Large Energy Capacitive High-Entropy Lead-Free Ferroelectrics

Advanced lead-free energy storage ceramics play an indispensable role in next-generation pulse power capacitors market.Here,an ultrahigh energy storage density of~13.8 J cm^(-3)and a large efficiency of~82.4%are achieved in high-entropy lead-free relaxor ferroelectrics by increasing configuration entropy,named high-entropy strategy,realizing nearly ten times growth of energy storage density compared with low-entropy material.Evolution of energy storage performance and domain structure with increasing configuration entropy is systematically revealed for the first time.The achievement of excellent energy storage properties should be attributed to the enhanced random field,decreased nanodomain size,strong multiple local distortions,and improved breakdown field.Furthermore,the excellent frequency and fatigue stability as well as charge/discharge properties with superior thermal stability are also realized.The significantly enhanced comprehensive energy storage performance by increasing configuration entropy demonstrates that high entropy is an effective but convenient strategy to design new high-performance dielectrics,promoting the development of advanced capacitors.

Recent progress on integrating two-dimensional materials with ferroelectrics for memory devices and photodetectors

Two-dimensional （2D） materials, such as graphene and MoS2 related transition metal dichalcogenides （TMDC）, have attracted much attention for their potential applications. Ferroelectrics, one of the special and traditional dielectric materials, possess a spontaneous electric polarization that can be reversed by the application of an external electric field. In recent years, a new type of device, combining 2D materials with ferroelectrics, has been fabricated. Many novel devices have been fabricated, such as low power consumption memory devices, highly sensitive photo-transistors, etc. using this technique of hybrid systems incorporating ferroelectrics and 2D materials. This paper reviews two types of devices based on field effect transistor （FET） structures with ferroelectric gate dielectric construction （termed FeFET）. One type of device is for logic applications, such as a graphene and TMDC FeFET for fabricating memory units. Another device is for optoelectric applications, such as high performance phototransistors using a graphene p-n junction. Finally, we discuss the prospects for future applications of 2D material FeFET.

Effect of an electric field on the electrocaloric response of ferroelectrics

The electrocaloric effect of the model ferroelectric BaTiO3was investigated using phenomenological theory. The results indicate that the applied electric field strength is a key factor for the induced electrocaloric response and there are two distinguishing electrocaloric responses. When a moderate electric field is applied, the electrocaloric temperature variation is small but the electrocaloric strength is high. In contrast, the electrocaloric temperature variation is large but electrocaloric strength is low when a very high electric field is applied. These results are consistent with the experimental observations on BaTiO3based bulk and thin film ferroelectric materials.

NUMERICAL ANALYSIS OF DIELECTRIC RESPONSE IN RELAXOR FERROELECTRICS

The dielectric response of complex perovskite relaxor ferrolectrics Pb(Mg1/3Nb2/3) O3 with respect to temperature and frequency was carefully measured. Using a normalized method of the 'universal' many-body theory, the relaxation process was analyzed around the temperature of dielectric absorption maximum. There is no structural phase transition near this temperature and the behavior is closely like that of a polar dipole medium. The functional relationship about frequency and temperature of dielectric pormittivity maximum was also fitted to discuss the dynamic behavior of polar microregion. It is confirmed that a new power exponential Arrhenius relation is better to characterize the relaxation behavior than the Vogel-Fulcher and Debye relations. Based on the polarization theory of polar dipoles, we analyzed the relaxation mechanism of ferroelectric microdomains of relaxor ferroelectrics, and get an ideal distribution function of relaxation time. Consequently, a simulated dielectric response dependence on temperature and frequencies can be expressed, which is well coincided with experiment results.

An energy-consistent fracture model for ferroelectrics

The fracture behavior of ferroelectrics has been intensively studied in recent decades, though currently a widely accepted fracture mechanism is still lacking. In this work, enlightened by previous experimental observations that crack propagation in ferroelectrics is always accompanied by domain switching, we propose a micromechanical model in which both crack propagation and domain switching are controlled by energy-based criteria. Both electric energy and mechanical energy can induce domain switching, while only mechanical energy can drive crack propagation. Furthermore, constrained domain switching is considered in this model, leading to the gradient domain switching zone near the crack tip. Analysis results show that stress-induced ferroelastic switching always has a toughening effect as the mechanical energy release rate serves as the driving force for both fracture and domain switching. In comparison, the electric-field-induced switching may have either a toughening or detoughening effect. The proposed model can qualitatively agree with the existing experimental results.

