Phase engineering in NaNbO_(3) antiferroelectrics for high energystorage density

The NaNbO_(3) antiferroelectrics have been considered as a potential candidate for dielectric capacitorsapplications. However, the high-electric-field-unstable antiferroelectric phase resulted in low energystorage density and efficiency. Herein, good energy storage properties were realized in (1-x)NaNbO_(3)- xNaTaO_(3) ceramics, by building a new phase boundary. As a result, a high recoverable energy density(Wrec) of 2.2 J/cm3 and efficiency (h) of 80.1% were achieved in 0.50NaNbO_(3)-0.50NaTaO_(3) ceramic at300 kV/cm. The excellent energy storage performance originates from an antiferroelectric-paraelectricphase boundary with simultaneously high polarization and low hysteresis, by tailoring the ratio ofantiferroelectric and paraelectric phases. Moreover, the 0.50NaNbO_(3)-0.50NaTaO_(3) ceramic also exhibitedgood temperature and frequency stability, together with excellent charge-discharge performance. Theresults pave a good way of designing new NaNbO_(3)-based antiferroelectrics with good energy storageperformance.

Perspective on antiferroelectrics for energy storage and conversion applications

As a close relative of ferroelectricity,antiferroelectricity has received a recent resurgence of interest driven by technological aspirations in energy-efficient applications,such as energy storage capacitors,solid-state cooling devices,explosive energy conversion,and displacement transducers.Though prolonged efforts in this area have led to certain progress and the discovery of more than 100 antiferroelectric materials over the last 70 years,some scientific and technological issues remain unresolved.Herein,we provide perspectives on the development of antiferroelectrics for energy storage and conversion applications,as well as a comprehensive understanding of the structural origin of antiferroelectricity and field-induced phase transitions,followed by design strategies for new lead-free antiferroelectrics.We also envision unprecedented challenges in the development of promising antiferroelectric materials that bridge materials design and real applications.Future research in these directions will open up new possibilities in resolving the mystery of antiferroelectricity,provide opportunities for comprehending structure-property correlation and developing antiferroelectric/ferroelectric theories,and suggest an approach to the manipulation of phase transitions for real-world applications.

Domain size and charge defects affecting the polarization switching of antiferroelectric domains

The switching behavior of antiferroelectric domain structures under the applied electric field is not fully understood.In this work,by using the phase field simulation,we have studied the polarization switching property of antiferroelectric domains.Our results indicate that the ferroelectric domains nucleate preferably at the boundaries of the antiferroelectric domains,and antiferroelectrics with larger initial domain sizes possess a higher coercive electric field as demonstrated by hysteresis loops.Moreover,we introduce charge defects into the sample and numerically investigate their influence.It is also shown that charge defects can induce local ferroelectric domains,which could suppress the saturation polarization and narrow the enclosed area of the hysteresis loop.Our results give insights into understanding the antiferroelectric phase transformation and optimizing the energy storage property in experiments.

Electromechanical-induced antiferroelectric-ferroelectric phase transition in PbLa(Zr,Sn,Ti)O_3 ceramic

Antiferroelectric ferroelectric （AFE-FE） phase transition in ceramic Pbo.97Lao.02（Zro.75Snon36Tion14）O3 （PLZST） was studied by dielectric spectroscopy as functions of frequency （102-105 Hz） and pressure （0-500 MPa） under a DC electric field. The hydrostatic pressure-dependent remnant polarization and dielectric constant were mea- sured. The results show that remnant polarization of the metastable rhombohedral ferroelectric PLZST poled ceramic decreases sharply and depoles completely at phase transition under hydrostatic pressure. The dielectric constant um dergoes an abrupt jump twice during a load and unload cycle under an electric field. The two abrupt jumps correspond to two phase transitions, FE AFE and AFE-FE.

