−1) as well as relatively low dielectric permittivity (~370) and low dielectric loss (~0.011), the optimal FOMs at RT were obtained at x = 0.02 with Fi = 2.66 × 10−10 m/V, Fv = 8.07 × 10−2 m2/C, and Fd = 4.22 × 10−5 Pa−1/2, which are superior to other reported lead‐free ceramics. Furthermore, the compositions with x ≤ 0.03 exhibited excellent temperature stability in a wide temperature range from 20 to 80°C because of high depolarization temperature (≥110°C). Those results unveil the potential of BNT–BA–xNN ceramics for infrared detector applications. [ABSTRACT FROM AUTHOR]

Abstract: The effect of lanthanum (La) content on the phase transformation of Pb1−3x/2Lax(Zr0.42Sn0.40Ti0.18)O3 (PLZST 100x/42/40/18, 0 ≤ x ≤ 0.06) ceramics was investigated by the dielectric and ferroelectric properties. The base composition PLZST 0/42/40/18 located in the ferroelectric (FE) rhombohedral phase region. As x increased, the compositions showed successively FE and antiferroelectric (AFE) state at room temperature, and their peak temperatures (Tmax) decreased gradually in line as Tmax = 162.21‐1507x. Evidence was presented that there were two dielectric anomalies in PLZST 2/42/40/18, which were corresponding to the FE‐AFE and AFE‐paraelectric (PE) phase transformations, respectively. With increasing the dc bias fields, the two phases merged into one. PLZST 3/42/40/18 showed AFE characteristics with the first loop outside of the second loop and there was only one dielectric inflection. The critical lanthanum content occurred at x = 0.03 from the dielectric temperature spectra and hysteresis loops. Furthermore increase in La above 0.03, these compositions showed typical antiferroelectric behaviors with double hysteresis loops. The stored energy properties of the three compositions (PLZST 4/42/40/18, 5/42/40/18 and 6/42/40/18) displayed different temperature dependencies from room temperature to 140°C (over their respective Tmax). Comparing the above results with previous investigations on PLZSTs, some questions were discussed. [ABSTRACT FROM AUTHOR]

Microstructure, phase transition and electric properties of Pb 0.99 (Zr 0.95 Ti 0.05 ) 0.98 Nb 0.02 O 3 (PZTN 95/5) ferroelectric ceramics modified with x wt% ZnO additive (where x  = 0, 0.1, 0.2, 0.3 and 0.4) were systematically investigated. It was found that ZnO modification brought out an improvement of densification and an increase in grain size of PZTN 95/5 ceramics. Results of dielectric and pyroelectric measurements demonstrated that, the low temperature rhombohedral-high temperature rhombohedral ferroelectric phase transition temperature ( T LH ) gradually decreased with increasing x to 0.2, while the Curie temperature ( T c) gradually increased. With further increasing ZnO content, however, T LH and T C almost showed no change. Additionally, the excellent ferroelectric, pyroelectric and piezoelectric properties were all achieved by less than 0.2 wt% ZnO modification. It is suggested that, due to superior room–temperature pyroelectric properties, the 0.2 wt% ZnO-modified PZTN 95/5 ceramics may be a promising material for applications in uncooled pyroelectric infrared detectors. [ABSTRACT FROM AUTHOR]

In this paper, the influence of phase evolution on polarization change and electrocaloric response in lead-free (Ba0.9Ca0.1)(Ti1− x Zr x)O3 ceramics ( BCTZ) was systematically investigated. With increasing Zr/Ti ratio, the phase structure and phase transition behavior were greatly changed, resulting in various temperature and electric field dependence of electrocaloric responses. For x=0.05, a peak electrocaloric temperature change 1.64 K (at 130°C) and corresponding entropy change 1.78 J·kg−1·K−1 were obtained for 0-7 kV·mm−1 electric field. Negative electrocaloric temperature change in −0.1 K was obtained below Curie temperature ( Tc), which may be induced by the orthorhombic-tetragonal ferroelectric phase transition. With the increase in x, the peak value of the electrocaloric response decreased but much better temperature stability was observed. Simultaneously the negative electrocaloric response gradually disappeared with the disappearance of the low temperature ferroelectric-ferroelectric phase transition. For x=0.2, electrocaloric response showed good temperature stability ranging from room temperature to 130°C, attributing to the relaxor ferroelectric feature. [ABSTRACT FROM AUTHOR]