Monte Carlo simulation on dielectric relaxation and dipole cluster state in relaxor ferroelectrics

The Ginzburg-Landau theory on ferroelectrics with random field induced by dipole defects is studied by using Monte Carlo simulation, in order to investigate the dipole configuration and the dielectric relaxation of relaxor ferro-electrics. With the increase of random field, the dipole configuration evolves from the long-range ferroelectric order into the coexistence of short-range dipole-clusters and less polarized matrix. The dipole-cluster phase above the transition temperature and superparaelectric fluctuations far below this temperature are identified for the relaxor ferroelectrics. We investigate the frequency dispersion and the time-domain spectrum of the dielectric relaxation, demonstrating the Vogel-Fulcher relationship and the multi-peaked time-domain distribution of the dielectric relaxation.

Synthesis and Microstructure of Partly-oriented Bismuth Layer Structure Ferroelectrics Ceramics SrBi_4Ti_4O_(15)

SrBi4Ti4O15 powder was synthesized by conventional solid state synthesis （ CS ） and molten salt synthesis （ MSS ） . MSS method can synthesize plate-like SrBi4Ti4O15 at lower temperature （900℃） than CS method. Plate-like form becomes more distinct when the synthesis temperature increases. This would help cause the grain orientation of the ceramics after sintering. The sintered samples of MSS had grain orientation at （0,0, 10） plane. The degree of （0,0,10） grain orientation F was 62.1% . Hot pressing made （0,0,10） grain orientation more distinct （ F = 85.7% ）. The microstructures of the sintered samples were detected by SEM. Due to the grain orientation the density of samples fabricated by MSS was lower than that of prepared by CS.

Recent progress on two-dimensional ferroelectrics:Material systems and device applications

Ferroelectrics are a type of material with a polar structure and their polarization direction can be inverted reversibly by applying an electric field.They have attracted tremendous attention for their extensive applications in non-volatile memory,sensors and neuromorphic computing.However,conventional ferroelectric materials face insulating and interfacial issues in the commercialization process.In contrast,two-dimensional(2D)ferroelectric materials usually have excellent semiconductor performance,clean van der Waals interfaces and robust ferroelectric order in atom-thick layers,and hold greater promise for constructing multifunctional ferroelectric optoelectronic devices and nondestructive ultra-high-density memory.Recently,2D ferroelectrics have obtained impressive breakthroughs,showing overwhelming superiority.Herein,firstly,the progress of experimental research on 2D ferroelectric materials is reviewed.Then,the preparation of 2D ferroelectric devices and their applications are discussed.Finally,the future development trend of 2D ferroelectrics is looked at.

Domain Wall Width in Different Ferroelectrics via Perturbation Route

The domains are of fundamental interest for engineering a ferroelectric material. The domain wall and its width control the ferroelectric behavior to a great extent. The stability of polarization in the context of Landau-Ginzburg free energy functional has been worked out in a previous work by a perturbation approach, where two limits of domain wall width were estimated within the stability zone and they were also found to correspond well with the data on lithium niobate and lithium tantalate. In the present work, it is shown that this model is valid for a wide range of ferroelectric materials and also for a given ferroelectric, such as lithium niobate with different levels of impurities, which are known to affect the domain wall width.

Surface Ferron Excitations in Ferroelectrics and Their Directional Routing

The duality between electric and magnetic dipoles inspires recent comparisons between ferronics and magnonics.Here we predict surface polarization waves or“ferrons”in ferroelectric insulators,taking the long-range dipolar interaction into account.We predict properties that are strikingly different from the magnetic counterpart,i.e.the surface Damon-Eshbach magnons in ferromagnets.The dipolar interaction pushes the ferron branch with locked circular polarization and momentum to the ionic plasma frequency.The low-frequency modes are on the other hand in-plane polarized normal to their wave vectors.The strong anisotropy of the lower branch renders directional emissions of electric polarization and chiral near fields when activated by a focused laser beam,allowing optical routing in ferroelectric devices.

Potts-Ising model for simulation of polarization switching in polycrystalline ferroelectrics

This paper proposes a scheme based on the Potts and Ising models for simulating polarization switching of polycrystalline ferroelectrics using the Monte Carlo method. The polycrystalline texture with different average grain size is produced from the Potts model. Then Ising model is implemented in the polycrystalline texture to produce the domain pattern and hysteresis loop. The domain patterns and hysteresis loops have been obtained for polycrystalline texture with different average grain size. From the results of domain pattern evolution process under an applied electric field using this scheme, an extended domain, which covers more than one grain with polarization aligned roughly in the same direction, has been observed during the polarization reversal. This scheme can well reproduce the basic properties of polycrystalline ferroelectrics and is a valuable tool for exploring the physical properties of polycrystalline ferroelectrics.