Enhanced energy storage behaviors in free-standing antiferroelectric Pb(Zr_(0.95)Ti_(0.05))O_3 thin membranes

Free-standing antiferroelectric Pb（Zr0.95Ti0.05O3（PZT（95/5）） thin film is fabricated on 200-nm-thick Pt foil by using pulsed laser deposition.X-ray diffraction patterns indicate that free-standing PZT（95/5） film possesses an α-axis preferred orientation.The critical electric field for the 300-nm-thick free-standing PZT（95/5） film transiting from antiferroelectric to ferroelectric phases is increased to 770 kV/cm,but its saturation polarization remains almost unchanged as compared with that of the substrate-clamped PZT（95/5） film.The energy storage density and energy efficiency of the substrate-clamped PZT（95/5） film are 6.49 J/cm^3 and 54.5%,respectively.In contrast,after removing the substrate,the energy storage density and energy efficiency of the free-standing PZT（95/5） film are enhanced up to 17.45 J/cm^3 and 67.9%,respectively.

Release of charges under external fields of PbLa(Zr,Sn,Ti)O_3 ceramic

This paper investigates the pyroelectric of poled antiferroelectric （AFE） ceramic Pbo.97Lao.02 （Zro.69Sno.196 Ti0.114）03 and its remnant polarization dependence of hydrostatic pressure. The results show that the bound charges of poled sample can be released in short time by temperature field or pressure field. The released charge abruptly forms a large pulse current. The phenomena of released charge under external fields result in the ferroelectric-AFE phase transition induced by temperature or hydrostatic pressure.

基于 PSZT的 RAINBOW型驱动器研究(英文)

A new type of large\|displacement actuator called RAINBOW (Reduced And Internally Biased Oxide Wafer) was fabricated by a chemical reduction of PSZT antiferroelectric ceramic. It is found that PSZT was easily reduced and the optimal conditions for producing RAINBOW samples were determined to be 870℃ for 2~3 h. The AFE\|FE phase transitions occur at lower field strength in RAINBOWs compared with normal PSZT. Larger axial displacement (about 190μm) was obtained from the RAINBOWs by application of electric ...

Electric properties and phase transition behavior in lead lanthanum zirconate stannate titanate ceramics with low zirconate content

The phase transitions, dielectric properties, and polarization versus electric field （P-E） hysteresis loops of Pbo.97Lao.02（Zr0.42Sn0.58-xTix）O3 （0.13≤ x ≤0.18） （PLZST） bulk ceramics were systematically investigated. This study exhibited a sequence of phase transitions by analyzing the change of the P-E hysteresis loops with increasing temperature. The anfiferroelectric （AFE） to ferroelectric （FE） phase boundary of PLZST with the Zr content of 0.42 was found to locate at the Ti content between 0.14 and 0.15. This work is aimed to improve the ternary phase diagram of lanthanum-doped PZST with the Zr content of 0.42 and will be a good reference for seeking high energy storage density in the PLZST system with low-Zr content.

Geometric and Electronic Structure of Squaric Acid from DFT Calculation

The crystal and electronic structure of antiferroelectric squaric acid is studied using density functional theory method, and the exchange correlation effects are treated by the generalized approximation. In order to understand the ferroelectricity of H2SQ in the molecular plane and the antiferroelectricity in whole crystal, the density of states, charge density distribution and band structure are calculated. The result showed that O2p and C2p play important roles in the interactions between layers. The hybridizations of 02s-Hls and 02p-Hls are responsible for the tendency to ferroelectricity within each layer.

Effects of precursor solution concentration on dielectric properties of (Pb,La)(Zr,Ti)O_3 antiferroelectric thick films by sol-gel processing

Pb0.97La0.02Zr0.95Ti0.05O3(PLZT)antiferroelectric thick films derived from different precursor solution concentrations are prepared on platinized silicon substrates by sol-gel processing.The films present polycrystalline perovskite structure with a(100)preferred orientation by X-ray diffraction(XRD)analysis.The antiferroelectricity of the films is confirmed by the double hysteresis behaviors of polarization and double-bufferfly response of dielectric constant under the applied electrical field.Antiferroelectric properties and dielectric constant are improved while the polarization characteristic values are reduced with the increase of precursor solution concentration.The films at higher precursor solution concentration exhibit excellent dielectric properties.