The phase transition behaviors of Pb 0.99 (Zr 0.95 Ti 0.05 ) 0.98 Nb 0.02 O 3 ferroelectric ceramics doped with different MgO concentrations (0–0.2 wt%) were systematically investigated by Raman and dielectric measurements. Raman results showed that the phase transitions were strongly dependent on MgO concentration. It was found that the low temperature rhombohedral (F R(LT) )–high temperature rhombohedral (F R(HT) ) ferroelectric phase transition shifted toward a lower temperature with increasing MgO concentration up to 0.1 wt%, while the F R(HT) –cubic paraelectric (P C ) phase transition changed to a higher temperature. The Raman results were in good agreement with phase transition determined by dielectric measurements. Moreover, it was indicated that the changes of Raman active modes were related to distortion of BO 6 octahedra during the phase transitions. Then, the distortion of BO 6 octahedron caused by B-site replacement of Mg 2+ ions was proposed to explain the observed behaviors. In addition, the effects of MgO doping on the dielectric, ferroelectric and pyroelectric properties were also discussed. [ABSTRACT FROM AUTHOR]

Highlights: [•] The FR(LT)–FR(HT) phase transition was reduced from 41°C to 24°C with MgO addition. [•] Superior pyroelectric properties were obtained in 0.10wt% MgO-modified sample. [•] The largest p of 65×10−8 Ccm−2 K−1 was achieved at room temperature. [•] Fd of 20×10−5 Pa−1/2 and Fv of 0.91m2C−1 were also attained at room temperature. [ABSTRACT FROM AUTHOR]

Abstract: Sr x Ba1−x Nb2O6 (with x=0.50, 0.45, 0.40 and 0.30) ceramics were synthesized by conventional solid-state method and sintered at 1350°C for 3h. The phase structure, microstructure, dielectric, ferroelectric and pyroelectric properties of obtained ceramics were systematically investigated. Pure tungsten bronze phase could be obtained in all ceramics. The dielectric characteristics showed that SBN ceramic was a relaxor with strong diffuse phase transition and weak frequency dispersion. As Sr molar fraction x increases from 0.30 to 0.50, the transition temperature T C decreased linearly while the diffusivity parameter γ declined from 1.88 to 1.68. The saturated polarization, remnant polarization and pyroelectric coefficient were also found to be enhanced in SBN ceramics with increasing Sr content. The pyroelectric coefficient of about 2×10−8 C/cm2K can be obtained for polarized SBN50 ceramics at room temperature. [Copyright &y& Elsevier]

Energy-storage properties of 0.89 Bi0.5Na0.5TiO3-0.06 BaTiO3-0.05 K0.5Na0.5NbO3 (0.89 BNT-0.06 BT-0.05 KNN) lead-free ceramics were first investigated. Measurements of dielectric properties together with switching current curves indicate a rather diffuse ferroelectric ( FE) to anti-ferroelectric ( AFE) phase transition when heating from 20°C to 90°C. The energy density ( W), which was calculated from P-E hysteresis loops, increases linearly with the external electric field when E exceeds AFE- FE transition field. W is independent of temperature and frequency, and maintains around 0.59 J/cm3 under 5.6 kV/mm in the stable AFE phase region. These properties indicate that 0.89 BNT-0.06 BT-0.05 KNN ceramics might be a promising lead-free AFE material for energy-storage capacitor application. [ABSTRACT FROM AUTHOR]

The hysteresis behaviors and phase characteristics of Pb0.97La0.02(Zr0.90Sn0.025Ti0.075)O3 ( PLZST) ceramics were investigated in this work. A single mini hysteresis loop at 3 kV/mm with the maximum polarization ( Pmax) of 8.3 μC/cm2 and triple hysteresis loops at 6.6 kV/mm were observed, which indicates the coexistence of rhombohedral ferroelectric phase and tetragonal antiferroelectric phase. The X-ray Diffraction patterns and dielectric temperature spectra both demonstrate this coexistence. Moreover, the hysteresis loops with increasing temperature indicated that a ferroelectric-antiferroelectric phase transition occurred at about 60°C. These phenomena would be useful for understanding the domain evolution during ferroelectric and antiferroelectric phase transition. [ABSTRACT FROM AUTHOR]