Candidate ferroelectrics via ab initio high-throughput screening of polar materials

Ferroelectrics are a class of polar and switchable functional materials with diverse applications,from microelectronics to energy conversion.Computational searches for new ferroelectric materials have been constrained by accurate prediction of the polarization and switchability with electric field,properties that,in principle,require a comparison with a nonpolar phase whose atomic-scale unit cell is continuously deformable from the polar ground state.For most polar materials,such a higher-symmetry nonpolar phase does not exist or is unknown.Here,we introduce a general high-throughput workflow that screens polar materials as potential ferroelectrics.We demonstrate our workflow on 1978 polar structures in the Materials Project database,for which we automatically generate a nonpolar reference structure using pseudosymmetries,and then compute the polarization difference and energy barrier between polar and nonpolar phases,comparing the predicted values to known ferroelectrics.Focusing on a subset of 182 potential ferroelectrics,we implement a systematic ranking strategy that prioritizes candidates with large polarization and small polar-nonpolar energy differences.To assess stability and synthesizability,we combine information including the computed formation energy above the convex hull,the Inorganic Crystal Structure Database id number,a previously reported machine learning-based synthesizability score,and ab initio phonon band structures.To distinguish between previously reported ferroelectrics,materials known for alternative applications,and lesser-known materials,we combine this ranking with a survey of the existing literature on these candidates through Google Scholar and Scopus databases,revealing~130 promising materials uninvestigated as ferroelectric.Our workflow and large-scale high-throughput screening lays the groundwork for the discovery of novel ferroelectrics,revealing numerous candidates materials for future experimental and theoretical endeavors.

Excellent energy storage performance in Bi_(0.5)Na_(0.5)TiO_(3)-based lead-free high-entropy relaxor ferroelectrics via B-site modification

Next-generation advanced high/pulsed power capacitors urgently require dielectric materials with outstanding energy storage performance.Bi_(0.5)Na_(0.5)TiO_(3)-based lead-free materials exhibit high polarization,but the high remanent polarization and large polarization hysteresis limit their applications in dielectric capacitors.Herein,high-entropy perovskite relaxor ferroelectrics(Na_(0.2)Bi_(0.2)Ba_(0.2)Sr_(0.2)Ca_(0.2))(Ti1-x%Zrx%)O_(3)are designed by adding multiple ions in the A-site and replacing the B-site Ti^(4+)with a certain amount of Zr^(4+).The newly designed system showed high relaxor feature and slim polarization-electric(P-E)loops.Especially,improved relaxor feature and obviously delayed polarization saturation were found with the increasing of Zr^(4+).Of particular importance is that both high recoverable energy storage density of 6.6 J/cm^(3) and energy efficiency of 93.5%were achieved under 550 kV/cm for the ceramics of x=6,accompanying with excellent frequency stability,appreciable thermal stability,and prosperous discharge property.This work not only provides potential dielectric materials for energy storage applications,but also offers an effective strategy to obtain dielectric ceramics with ultrahigh comprehensive energy storage performance to meet the demanding requirements of advanced energy storage applications.

Two new high-temperature molecular ferroelectrics[1,5-3.2.2-Hdabcn]X(X=ClO_(4)^(-),ReO_(4)^(-))

Molecular ferroelectrics have attracted much attention because of their excellent piezoelectricity,mechanical workability,and second harmonic effect.Here,we successfully prepared two molecular ferroelectrics[1,5-3.2.2-Hdabcn]X(X=ClO_(4)^(-),1;ReO_(4)^(-),2)by reactions of a quasi-spherical amine 1,5-diazabicycle[3.2.2]nonane(1.5-3.2.2-dabcn)with HX aqueous solution.Compounds 1 and 2 undergo hightemperature phase transitions at 381 K(1)and 396 K(2).Before and after the phase transition,they crystallize in the polar point group mm2,and the centrosymmetric point groups mmm and 4/mmm,respectively.According to Aizu rules,these two compounds experience mmm Fmm2 and 4/mmm Fmm2 type ferroelectric phase transitions,respectively.The ferroelectricity of both compounds is well expressed in their polycrystalline film at room temperature with low coercive voltages of 13 V for 1 and 25 V for 2.Using piezoelectric force microscopy(PFM),the 180°anti-parallel ferroelectric domains and the reversible polarization switching can be clearly observed in 1 and 2.This high-temperature molecular ferroelectric material has great application potential in flexible materials,biomechanics,intelligent wearables and other fields.

Nanostructures formation in ferroelectrics in the process of phase transformation

Received 26 June 2014;Revised 13 October 2014;Accepted 20 October 2014;Published 12 November 2014 Inhomogeneous states caused by the coexistence of the ferroelectric(FE)and antiferroelectric(AFE)phases in lead–zirconate–titanate based solid solutions have been investigated.It has been found that the domains of the FE and AFE phases with sizes of the order of 20 nm to 30 nm coexist in the bulk of the samples due to a small difference in the free energies of these phases.The coherent character of the interphase boundaries(IPBs)leads to the concentration of the elastic stresses along these boundaries.These elastic stresses cause the local decomposition of the solid solution and formation of segregates near the IPBS due to the condition that equivalent positions of the crystal lattice are occupied by the ions with different sizes.The sizes of the segregates formed in this way are of the order 8 nm to 15 nm.Some physical effects caused by the presence of these segregate nanostructures are analyzed and discussed.