FABRICATION AND PROPERTIES OF ANTIFERROELECTRIC RAINBOW ACTUATOR

A new type of large-displacement actuator called reduced and internally biased oxide wafer （RAINBOW） is fabricated by chemical reduction of Pb（Sn, Zr, Ti）O3（PSZT） antiferroelectric ceramics and its properties are investigated. It is found that PSZT is easily reduced and the optimal conditions for producing RAINBOW samples are determined to be 870 ℃ for 2-3 h. The antiferroelectrics-ferroelectrics phase transitions occur at lower field strength in RAINBOW actuators compared with normal PSZT actuators. Large axial displacements are also obtained from the RAINBOW actuator by application of electric fields exceeding the phase switching level. However, the field-induced displacement of the RAINBOW actuator is dependent on the manner of applying load on the samples.

Dielectric Properties and the Phase Transition of Pure and Cerium Doped Calcium-Barium-Niobate

The complex dielectric constant of pure and cerium doped calcium-barium-niobate (CBN) was studied at frequencies 20 Hz ≤ f ≤ 1 MHz in the temperature range 300 K ≤ T ≤ 650 K and compared with the results for the well known ferroelectric relaxor strontium-barium-niobate (SBN). By the analysis of the systematically taken temperature and frequency dependent measurements of the dielectric constant the phase transition characteristic of the investigated materials was evaluated. From the results it must be assumed that CBN shows a slightly diffuse phase transition without relaxor behavior. Doping with cerium yields a definitely different phase transition characteristic with some indications for a relaxor type ferroelectric material, which are common from SBN.

Substitution of Pb with (Li_(1/2)Bi_(1/2)) in PbZrO_(3)-based antiferroelectric ceramics

PbZrO_(3)-based antiferroelectric(AFE)ceramics are promising dielectrics for high-energy-density capacitors due to their reversible phase transitions during charge-discharge cycles.In this work,a new composition series,[Pb_(0.93-x)La_(0.02)(Li_(1/2)Bi_(1/2))_(x)Sr_(0.04)][Zr_(0.57)Sn_(0.34)Ti_(0.09)]O_(3),with Li^(+)and Bi^(3+)substitution of Pb^(2+)at x=0,0.04,0.08,0.12,0.16 is investigated for the microstructure evolution,ferroelectric(FE)and dielectric properties.It is found that Li^(+) and Bi^(3+) substitution can significantly reduce the sintering temperature and simultaneously enhance the dielectric breakdown strength.An ultrahigh energy efficiency(94.0%)and a large energy density(3.22 J/cm^(3))are achieved in the composition of x=0.12 with a low sintering temperature(1075℃).

Relaxor antiferroelectric-relaxor ferroelectric crossover in NaNbO_(3)-based lead-free ceramics for high-efficiency large-capacitive energy storage

Relaxor ferroic dielectrics have garnered increasing attention in the past decade as promising materials for energy storage.Among them,relaxor antiferroelectrics(AFEs)and relaxor ferroelectrics(FEs)have shown great promise in term of high energy storage density and efficiency,respectively.In this study,a unique phase transition from relaxor AFE to relaxor FE was achieved for the first time by introducing strong-ferroelectricity BaTiO_(3)into NaNbO_(3)-BiFeO_(3)system,leading to an evolution from AFE R hierarchical nanodomains to FE polar nanoregions.A novel medium state,consisting of relaxor AFE and relaxor FE,was identified in the crossover of 0.88NaNbO_(3)–0.07BiFeO_(3)–0.05BaTiO_(3)ceramic,exhibiting a distinctive core-shell grain structure due to the composition segregation.By harnessing the advantages of high energy storage density from relaxor AFE and large efficiency from relaxor FE,the ceramic showcased excellent overall energy storage properties.It achieved a substantial recoverable energy storage density W_(rec)~13.1 J/cm^(3)and an ultrahigh efficiencyη~88.9%.These remarkable values shattered the trade-off relationship typically observed in most dielectric capacitors between W_(rec)andη.The findings of this study provide valuable insights for the design of ceramic capacitors with enhanced performance,specifically targeting the development of next generation pulse power devices.