PbZr0.35Ti0.65O3 (PZT), PbZrO3 (PZO), and PZT/PZO ferroelectric/antiferroelectric multilayer films were prepared on a Pt/Ti/SiO2/Si substrate using the sol–gel method. Microstructures and physical properties such as the polarization behaviors, leakage current, dielectric features, and energy-storage characteristics of the three films were systematically explored. All electric field-dependent phase transitions, from sharp to diffused, can be tuned by layer structure, indicated by the polarization, shift current, and dielectric properties. The leakage current behaviors suggested that the layer structure could modulate the current mechanism, including space-charge-limited bulk conduction for single layer films and Schottky emission for multilayer thin films. The electric breakdown strength of a PZT/PZO multilayer structure can be further enhanced to 1760 kV/cm, which is higher than PZT (1162 kV/cm) and PZO (1373 kV/cm) films. A recoverable energy-storage density of 21.1 J/cm3 was received in PZT/PZO multilayers due to its high electric breakdown strength. Our results demonstrate that a multilayer structure is an effective method for enhancing energy-storage capacitors. [ABSTRACT FROM AUTHOR]

(Pb,La)(Zr,Ti)O3 antiferroelectric (AFE) ceramics have attracted considerable interest due to their high‐energy storage density and numerous field‐induced phase transitions. However, the positional equilibrium of the A‐site and B‐site is typically maintained without considering that heterovalent doping of La3+ can induce defects within the material, leading to high‐temperature leakage conduction. In this work, we introduced the acceptor ion Na+ at the A‐site simultaneously and designed Pb0.9175–0.5xLa0.055NaxZr0.975Ti0.025O3 (x = 0.01, 0.03, 0.055, 0.07, 0.10) AFE ceramics. The dielectric properties of these ceramics exhibited a consistent pattern of improvement followed by deterioration as the content of Na+ increased. Notably, when x = 0.055 (Na5.5), the AFE ceramic demonstrated superior high‐temperature frequency stability with negligible leakage conduction. Impedance spectroscopy analysis suggested that Na5.5 displays the greatest resistance and highest Edc. Concurrently, the thermally stimulated depolarization current indicates that Na5.5 possesses the lowest defect concentration and the largest Ea. This can be attributed to the internal generation of defect dipole clusters (VPb′′−VO••−NaPb′−LaPb•$V_{{\mathrm{Pb}}}^{{\prime\prime}} - V_{\mathrm{O}}^{ \bullet \bullet } - {\mathrm{Na}}_{{\mathrm{Pb}}}^{\prime} - {\mathrm{La}}_{{\mathrm{Pb}}}^ \bullet $), which effectively restrict the movement of charged defects. These findings suggest that Na5.5 holds significant potential for application and offer insights into the understanding of internal defects in lead‐based AFE materials. [ABSTRACT FROM AUTHOR]

Pure and Nb-doped Pb(Zr 1− x Ti x )O 3 ( x = 0.47, 0.48, 0.50) ceramics were prepared by conventional solid-state reaction technique. Dielectric anomalies are observed in both kinds of samples near room temperature. The anomalies could be depressed by donor doping and prefer to be significant in ceramics with tetragonal crystallographic phase. Phase transition mechanism and domain wall pinning effect are proposed to explain this anomaly, and the former is considered as the dominated reason. Further results of the pyroelectric measurements confirm the existence of the ferroelectric–ferroelectric phase transition. [ABSTRACT FROM AUTHOR]

Abstract: Dielectric properties of Pb0.99375(Zr0.52Ti0.48)0.9875Nb0.0125O3 (PZTN) ceramics were measured during heating and cooling processes before and after poling. A dielectric anomaly from 220K to 290K was only observed in poled PZTN samples. The frequency dependence of the ε′′ peaks was fitted using the Vogel–Fulcher law, which indicated that this dielectric anomaly could be associated with the poling induced monoclinic distortion. Meanwhile, the existence of the low-temperature transformation involving rotations of the octahedra was confirmed by the broadening peaks in ε′′–T curves and the variation of slopes in ε′–T curves in both unpoled and poled samples. [Copyright &y& Elsevier]

