ELECTROMECHANICAL DEFORMATION AND FRACTURE OF PIEZOELECTRIC/FERROELECTRIC MATERIALS

This review presents the progress and current status of the investigation on electromechanical deformation and fracture of piezo electric/ferroelectric materials. An attempt is made to summarize a few fundamental aspects, which include electromechanical constitutive relations, piezoelectric micromechanics and electric fracture and fatigue, instead of describing all technological backgrounds, basic physics, experimental findings, and theoretical developments. A number of open questions and future prospective are presented. It is hoped that this review will encourage people to join the exploration of this important and interesting field.

Electrocaloric effect in ferroelectric materials:From phase field to first-principles based effective Hamiltonian modeling

Electrocaloric effect(ECE)of ferroelectrics has attracted considerable interest due to its potential application in environmentally friendly solid-state refrigeration.The discovery of giant ECE in ferroelectric thin films has greatly renewed the research activities and significantly stimulated experimental and theoretical investigations.In this review,the recent progress on the theoretical modeling of ECE in ferroelectric and antiferroelectric materials are introduced,which mainly focuses on the phase field modeling and first-principles based effective Hamiltonian method.We firstly provide the theoretical foundation and technique details for each method.Then a comprehensive review on the progress in the application of two methods and the strategies to tune the ECE are presented.Finally,we outline the practical procedure on the development of multi-scale computational method without experiemtal parameters for the screening of optimized electrocaloric materials.

Preparation and Microstrutures of BSTO/MgO Ferroelectric Materials for Phase Shift

Barium strontium titanate/magnesia （BSTO/MgO） ferroelectric material for phase shift was prepared by traditional solid phase synthesis. The phase distribution, microstructure and electric properties were investigated. The results show that no secondary phase appears in the composites and the dimension of grains distributes uniformly. With 50 wt% MgO content, the dielectric tunability reaches 17.5 % in the external DC field of 4 000 Vomm^-1 and the microwave loss at about 2.5 GHz is 8×10^-3. Hence, it can be applied in tunable microwave phase shifters.

Recent advances in memristors based on two-dimensional ferroelectric materials

In this big data era, the explosive growth of information puts ultra-high demands on the data storage/computing, such as high computing power, low energy consumption, and excellent stability. However, facing this challenge, the traditional von Neumann architecture-based computing system is out of its depth owing to the separated memory and data processing unit architecture. One of the most effective ways to solve this challenge is building brain inspired computing system with in-memory computing and parallel processing ability based on neuromorphic devices. Therefore, there is a research trend toward the memristors, that can be applied to build neuromorphic computing systems due to their large switching ratio, high storage density, low power consumption, and high stability. Two-dimensional (2D) ferroelectric materials, as novel types of functional materials, show great potential in the preparations of memristors because of the atomic scale thickness, high carrier mobility, mechanical flexibility, and thermal stability. 2D ferroelectric materials can realize resistive switching (RS) because of the presence of natural dipoles whose direction can be flipped with the change of the applied electric field thus producing different polarizations, therefore, making them powerful candidates for future data storage and computing. In this review article, we introduce the physical mechanisms, characterizations, and synthetic methods of 2D ferroelectric materials, and then summarize the applications of 2D ferroelectric materials in memristors for memory and synaptic devices. At last, we deliberate the advantages and future challenges of 2D ferroelectric materials in the application of memristors devices.

Ferroelectric materials for neuroinspired computing applications

In recent years,the emergence of numerous applications of artificial intelligence(AI)has sparked a new technological revolution.These applications include facial recognition,autonomous driving,intelligent robotics,and image restoration.However,the data processing and storage procedures in the conventional von Neumann architecture are discrete,which leads to the“memory wall”problem.As a result,such architecture is incompatible with AI requirements for efficient and sustainable processing.Exploring new computing architectures and material bases is therefore imperative.Inspired by neurobiological systems,in-memory and in-sensor computing techniques provide a new means of overcoming the limitations inherent in the von Neumann architecture.The basis of neural morphological computation is a crossbar array of high-density,high-efficiency non-volatile memory devices.Among the numerous candidate memory devices,ferroelectric memory devices with non-volatile polarization states,low power consumption and strong endurance are expected to be ideal candidates for neuromorphic computing.Further research on the complementary metal-oxide-semiconductor(CMOS)compatibility for these devices is underway and has yielded favorable results.Herein,we first introduce the development of ferroelectric materials as well as their mechanisms of polarization reversal and detail the applications of ferroelectric synaptic devices in artificial neural networks.Subsequently,we introduce the latest developments in ferroelectrics-based in-memory and in-sensor computing.Finally,we review recent works on hafnium-based ferroelectric memory devices with CMOS process compatibility and give a perspective for future developments.

