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 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.

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.

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.

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.

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.

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.

Enantiomeric hybrid high-temperature multiaxial ferroelectrics with a narrow bandgap and high piezoelectricity

Ferroelectric semiconductors have sparked growing attention in the field of optoelectronics,due to their unique ferroelectric photovoltaic effect.Recently,substantial efforts have been devoted to the development of ferroelectric semiconductors,including inorganic oxides,organic-inorganic hybrids,and metal-free perovskites.Nevertheless,reports of ferroelectric semiconductors with a bandgap of less than 2 eV have been scarce.Here,in combination with the incorporation of triiodide(I_(3)−)and the introduction of chiral cations,we successfully constructed a pair of enantiomeric organic-inorganic hybrid ferroelectric semiconductors,(S-1,2-DAP·I)_(4)·I_(3)·BiI_(6)and(R-1,2-DAP·I)_(4)·I_(3)·BiI_(6)(R/S-1,2-DAP=(R/S)-(–)-1,2-diaminopropane),which possess high-temperature multiaxial ferroelectric phase transition with an Aizu notation of 422F2(s)at 405 K,a narrow bandgap of 1.56 eV comparable to that of CH3NH3PbI_(3)(∼1.5 eV),and an impressive piezoelectric response(piezoelectric coefficient,d22 of 35 pC/N)on par with PVDF(polyvinylidene fluoride,30 pC/N).With intriguing attributes,(S-1,2-DAP·I)_(4)·I_(3)·BiI_(6)and(R-1,2-DAP·I)_(4)·I_(3)·BiI_(6)exhibit great potential for application of self-power polarized-light detection and piezoelectric sensors.

Machine learning assisted prediction of dielectric temperature spectrum of ferroelectrics

In material science and engineering,obtaining a spectrum from a measurement is often time-consuming and its accurate prediction using data mining can also be difficult.In this work,we propose a machine learning strategy based on a deep neural network model to accurately predict the dielectric temperature spectrum for a typical multi-component ferroelectric system,i.e.,(Ba_(1−x−y)Ca_(x)Sr_(y))(Ti_(1−u−v−w)Zr_(u)Sn_(v)Hf_(w))O_(3).The deep neural network model uses physical features as inputs and directly outputs the full spectrum,in addition to yielding the octahedral factor,Matyonov–Batsanov electronegativity,ratio of valence electron to nuclear charge,and core electron distance(Schubert)as four key descriptors.Owing to the physically meaningful features,our model exhibits better performance and generalization ability in the broader composition space of BaTiO3-based solid solutions.And the prediction accuracy is superior to traditional machine learning models that predict dielectric permittivity values at each temperature.Furthermore,the transition temperature and the degree of dispersion of the ferroelectric phase transition are easily extracted from the predicted spectra to provide richer physical information.The prediction is also experimentally validated by typical samples of(Ba_(0.85)Ca_(0.15))(Ti_(0.98–x)Zr_(x)Hf_(0.02))O_(3).This work provides insights for accelerating spectra predictions and extracting ferroelectric phase transition information.

Intrinsic ferroelectrics and carrier doping-induced metallic multiferroics in an atomic wire

Low-dimensional multiferroic metals characterized by the simultaneous coexistence of ferroelectricity,conductivity,and magnetism hold tremendous potential for scientific and technological endeavors.However,the mutually exclusive mechanisms among these properties impede the discovery of multifunctional conducting multiferroics,especially at the atomic-scale.Here,based on first-principles calculations,we design and demonstrate intrinsic one-dimensional(1D)ferroelectrics and carrier dopinginduced metallic multiferroics in an atomicWOF4 wire.TheWOF4 atomic wire that can be derived from a 1D van derWaals crystal exhibits pronounced ferroelectricity manifested in the form of large cooperative atomic displacements.By performing Monte Carlo simulations with an effective Hamiltonian method,we obtain the nanowire that can sustain a high Curie temperature,indicating its potential for roomtemperature applications.Moreover,doping with electrons is found to induce magnetism and metallic conductivity that coexists with the ferroelectric distortion in the nanowire.These appealing properties in conjunction with the experimental feasibility enable the doped WOF4 nanowire to act as a promising atomic-scale multifunctional material.

Multi-element B-site substituted perovskite ferroelectrics exhibit enhanced electrocaloric effect

Electrocaloric(EC)refrigeration holds the promise to achieve next-generation refrigeration technology that can be efficiently powered by electricity.BaTiO_(3)(BT)-based ferroelectric materials are attractive owing to their environmentally benign compositions,large polarization,and existing manufacturing method for multilayer ceramic capacitors(MLCC),which have stimulated intensive research efforts on these materials.Here,we report an enhanced electrocaloric effect(ECE)and the refrigeration capacity of multi-element B-site substituted BT-based ceramics.The compositions of the proposed Ba(Hf_(x)Sn_(x)Zr_(y))-Ti_(1-2x-y)O_(3)(BHSZT)ceramics were selected by fine-tuning each substituent against Titanium ions Ti^(4+),aiming to their respective morphotropic phase boundary(MPB).The BHSZT exhibited an ECE that is greater than that of the single-element substituted BaTiO_(3) ceramics by at least 50%,reaching an adiabatic temperature change of above 1.7 K under 40 kV/cm.Meanwhile,the operating temperature window of the BHSZT ceramics is observed to cover the room temperature,which is a critical feature that allows the device implementation in our daily life.The multi-element substitution improved the overall ECE performances,providing a high degree of freedom for polar reorientation and hence the large polar entropy that could be utilized by the external electric field.

Point-defect-driven flattened polar phonon bands in fluorite ferroelectrics

The scale-free ferroelectric polarization of fluorite MO_(2)(M=Hf,Zr)due to flat polar phonon bands are promising for nonvolatile memories.Defects are also widely introduced to improve the emergent ferroelectricity.However,their roles are still not fully understood at the atomic-level.Here,we report a significant effect of point-defect-driven flattening of polar phonon bands with more polar modes and polarization contribution in doped MO_(2).The polar phonon bands in La-doped MO_(2)(M=Hf,Zr)can be significantly flattened,compared with pure ones.However,the lower energy barrier with larger polarization of VO-only doped MO_(2) compared with La-doped cases suggest that VO and local lattice distortion should be balanced for high-performance fluorite ferroelectricity.The work is believed to bridge the relation between point defects and the generally enhanced induced ferroelectricity in fluorite ferroelectrics at the atomic-level and inspire their further property optimization via defect-engineering.

Deep learning for exploring ultra-thin ferroelectrics with highly improved sensitivity of piezoresponse force microscopy

Hafnium oxide-based ferroelectrics have been extensively studied because of their existing ferroelectricity,even in ultra-thin film form.However,studying the weak response from ultra-thin film requires improved measurement sensitivity.In general,resonance-enhanced piezoresponse force microscopy(PFM)has been used to characterize ferroelectricity by fitting a simple harmonic oscillation model with the resonance spectrum.However,an iterative approach,such as traditional least squares(LS)fitting,is sensitive to noise and can result in the misunderstanding of weak responses.In this study,we developed the deep neural network(DNN)hybrid with deep denoising autoencoder(DDA)and principal component analysis(PCA)to extract resonance information.The DDA/PCA-DNN improves the PFM sensitivity down to 0.3 pm,allowing measurement of weak piezoresponse with low excitation voltage in 10-nm-thick Hf_(0.5)Zr_(0.5)O_(2) thin films.Our hybrid approaches could provide more chances to explore the low piezoresponse of the ultra-thin ferroelectrics and could be applied to other microscopic techniques.