It is the behavior of electric-field induced antiferroelectric to ferroelectric (AFE-FE) phase transition that determines the specific application scenario of antiferroelectric materials. Here, we report that the evolution of the atomic displacement ordering from full-ordered to semi-ordered modulation should be responsible for the change in the behavior of the AFE-FE transition from sharp to diffuse. The novel semi-ordered configuration is originated from the competing interaction between long-range displacement modulation and compositional inhomogeneity, which just makes the AFE-FE transition diffuse but maintains the switching field. These results provide atomic-scale understanding for AFE-FE transition and new insights for designing hysteresis-free antiferroelectric materials. [Display omitted] [ABSTRACT FROM AUTHOR]

The grinding strain induced ferroelectric (FE) to antiferroelectric (AFE) phase transition with associated hysteresis loops tuning were found in bulk Pb 0.99 (Zr 0.97 Ti 0.03) 0.98 Nb 0.02 O 3 ceramics. The induced AFE phases can keep stable unless applying heat treatment or electric field. The atomic-scale characterizations reveal that the perfect coherent FE/AFE interface appears either diffuse or sharp depending on its relative orientation to polarization. The induced surface AFE layers on FE bulk can tune hysteresis loops from symmetric to asymmetric and this effect increased with the decrease of thickness of samples. These findings provide new pathway for manipulate phase state and discover novel properties in ferroics. Grinding strain induced ferroelectric-antiferroelectric phase transition with hysteresis loops tuning in bulk ceramics. Image, graphical abstract [ABSTRACT FROM AUTHOR]

Antiferroelectrics (AFE) are considered a promising energy storage material for components that require nanosecond-level discharge. Pb(Yb 1/2 Nb 1/2)O 3 (PYN) is an AFE material with potential energy storage applications. However, the unmatched critical phase transition field (E F) and breakdown electric field (E B) conceal most of energy storage capacitance. This work is aimed to settle imbalanced E F / E B via a compositional design strategy. E F and E B were tuned in order to obtain 5.18 J cm−3 in recoverable energy density, 65% energy efficiency, and thermal and frequency stability varying within 15%, producing excellent comprehensive energy storage properties. A modified kinetic model of energetic path was used to understand the mechanism governing the variation of E F. We expect our work to contribute to further development of novel AFE materials for energy storage. [ABSTRACT FROM AUTHOR]

Highlights • Temperature-dependent optical ellipsometry measurements have been performed. • The SCP model was used to analyze the complex dielectric function. • Phase transitions were clarified with the variation of CP energies. Abstract The dielectric functions and phase transitions of MgO modified Pb 0.99 (Zr 0.95 Ti 0.05) 0.98 Nb 0.02 O 3 (PZTN- x wt% MgO, x = 0, 0.1, 0.2, 0.5) ceramics have been investigated using temperature-dependent spectroscopic ellipsometry. With the aid of standard critical-point (SCP) model, four typical interband transitions can be observed from the second derivative of dielectric functions. Three transition process are observed and can be linked to antiferroelectric (AFE)-ferroelectric (FE) (T 1 ∼ 250 K), low temperature ferroelectric phase [FE R(LT) ]to high temperature one [FE R(HT) ] (T 2 ∼ 300 K), and ferroelectric-paraelectric phase (T C ∼ 500 K). [ABSTRACT FROM AUTHOR]

Abstract Currently, there is an urgent need of extraordinary comprehensive pyroelectric materials for the wide application in detectors and energy harvesters. In this study, the (Pb 1–1.5 x La x)(Zr 0.86 Ti 0.14)O 3 (abbreviated as PLZT, x = 0.02, 0.03, 0.04 and 0.05) ceramics located in ferroelectric-antiferroelectric (FE-AFE) phase boundary were designed and synthesized by using conventional solid-state reaction method. The microstructures, phase structures, dielectric, ferroelectric, thermal depolarization and pyroelectric properties of the PLZT ceramics with different La content were investigated thoroughly. The XRD results show that the PLZT ceramics change from FE phase to AFE phase with increasing La content. The significant improvement of pyroelectric coefficient p and figures of merit (FOMs) are achieved in the PLZT ceramics with the increase in La content because of the increased metastable ferroelectric phase under the application of electric field. The (Pb 0.955 La 0.03)(Zr 0.86 Ti 0.14)O 3 (x = 0.03) ceramic exhibits not only high p of 5.2 × 10 − 8 C / cm 2 K and high depolarization temperature (T d) of 179 ℃ but also excellent FOMs with F i = 2.2 × 10 − 10 m / V , F v = 5.0 × 10 − 2 m 2 / C , and F d = 3.47 × 10 − 5 Pa − 1 / 2 . In addition, the highest p of 6.8 × 10 − 8 C / cm 2 K is achieved in (Pb 0.94 La 0.04)(Zr 0.86 Ti 0.14)O 3 (x = 0.04) ceramic. These results demonstrate that the PLZT ceramics of x = 0.03 and 0.04 are promising candidates for pyroelectric applications. [ABSTRACT FROM AUTHOR]