Enhancing BiVO_(4)photoanode performance by insertion of an epitaxial BiFeO_(3)ferroelectric layer

BiVO_(4)(BVO)is a promising material as the photoanode for use in photoelectrochemical applications.However,the high charge recombination and slow charge transfer of the BVO have been obstacles to achieving satisfactory photoelectrochemical performance.To address this,various modifications have been attempted,including the use of ferroelectric materials.Ferroelectric materials can form a permanent polarization within the layer,enhancing the separation and transport of photo-excited electron-hole pairs.In this study,we propose a novel approach by depositing an epitaxial BiFeO_(3)(BFO)thin film underneath the BVO thin film(BVO/BFO)to harness the ferroelectric property of BFO.The self-polarization of the inserted BFO thin film simultaneously functions as a buffer layer to enhance charge transport and a hole-blocking layer to reduce charge recombination.As a result,the BVO/BFO photoanodes showed more than 3.5 times higher photocurrent density(0.65 mA cm^(-2))at 1.23 V_(RHE)under the illumination compared to the bare BVO photoanodes(0.18 m A cm^(-2)),which is consistent with the increase of the applied bias photon-to-current conversion efficiencies(ABPE)and the result of electrochemical impedance spectroscopy(EIS)analysis.These results can be attributed to the self-polarization exhibited by the inserted BFO thin film,which promoted the charge separation and transfer efficiency of the BVO photoanodes.

On the use of ferroelectric material LiNbO3 as novel photocatalyst in wastewater-fed microbial fuel cells

In this work, the use of lithium niobate （LiNbO3）, a ferroelectric and photocatalyst material, is investi- gated as a new type of cathode catalyst for wastewater-fed single-chamber microbial fuel cells （MFCs）. Carbon cloth electrodes coated with LiNbO3 were studied with and without UV-vis irradiation to assess its photocatalytic behavior in these devices. The synthesized phase of LiNbO3 was characterized by X- ray diffraction, differential scanning calorimetry, particle size distribution, and transmission electron microscopy analyses. The MFC containing a LiNbO3-based cathode exhibited a maximum open circuit potential and power output of 400 mV and 131 mW/m^3, respectively, under irradiation. This cathode configuration also achieved the maximum chemical oxygen demand removal of 84% after 120 h of MFC operation. These results show that ferroelectric materials such as LiNbO3 could be used as cathode cat- alysts in MFC devices. As a complementary analysis, the removal of the heavy metals detected in the wastewater was also monitored.

Ferroelectric materials for vibrational energy harvesting

Energy harvesting is an appealing technology that makes use of the ambient energy which is otherwise wasted. Piezoelectric materials directly convert the elastic energy to the electric energy, and thus have a great advantage in scavenging vibrational energy for simplicity in device structure with relatively high power density. This paper provides an overview on the research of piezoelectric materials in energy harvesting in recent decades, from basics of piezoelectricity and working principle of energy harvesting with piezoelectric materials, to the progress of development of high-performance piezoelectrics including ceramics, single crystals and polymers, then to experimental attempts on the device fabrication and optimization, finally to perspective applications of piezoelectric energy harvesting(PEH). The criteria for selection of materials for PEH applications are introduced. Not only the figure of merit but also maximum allowable stress of materials are taken into account in the evaluation of their potential in achieving high energy density and output power density. The influence of the device configuration on the performance is also acknowledged and discussed. The magnitude and distribution of induced stress in the piezoelectric unit upon excitation by the vibration source play an important role in determining the output power density and can be tuned via proper design of device configuration without changing its resonant frequency. Approaches to address the issue of frequency match accompanying with the resonant mode are illustrated with literature examples. Usage of PEH devices can be extended to a variety of vibration sources in everyday life as well as in nature. Some appealing applications of PEH, such as in implantable and wearable devices, are reviewed.