Role of polarization evolution in the hysteresis effect of Pb-based antiferroelecrtics

The electric field-induced irreversible domain wall motion results in a ferroelectric(FE) hysteresis. In antiferroelectrics(AFEs), the irreversible phase transition is the main reason for the hysteresis effects, which plays an important role in energy storage performance. Compared to the well-demonstrated FE hysteresis,the structural mechanism of the hysteresis in AFE is not well understood. In this work, the underlying correlation between structure and the hysteresis effect is unveiled in Pb(Zr,Sn,Ti)O_(3) AFE system by using in-situ electrical biasing synchrotron X-ray diffraction. It is found that the AFE with a canting dipole configuration, which shows a continuous polarization rotation under the electric field, tends to have a small hysteresis effect. It presents a negligible phase transition, a small axis ratio, and electric field-induced lattice changing, small domain switching. All these features together lead to a slim hysteresis loop and a high energy storage efficiency. These results offer a deep insight into the structure-hysteresis relationship of AFEs and are helpful for the design of energy storage material.

Observation of stabilized negative capacitance effect in hafnium-based ferroic films

A negative capacitance(NC)effect has been proposed as a critical pathway to overcome the‘Boltzmann tyranny’of electrons,achieve the steep slope operation of transistors and reduce the power dissipation of current semiconductor devices.In particular,the ferroic property in hafnium-based films with fluorite structure provides an opportunity for the application of the NC effect in electronic devices.However,to date,only a transient NC effect has been confirmed in hafnium-based ferroic materials,which is usually accompanied by hysteresis and is detrimental to low-power transistor operations.The stabilized NC effect enables hysteresis-free and low-power transistors but is difficult to observe and demonstrate in hafnium-based films.This difficulty is closely related to the polycrystalline and multi-phase structure of hafnium-based films fabricated by atomic layer deposition or chemical solution deposition.Here,we prepare epitaxial ferroelectric Hf_(0.5)Zr_(0.5)O_(2) and antiferroelectric ZrO_(2) films with single-phase structure and observe the capacitance enhancement effect of Hf_(0.5)Zr_(0.5)O_(2)/Al_(2)O_(3) and ZrO_(2)/Al_(2)O_(3) capacitors compared to that of the isolated Al_(2)O_(3) capacitor,verifying the stabilized NC effect.The capacitance of Hf_(0.5)Zr_(0.5)O_(2) and ZrO_(2) is evaluated as−17.41 and−27.64 pF,respectively.The observation of the stabilized NC effect in hafnium-based films sheds light on NC studies and paves the way for low-power transistors.

Achieving a high energy storage density in Ag(Nb,Ta)O_(3) antiferroelectric films via nanograin engineering

Due to its lead-free composition and a unique double polarization hysteresis loop with a large maximum polarization(Pmax)and a small remnant polarization(Pr),AgNbO_(3)-based antiferroelectrics(AFEs)have attracted extensive research interest for electric energy storage applications.However,a low dielectric breakdown field(Eb)limits an energy density and its further development.In this work,a highly efficient method was proposed to fabricate high-energy-density Ag(Nb,Ta)O_(3) capacitor films on Si substrates,using a two-step process combining radio frequency(RF)-magnetron sputtering at 450℃and post-deposition rapid thermal annealing(RTA).The RTA process at 700℃led to sufficient crystallization of nanograins in the film,hindering their lateral growth by employing short annealing time of 5 min.The obtained Ag(Nb,Ta)O_(3) films showed an average grain size(D)of~14 nm(obtained by Debye-Scherrer formula)and a slender room temperature(RT)polarization-electric field(P-E)loop(Pr≈3.8 mC·cm^(−2) and P_(max)≈38 mC·cm^(−2) under an electric field of~3.3 MV·cm^(−1)),the P-E loop corresponding to a high recoverable energy density(W_(rec))of~46.4 J·cm^(−3) and an energy efficiency(η)of~80.3%.Additionally,by analyzing temperature-dependent dielectric property of the film,a significant downshift of the diffused phase transition temperature(T_(M2-M3))was revealed,which indicated the existence of a stable relaxor-like AFE phase near the RT.The downshift of the T_(M2-M3) could be attributed to a nanograin size and residual tensile strain of the film,and it led to excellent temperature stability(20-240℃)of the energy storage performance of the film.Our results indicate that the Ag(Nb,Ta)O_(3) film is a promising candidate for electrical energy storage applications.