Pb 0.99 (Sn x Zr 0.95− x Ti 0.05 ) 0.98 Nb 0.02 O 3 (PNZST( x ), 0.10 ≤ x ≤ 0.18) ceramics were fabricated by conventional solid state reaction method. Effects of tin (Sn) doping and its content x on their structure, phase transition behavior, and electrical properties were investigated. Analysis of X-ray diffraction patterns and Rietveld refinement results confirmed the crystal structures of different phases and also compositional driven phase transitions. The results indicated that with the increase in the value of x , orthorhombic phase was transformed into distorted tetragonal phase through rhombohedral phase. Ceramics exhibited the orthorhombic–rhombohedral phase coexistence for 0.10 ≤ x ≤ 0.16, and orthorhombic–rhombohedral–distorted tetragonal multiphase coexistence for x = 0.18. Although the orthorhombic antiferroelectric (AFE) phase was the major phase, no double hysteresis loops were detected through electrical hysteresis loop measurements because the electric field-induced AFE to ferroelectric (FE) phase transition occurred under the applied electric field, and the induced FE phase could not reverse back to AFE state after the removal of electric field. However, the trace of AFE behavior could be observed at a lower testing electric field. Moreover, increasing Sn content led to linear increment in phase transition temperature of FE RL -FE RH , up to 98.7 °C for x = 0.18. [ABSTRACT FROM AUTHOR]

Lead-free antiferroelectric materials can be used in environmental-friendly energy applications and are receiving tremendous attention owing to their high energy-storage density, which is achieved through a phase transition between antiferroelectric and ferroelectric state. Here, by slowing down the antiferroelectric-ferroelectric transition via controllable beam irradiation in a transmission electron microscope, we demonstrate that such a transition in NaNbO 3 undergoes by means of forming a buffer-area (about 40–150 nm wide) at the on-going transition front. The spatial buffer-area approximately maintains its shape during moving and are characterized to be the antiferroelectric phase but exhibits a gradual variation of lattice spacing along the [010] proceeding direction of phase transition. With help of such buffer-area, the overall stress or barrier between the two phases could be considerably reduced compared to the direct change between the two structures. Therefore, our findings provide new insights for understanding the dynamical energy-storage process in antiferroelectric materials. [Display omitted] [ABSTRACT FROM AUTHOR]

The composition dependent dielectric, ferroelectric and energy storage properties of tetragonal lead lanthanum zirconate stannate titanate (PLZST) antiferroelectric ceramics were systematically studied in this paper. Two sets of simple linear scaling relations were established for the forward switching field E AFE-FE , the backward switching field E FE-AFE and recoverable energy density W re . As Zr content increases (Ti fixed), E AFE-FE , E FE-AFE , W re decreases linearly, while the stored energy density W st declines first and then increases. In addition, decreasing Ti content (Zr fixed) leads to linear increments in all of E AFE-FE , E FE-AFE , W re and W st . These results not only reveal the superiority of PLZST with lower Zr and lower Ti contents for energy storage capacitors, but also provide a fast way to design PLZST ceramics with specific energy storage properties. Our work may also be very helpful for better understanding the mechanism of phase transition behaviors of antiferroelectric materials. [ABSTRACT FROM AUTHOR]