Tensile stress regulated microstructures and ferroelectric properties of Hf_(0.5)Zr_(0.5)O_(2) films

The discovery of ferroelectricity in HfO_(2) based materials reactivated the research on ferroelectric memory.However,the complete mechanism underlying its ferroelectricity remains to be fully elucidated.In this study,we conducted a systematic study on the microstructures and ferroelectric properties of Hf_(0.5)Zr_(0.5)O_(2)(HZO)thin films with various annealing rates in the rapid thermal annealing.It was observed that the HZO thin films with higher annealing rates demonstrate smaller grain size,reduced surface roughness and a higher portion of orthorhombic phase.Moreover,these films exhibited enhanced polarization values and better fatigue cycles compared to those treated with lower annealing rates.The grazing incidence x-ray diffraction measurements revealed the existence of tension stress in the HZO thin films,which was weakened with decreasing annealing rate.Our findings revealed that this internal stress,along with the stress originating from the top/bottom electrode,plays a crucial role in modulating the microstructure and ferroelectric properties of the HZO thin films.By carefully controlling the annealing rate,we could effectively regulate the tension stress within HZO thin films,thus achieving precise control over their ferroelectric properties.This work established a valuable pathway for tailoring the performance of HZO thin films for various applications.

Evaluation of the differential capacitance for ferroelectric materials using either charge-based or energy-based expressions

Differential capacitance is derived based upon energy,charge or current considerations,and determined when it may go negative or positive.These alternative views of differential capacitances are analyzed,and the relationships between them are shown.Because of recent interest in obtaining negative capacitance for reducing the subthreshold voltage swing in field effect type of devices,using ferroelectric materials characterized by permittivity,these concepts are now of paramount interest to the research community.For completeness,differential capacitance is related to the static capacitance,and conditions when the differential capacitance may go negative in relation to the static capacitance are shown.

Strain engineering and hydrogen effect for two-dimensional ferroelectricity in monolayer group-Ⅳmonochalcogenides MX(M=Sn,Ge;X=Se,Te,S)

Two-dimensional(2D)ferroelectric compounds are a special class of materials that meet the need for devices miniaturization,which can lead to a wide range of applications.Here,we investigate ferroelectric properties of monolayer group-IV monochalcogenides MX(M=Sn,Ge;X=Se,Te,S)via strain engineering,and their effects with contaminated hydrogen are also discussed.GeSe,GeTe,and GeS do not go through transition up to the compressive strain of-5%,and consequently have good ferroelectric parameters for device applications that can be further improved by applying strain.According to the calculated ferroelectric properties and the band gaps of these materials,we find that their band gap can be adjusted by strain for excellent photovoltaic applications.In addition,we have determined the most stable hydrogen occupancy location in the monolayer SnS and SnTe.It reveals that H prefers to absorb on SnS and SnTe monolayers as molecules rather than atomic H.As a result,hydrogen molecules have little effect on the polarization and electronic structure of monolayer SnTe and SnS.

Self-Adaptive and Electric Field-Driven Protective Layer with Anchored Lithium Deposition Enable Stable Lithium Metal Anode

Lithium metal battery has great development potential because of its lowest electrochemical potential and highest theoretical capacity.However,the uneven deposition of Li^(+)flux in the process of deposition and stripping induces the vigorous growth of lithium dendrites,which results in severely battery performance degradation and serious safety hazards.Here,the tetragonal BaTiO3 polarized by high voltage corona was used to build an artificial protective layer with uniform positive polarization direction,which enables uniform Li^(+)flux.In contrast to traditional strategies of using protective layer,which can guide the uniform deposition of lithium metal.The ferroelectric protective layer can accurately anchor the Li^(+)and achieve bottom deposition of lithium due to the automatic adjustment of the electric field.Simultaneously,the huge volume changes caused by Li^(+)migration change of the lithium metal anode during charging and discharging is functioned to excite the piezoelectric effect of the protective layer,and achieve seamless dynamic tuning of lithium deposition/stripping.This dynamic effect can accurately anchor and capture Li^(+).Finally,the layer-modified Li anode enables reversible Li plating/stripping over 1500 h at 1 mA cm^(-2)and 50℃in symmetric cells.In addition,the assembled Li-S full cell exhibits over 300 cycles with N/P≈1.35.This work provides a new perspective on the uniform Li^(+)flux at the Li-anode interface of the artificial protective layer.