Local probing of the non-uniform distribution of ferrielectric and antiferroelectric phases

Piezoresponse force microscopy(PFM)is an indispensable tool in the investigation of local electromechanical responses and polarization switching.The acquired data provide spatial information on the local disparity of polarization switching and electromechanical responses,making this technique advantageous over macroscopic approaches.Despite its widespread application in ferroelectrics,it has rarely been used to investigate the ferrielectric(FiE)behaviors in antiferroelectric(AFE)materials.Herein,the PFM was utilized to study the local electromechanical behavior and distribution of FiE,and the AFE phases of PbZrO_(3)thin-film were studied,where only the FiE behavior is observable using a macroscopic approach.The FiE region resembles a ferroelectric material at low voltages but exhibits a unique on-field amplitude response at high voltages.In contrast,the AFE region only yields an observable response at high voltages.Phase-field simulations reveal the coexistence of AFE and FiE states as well as the phase-transition processes that underpin our experimental observations.Our work illustrates the usefulness of PFM as an analytical tool to characterize AFE/FiE materials and their phase-coexistence behavior,thereby providing insights to guide property modification and potential applications.

Realizing simultaneously excellent energy storage and discharge properties in AgNbO_(3)based antiferroelectric ceramics via La^(3t)and Ta^(5+)co-substitution strategy

AgNbO_(3)based antiferroelectric(AFE)ceramics have large maximum polarization and low remanent polarization,and thus are important candidates for fabricating dielectric capacitors.However,their energy storage performances have been still large difference with those of lead-based AFEs because of their room-temperature ferrielectric(FIE)behavior.In this study,novel La^(3+)and Ta^(5+)co-substituted AgNbO_(3)ceramics are designed and developed.The introduction of La^(3+)and Ta^(5+)decreases the tolerance factor,reduces the polarizability of B-site cations and increases local structure heterogeneity of AgNbO_(3),which enhance AFE phase stability and refine polarization-electric field(PeE)loops.Besides,adding La^(3+)and Ta^(5+)into AgNbO_(3)ceramics causes the decrease of the grain sizes and the increase of the band gap,which contribute to increased Eb.As a consequence,a high recoverable energy density of 6.79 J/cm3 and large efficiency of 82.1%,which exceed those of many recently reported AgNbO_(3)based ceramics in terms of overall energy storage properties,are obtained in(Ag0.88La0.04)(Nb0.96Ta0.04)O_(3)ceramics.Furthermore,the discharge properties of the ceramic with discharge time of 16 ns and power density of 145.03 MW/cm3 outperform those of many lead-free dielectric ceramics.

Review on field-induced phase transitions in lead-free NaNbO_(3)-based antiferroelectric perovskite oxides for energy storage

Emerging new applications of antiferroelectric perovskite oxides based on their fascinating phase transformation between polar and nonpolar states have provided considerable attention to this class of materials even decades after the discovery of antiferroelectricity.After presenting the challenge of formulating a precise definition of antiferroelectric materials,we briefly summarize proposed applications.In the following,we focus on the crystallographic structures of the antiferroelectric and ferroelectric phases of NaNbO_(3),which is emerging as a promising alternative to PbZrO_(3)-based systems.The field-induced phase transition behavior of NaNbO_(3)-based AFE materials in the form of single crystals,bulk ceramics,and multilayer ceramic capacitors is reviewed.Recent advances in a group of materials exhibiting high energy storage performance and relaxor-like behavior are also covered.The influence of electrode geometry on phase transition behavior and thus on the energy storage property is briefly addressed.The review concludes with an overview of the remaining challenges related to the fundamental understanding of the scientific richness of AFE materials in terms of structure,microstructure,defect transport under high fields,and phase transition dynamics required for their future development and applications.