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.

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.

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.

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.

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.

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.

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.

Theoretical study of mutual control mechanism between magnetization and polarization in multiferroic materials

The mutual control mechanism between magnetization and polarization in multiferroic materials is studied. The system contains a ferromagnetic sublattice and a ferroelectric sublattice. To describe the magneto–electric coupling, we propose a linear coupling Hamiltonian between ferromagnetism and ferroelectricity without microscopic derivation. This coupling enables one to retrieve the hysteresis loops measured experimentally. The thermodynamic properties of the system are calculated, such as the temperature dependences of the magnetization, polarization, internal energy and free energy.The ferromagnetic and ferroelectric hysteresis loops driven by either a magnetic or an electric field are calculated, and the magnetic spin and pseudo-spin are always flipped synchronously under the external magnetic and electric field. Our theoretical results are in agreement with the experiments.

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.

Ferroelectric solid solutions with perovskite- and columbite-type components: From structures formation to domain and hysteresis phenomena

The paper reports results on the complex study on ferroelectric ceramics that represent solid solutions containing components with a perovskite-type or columbite-type structure.Solid solutions of a three-component(1−x−y)NaNbO_(3)−xKNbO_(3)−yCdNb_(2)O_(6) system are manufactured at x=0.05-0.20 and y=0.10.Domain structures in ceramic grains are studied.The consistency between experimental and calculated results is examined for coexisting phases split into non-180°domains(mechanical twins)in the solid solution with x=0.15.A correlation between the internal structure(crystal,domain,granular,and defect)and fundamental elec­tromechanical and polarization properties is stated for the studied three-component solid solutions.

Strong emissions of blue-yellow-red regions of La and Ti modified KNaNbO_(3) ferroelectric ceramics

In this work,the results of the study on the optical properties of the perovskite structure ABO3 with La^(3+) substitution for ions K^(+) and Na^(+) in the A site and Ti^(4+) substitution for ion Nb^(5+) in the B site are presented.The ceramics were sintered at 1100℃ and 1190℃ and formed at 10 MPa and 80 MPa.Dense ceramics were obtained with 94% of the theoretical density.The piezoresponse force microscopy(PFM)showed needle-shaped grains with a size of 30 nm for the samples formed at 10 MPa at both sintering temperatures.Apparently,the high temperature and high pressure used in formation reduced the energy of the band gap(Eg)from 3.36 to 3.09 eV.Strong emissions to 2.19,1.86,2.5,and 2.31 eV were obtained by exciting the samples at 325,373,457,and 500 nm,respectively;these emissions corresponded to blue-yellow-red regions of the visible spectrum.

CO Catalytic Oxidation of Pt-Loaded Perovskite BaTiO_3 Near Ferroelectric-Phase Transition Temperature

Perovskite BaTiO3 （BTO） nanocrystals with a size of 150-200 nm have successfully been synthesized via a facile hydrothermal method by employing titanate nanowires as synthetic precursor. Tetragonality and spontaneous ferroelectric polarization of BTO nanocrystals have been determined by X-ray diffraction and transmission electron microscopy investigations. BTO nanocrystals loaded with Pt nanoparticles in a size of 2-5 nm have been explored as a catalyst towards CO oxidation to CO2. It is interesting to find that CO catalytic conversion rate over Pt-BTO nanocrystals gradually decreased and further increased near 100 ℃ when the catalytic temperature keeps increasing, whereas the conversion behavior in oxides is expected to be enhanced upon the catalytic temperature grows. Using differential scanning calorimetry and first-principle calculations, the observed catalytic behavior has been discussed on the basis of the ferroelectric polarization effect and the ferroelectric-paraelectric transition of BTO nanocrystals with a Curie temperature of 110 ℃. Below Curie temperature, CO catalytic oxidation could be significantly tailored by ferroelectric polarization of BTO nanocrystals via a promoted dissociation of O2 molecules. The findings suggest that a ferroelectric polarization in perovskite oxides could be an alternative way to modify the CO catalytic oxidation.

Diffractive self-imaging based on selective etching of a ferroelectric domain inversion grating

A hexagonal array grating based on selective etching of a 2D ferroelectric domain inversion in a periodically poled Mg O-doped Li Nb O3 crystal is fabricated. The effects to the diffractive self-imaging as a function of diffraction distance for a fixed phase difference and array duty cycle of the grating is theoretically analyzed.The Talbot diffractive self-imaging properties after selective etching of a 2D ferroelectric domain inversion grating under a fixed phase difference are experimentally demonstrated. A good agreement between theoretical and experimental results is observed.

Research Advances of Ferroelectric Semiconductors of 2D Hybrid Perovskites toward Photoelectronic Applications

Ferroelectric materials, characterized by the switchable spontaneous polarization(Ps) through reversing the directions of external electric field, exhibit versatile physical attributes that have been extensively used for practical device applications. Two-dimensional(2D) organic-inorganic hybrid perovskites are recently emerging as a robust family of candidate ferroelectrics, termed ferroelectric semiconductors. In particular, the coexistence and/or coupling of ferroelectric polarization with their semiconducting properties enables new physical concepts, thus providing a potential platform for the development of new multifunctional optoelectronic devices. This review primarily describes the structural origin of symmetry breaking for generating ferroelectric orders in 2D hybrid perovskites, and then presents the combination of ferroelectric Ps with other semiconducting optoelectronic activities. Regarding the emergence of new photoelectric behaviors, the prospects for this 2D family of ferroelectric semiconductors are further discussed, along with their development tendency for the future photoelectronic device applications.