Analysis of the electromechanical behavior of ferroelectric ceramics based on a nonlinear finite element model

A nonlinear finite element （FE） model based on domain switching was proposed to study the electromechanical behavior of ferroelectric ceramics. The incremental FE formulation was improved to avoid any calculation instability. The problems of mesh sensitivity and convergence, and the efficiency of the proposed nonlinear FE technique have been assessed to illustrate the versatility and potential accuracy of the said technique. The nonlinear electromechanical behavior, such as the hysteresis loops and butterfly curves, of ferroelectric ceramics subjected to both a uniform electric field and a point electric potential has been studied numerically. The results obtained are in good agreement with those of the corresponding theoretical and experimental analyses. Furthermore, the electromechanical coupling fields near （a） the boundary of a circular hole, （b） the boundary of an elliptic hole and （c） the tip of a crack, have been analyzed using the proposed nonlinear finite element method （FEM）. The proposed nonlinear electromechanically coupled FEM is useful for the analysis of domain switching, deformation and fracture of ferroelectric ceramics.

Intrinsic photocatalytic water oxidation activity of Mn-doped ferroelectric BiFeO3

The development of stable and efficient visible light-absorbing oxide-based semiconductor photocatalysts is a desirable task for solar water splitting applications.Recently,we proposed that the low photocurrent density in film-based BiFeO_(3)(BFO)is due to charge recombination at the interface of the domain walls,which could be largely reduced in particulate photocatalyst systems.To demonstrate this hypothesis,in this work we synthesized particulate BFO and Mn-doped BiFeO_(3)(Mn-BFO)by the sol-gel method.Photocatalytic water oxidation tests showed that pure BFO had an intrinsic photocatalytic oxygen evolution reaction(OER)activity of 70μmol h^(-1) g^(-1),while BFO-2,with an optimum amount of Mn doping(0.05%),showed an OER activity of 255μmol h^(-1) g^(-1) under visible light(λ≥420 nm)irradiation.The bandgap of Mn-doped BFO could be reduced from 2.1 to 1.36 eV by varying the amount of Mn doping.Density functional theory(DFT)calculations suggested that surface Fe(rather than Mn)species serve as the active sites for water oxidation,because the overpotential for water oxidation on Fe species after Mn doping is 0.51 V,which is the lowest value measured for the different Fe and Mn species examined in this study.The improved photocatalytic water oxidation activity of Mn-BFO is ascribed to the synergistic effect of the bandgap narrowing,which increases the absorption of visible light,reduces the activation energy of water oxidation,and inhibits the recombination of photogenerated charges.This work demonstrates that Mn doping is an effective strategy to enhance the intrinsic photocatalytic water oxidation activity of particulate ferroelectric BFO photocatalysts.

Ferroelectric Properties and Applications of Hybrid Organic-Inorganic Perovskites

Hybrid organic-inorganic perovskites （e.g. CH;NH;PbI;） have attracted tremendous attention due to their promise for achieving next-generation cost-effective and high performance optoelectronic devices.These hybrid organic-inorganic perovskites possess excellent optical and electronic properties, including strong light absorption, high carrier abilities, optimized charge diffusion lengths, and reduced charge recombination etc., leading to their widespread applications in advanced solar energy technologies （e.g.high efficiency perovskite solar cells）. However, there is still a lack of investigations regarding fundamental properties such as ferroelectricity in these perovskites.As conventional ferroelectric ceramics are prepared at high temperature and have no mechanically flexibility,low-temperature proceed and flexible perovskite ferroelectrics have become promising candidates and should be exploited for future flexible ferroelectric applications. Here, ferroelectric properties in hybrid organic-inorganic perovskites and several state-of-the-art perovskite ferroelectrics are reviewed. Novel ferroelectric applications of hybrid organic-inorganic perovskites are discussed as well, providing guideline for realizing future high performance and flexible ferroelectric devices.