DIELECTRIC RELAXATION IN RELAXOR FERROELECTRICS

In this review the dielectric properties of relaxor ferroelectrics are discussed and compared withthe properties of normal dielectrics and ferroelectrics. We try to draw a general picture ofdielectric relaxation starting from a textbook review of the underlying concepts and pay attentionto common behavior of relaxors rather than to the features observed in specific materials. We hopethat this general approach is beneficial to those physicists, chemists, material scientists and deviceengineers who deal with relaxors. Based on the analysis of dielectric properties, a comprehensivedefinition of relaxors is proposed: relaxors are defined as ferroelectrics in which the maximum inthe temperature dependence of static susceptibility occurs within the temperature range ofdielectric relaxation, but does not coincide with the temperature of singularity of relaxation timeor soft mode frequency.

Dielectric behavior of poled complex perovskite relaxor ferroelectrics

RELAXOR ferroelectric ceramics with complex perovskite structure is considered as the first material chosen for multilayer capacitors (MLC) in technology and economy, because of their high permittivity, lower sintering temperature and lower capacitors changing rate with temperature (temperature coefficient) for diffuse phase transition (DPT). Thus, preparations and properties about the materials received more attention. There are many reports about their dielectric properties but there are few about their poled dielectric behavior. In the

Neuromorphic devices based on fluorite-structured ferroelectrics

A continuous exponential rise has been observed in the storage and processing of the data that may not curtail in the foreseeable future.The required data processing speed and power consumption are restricted by the buses between the logic and memory devices that are characteristic of the von Neumann computing architecture.Bio-mimicking neuromorphic computing has garnered considerable academic and industrial interest to resolve these challenges.Additionally,devices based on emerging nonvolatile memories capable of mimicking the behaviors of synapses and neurons,which are the main elements in biological computing systems(brains),are attracting significant interest from the device community.With the discovery of ferroelectricity in fluorite-structured oxides,such as HfO2 and ZrO2,which are compatible with the state-of-the-art complementary-metal-oxide-semiconductor processes,ferroelectric devices have rapidly evolved as the main direction of these research and development activities.Fundamental science related to fluorite-structured ferroelectrics has been intensively studied over the last decade.At present,the focus is gradually moving to practical applications,including neuromorphic computing and advanced classical processing or memory units in the conventional von Neumann architecture.However,despite its rapid development,the wealth of recent progress in neuromorphic computing devices based on fluorite-structured ferroelectrics has not been reviewed and systemized.This progress report comprehensively reviews and systemizes the recent progress in artificial synaptic and spiking neuron devices for neuromorphic computing based on fluorite-structured ferroelectrics.

Abnormal phase transition and polarization mismatch phenomena in BaTiO_(3)-based relaxor ferroelectrics

Relaxor ferroelectrics have been extensively studied due to their outstanding dielectric,piezoelectric,energy storage,and electro-optical properties.Although various theories were proposed to elaborate on the relaxation phenomena,polar nanoregions formed by disruption of the long-range-order structures are considered to play a key role in relaxor ferroelectrics.Generally,relaxor ferro-electrics are formed by aliovalent substitution or isovalent substitution in normal ferroelectrics,or further combinations of solid solutions.Herein,one category of BaTiO_(3)-based relaxor ferroelectrics with abnormal phase transition and polarization mismatch phenomena is focused.Characteristic parameters of such BaTiO_(3)-based relaxor ferroelectrics,including the Curie temperature,polarization,and lattice parameter,show a typical“U”-shaped variation with compositions.The studied BaTiO_(3)-based relaxor ferroelectrics are mostly solid solutions of A-site coupling and B-site coupling ferroelectrics,exhibiting polarization mismatch in certain compositions[e.g.,0.9BaTiO_(3)-0.1BiScO_(3),0.8BaTiO_(3)-0.2Bi(Mg_(1/2)Ti_(1/2)O_(3),0.8BaTiO_(3)-0.2Bi(Mg_(2/3)Nb_(1/3)O_(3),0.5BaTiO_(3)-0.5Pb(Mg_(1/3)Nb_(2/3)O_(3),0.4BaTiO_(3)-0.6Pb(Zn_(1/3)Nb_(2/3)O_(30,etc.].Of particular interest is that excellent electrical properties can be achieved in the studied relaxor ferroelectrics.Therefore,polarization mismatch theory can also provide guidance for the design of new high-performance lead-free relaxor ferroelectrics.