Optical phonons and phase transitions of (Pb 0.97 La 0.02 ) (Zr 0.60 Sn 0.40− y Ti y )O 3 (PLZST 97/2/60/40-100 y /100 y ) ceramics with different compositions have been investigated by x-ray diffraction and temperature dependent Raman spectra. From the temperature dependence of low wavenumber phonon modes, two phase transitions (antiferroelectric orthorhombic to intermediate phase and intermediate phase to paraelectric cubic phase) were detected. The intermediate phase could be the coexistence one of antiferroelectric orthorhombic and ferroelectric rhombohedral phase. In addition, two modes (a soft mode and an anharmonic hopping central mode) were found in the high temperature paraelectric cubic phase. On cooling, the anharmonic hopping central mode splits into two modes in the terahertz range. Moreover, the antiferrodistortive mode appears in the antiferroelectric orthorhombic phase. Based on the analysis, the phase diagram of PLZST ceramics can be well improved. [ABSTRACT FROM AUTHOR]

In this study, we investigated the scaling behavior of dynamic hysteresis with frequency f and electric field E in epitaxial PbZrO 3 antiferroelectric film on (111)-oriented SrTiO 3 substrate. The scaling relation for the saturated hysteresis loops takes the form of hysteresis area ∝ f 0.03 ( E − 499) 0.20 at relatively low testing f . However, when frequency exceeds 30 Hz, the shows stronger dependence on f while remains basically unchanged relation with E , leading to a form of ∝ f 0.10 ( E − 499) 0.20 . The scaling behavior is modeled as occurring in a viscous medium where several forces, such as viscous and restoring forces, act on the phase transition process. [ABSTRACT FROM AUTHOR]

Abstract: Grain size effect on phase transition, dielectric and pyroelectric properties of BST ceramics under DC bias field was reported for the first time. With the grain size increased by one order of magnitude, phase transition diffuseness parameters δ and γ decreased from 282 to 63 and 1.64–1.33, respectively. This resulted in the dielectric constant maximum increased by 65%, the pyroelectric coefficient maximum and corresponding figure of merit were quadrupled and tripled, respectively. The physical essence of the great size effect can be attributed to a combination of surface effect, mechanical stress effect and extrinsic effect of grain boundary. A well understanding of the grain size effect and its mechanism will be useful for the BaTiO3-based ceramics and other ferroelectrics. [Copyright &y& Elsevier]

Abstract: The dielectric properties of unpoled and poled Pb0.88Ba0.06Sr0.06(Mg1/3Nb2/3)0.37Zr0.375Ti0.255O3 (modified PMN–PZT) ceramics were investigated. It was found that the dielectric constant increased while the loss tangent decreased after poling. A frequency independent abrupt transition in the dielectric constant and loss tangent responses was observed for the poled ceramics. This abnormal behavior was believed to be correlated with the macro–micro domain transition and the corresponding pyroelectric measurement exhibited a narrow peak at the normal-relaxor transition temperature T nr. Furthermore, the presence of double-loop-like hysteresis and two types of current peaks at a temperature slightly higher than T nr showed another strong evidence of this transition. [Copyright &y& Elsevier]

Abstract: xPb(Mg1/3Nb2/3)O3–(1−x)Pb(Zr0.47Ti0.53)O3(xPMN–(1−x)PZT) (0.15≤x≤0.30) ceramics were prepared by the conventional oxide-mixed method. The phase structure, ferroelectric and piezoelectric properties and field-induced strain behavior were systematically investigated. It was found that 0.25PMN−0.75PZT possessed superior electrical properties due to its composition close to the MPB (Morphotropic Phase Boundary). The composition near the MPB enables the existence of multiple polarization directions and consequently facilitates the domain reorientation, which should be responsible for the superior electrical properties. A large remnant polarization (P r ) of 34.2µC/cm2 and a high piezoelectric coefficient (d 33) of 698pC/N were obtained. Especially, a large field-induced strain of 2.2‰ (at 40kV/cm) was attained, which shows a great promise for actuator applications. [Copyright &y& Elsevier]

Abstract: A phase diagram for the lead-free ceramics in the (1−x%)(0.89Bi0.5Na0.5TiO3–0.06BaTiO3–0.05K0.5Na0.5NbO3)–x%MnO2 (BNBKN-x%Mn) binary system is constructed for the first time based on the ferroelectric and dielectric measurements. The ferroelectric behaviors under different temperatures suggest that the ceramics are basically of relaxor anti-ferroelectric nature near room temperature. The temperature dependent dielectric properties show that when the addition of MnO2 increases, the relaxor anti-ferroelectric phase can be stabilized to be close to the Curie point, which corresponds to a relaxor anti-ferroelectric to paraelectric phase transition. [Copyright &y& Elsevier]