Ferroelectric solid solution Li1-xTa1-xWxO3 as potential photocatalysts in microbial fuel cells:Effect of the W content

Microbial fuel cells(MFCs)are bio-electrochemical systems that can directly convert the chemical energy contained in an effluent into bioelectricity by the action of microorganisms.The performance of these devices is heavily impacted by the choice of the material that forms the cathode.This work focuses on the assessment of ferroelectric and photocatalytic materials as a new class of non-precious catalysts for MFC cathode construction.A series of cathodes based on mixed oxide solid solution of LiTaO_3with WO_3formulated as Li_(1-x)Ta_(1-x)W_xO_3(x=0,0.10,0.20 and0.25),were prepared and investigated in MFCs.The catalyst phases were synthesized,identified and characterized by DRX,PSD,MET and UV–Vis absorption spectroscopy.The cathodes were tested as photoelectrocatalysts in the presence and in the absence of visible light in devices fed with industrial wastewater.The results revealed that the catalytic activity of the cathodes strongly depends on the ratio of substitution of W^(6+)in the LiTaO_3matrix.The maximum power densities generated by the MFC working with this series of cathodes increased from60.45 mW·m^(-3)for x=0.00(LiTaO_3)to 107.2 mW·m^(-3)for x=0.10,showing that insertion of W^(6+)in the tantalate matrix can improve the photocatalytic activity of this material.Moreover,MFCs operating under optimal conditions were capable of reducing the load of chemical oxygen demand by 79%(COD_(initial)=1030 mg·L^(-1)).

Impedance and ferroelectric properties of Sr^(2+) modified PZT-PMN ceramics

Sr^2＋ modified polycrystalline PZT-PMN ceramics were synthesized by a semi-wet route. Impedance spectroscopy studies indicate the bulk and grain boundary effects of PZT-PMN material along with the negative temperature coefficient of resistance. The bulk conductiv-ity exhibits an Arrhenius-type thermally activated hopping process which is supported by the AC conductivity behavior as a function of fre-quency and temperature. It is observed that the remnant polarization increases with an increase in the Sr2＋content in PZT-PMN.

High-performance ferroelectric based materials via high-entropy strategy:Design,properties,and mechanism

High-performance ferroelectric materials are widely used in various electronic devices owing to the function of mutual conversion among different energies,which mainly relates to their special structure gene of polarization configuration.Recent researches show that the high-entropy strategy has emerged as an effective and flexible approach for boosting physical properties in high-entropy ferroelectrics via the delicate design of local polarization configurations and other intrinsic effects caused by entropy increment,such as entropy stabilization,lattice disorder,inhibition of grain coarsening,improved mechanical properties,cocktail effect,and so on.In this review,the recent research progress about high-entropy ferroelectrics has been summarized,especially for the directional design of novel local polarization configurations according to the characteristics of different electrical properties such as high piezoelectricity,high-efficiency energy storage,and large electrostriction,providing a guidance for designing and exploring more novel local polarization configurations in high-entropy ferroelectrics for generating higher performance.

Research progress on 2D ferroelectric and ferrovalley materials and their neuromorphic application

Two-dimensional(2D)ferroelectric and ferrovalley materials have recently received extensive attention due to their significant advantages for modern electronic devices,such as miniaturization,low-dissipation,non-volatility,and multi-functionality.More interestingly,the couplings between the ferroic orders in these materials have enriched the development of intelligent devices,especially in neuromorphic computing.In this paper,the research progress of 2D ferroelectric and ferrovalley materials is introduced and the coupling effects between them are also described.Then,we briefly introduce recent neuromorphic computing reports based on 2D ferroelectric materials and give perspectives on ferrovalley neuromorphic devices.

Visualizing interface states in In_(2)Se_(3)–WSe_(2)monolayer lateral heterostructures

Recent findings of two-dimensional(2D)ferroelectric(FE)materials provide more possibilities for the development of 2D FE heterostructure electronic devices based on van der Waals materials and the application of FE devices under the limit of atomic layer thickness.In this paper,we report the in-situ fabrication and probing of electronic structures of In_(2)Se_(3)–WSe_(2) lateral heterostructures,compared with most vertical FE heterostructures at present.Through molecular beam epitaxy,we fabricated lateral heterostructures with monolayer WSe_2(three atomic layers)and monolayer In_(2)Se_(3)(five atomic layers).Type-Ⅱband alignment was found to exist in either the lateral heterostructure composed of anti-FEβ′-In_(2)Se_(3) and WSe_(2) or the lateral heterostructure composed of FEβ*-In_(2)Se_(3)and WSe_2,and the band offsets could be modulated by ferroelectric polarization.More interestingly,interface states in both lateral heterostructures acted as narrow gap quantum wires,and the band gap of the interface state in theβ*-In_(2)Se_(3)–WSe_(2)heterostructure was smaller than that in theβ′-In_(2)Se_(3)heterostructure.The fabrication of 2D FE heterostructure and the modulation of interface state provide a new platform for the development of FE devices.