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.

Phase transition of nanophase ferroelectric PbTiO_3 ultrafine powder

With the development of optoelectronics, nanometer materials play a more and moreimportant role. Recent theoretical researches indicate that the nanosized semiconductorcrystallites demonstrate a high nonlinear optical susceptibility and a fast response speed.Studies on nanometer-sized particles are very active. Because of the multielements of chemi-cal composition and higher crystallization temperature, it is very difficult to preparenanosized ferroelectric particles through conventional ceramic method.

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.

Study of Dielectric and Mechanical Spectra on Point Defects and Phase Transition in Ferroelectric Ceramics

Ferroelectric materials have enormous potential applications in advanced techniques. However, there are still many problems in its practical application. Dielectric and mechanical (internal friction) measurements are very sensitive to phase transitions, relaxation process of point defects, domain walls and their mobility, which have severe effect on ferroelectric properties. These make them become very good means to investigate substantial information on structural features and to explore the fundamental principles in ferroelectric materials and their applications. In this paper, the dielectric and internal friction measurement were used to investigate the behaviors for point defects and phase transition in ferroelectric ceramics such as Bi_ 4-x La_ x Ti_ 3 O_ 12 , Bi_ 4 Ti_ 3-y Nb_ y O_ 12 , SrBi_ 2 Ti_ 2 O_ 9 , PbZr_ x Ti_ 1-x O_ 3 ,_ PMN-PT. They were used to clarify the mechanism for some ferroelectric behaviors.

Study of Phase Transition Properties in Epitaxial Ferroelectric Film

Based on the transverse Ising model and using decoupling approximation to the Fermi-type Green＇s function, we study the phase transition properties of the epitaxial ferroeleetric film with one substrate. A general recursive equation of the ferroelectric thin film with two n-layer materials is obtained, which enables us to study the phase transition properties for any number layers for epitaxial ferroelectric thin film. With the help of this equation, we analyze the effect of the exchange interaction and the transverse field in the phase diagram, the influence to the polarizations and Curie temperature numerically. The results show that epitaxial ferroelectric film are able to induce a strong increase or decrease of Curie temperature to different exchange interactions and transverse fields within the epitaxial film layers. The theoretical results are in reasonable accordance with experimental data of different ferroelectric thin film.

Paraelectric-ferroelectric interface dynamics induced by latent heat transfer and irreversibility of ferroelectric phase transitions

The temperature gradients that arise in the paraelectric-ferroelectric interface dynamics induced by the latent heat transfer are studied from the point of view that a ferroelectric phase transition is a stationary, thermal-electric coupled transport process. The local entropy production is derived for a ferroelectric phase transition system from the Gibbs equation. Three types of regions in the system are described well by using the Onsager relations and the principle of minimum entropy production. The theoretical results coincides with the experimental ones.

Dynamic phase transition of ferroelectric nanotube described by a spin-1/2 transverse Ising model

The dynamic phase transition properties for ferroelectric nanotube under a spin-1/2 transverse Ising model are studied under the effective field theory(EFT)with correlations.The temperature effects on the pseudo-spin systems are unveiled in three-dimensional(3-D)and two-dimensional(2-D)phase diagrams.Moreover,the dynamic behaviors of exchange interactions on the 3-D and 2-D phase transitions under high temperature are exhibited.The results present that it is hard to obtain pure ferroelectric phase under high temperature;that is,the vibration of orderly pseudo-spins cannot be eliminated completely.

Shape-induced phase transition of vortex domain structures in ferroelectric nanodots and their controllability by electrical and mechanical loads

Shape-induced phase transition of vortex domain structures （VDSs） in BaTiO3 （BT） nanodots under open circuit boundary condition have been investigated using an effective Hamiltonian method. Our calculation indicates the tetragonal VDS missing in cubic BT nanodots can be induced by varying the shape of a nanodot from cube to platelet. Interestingly, a novel VDS is found in BT nanoplatelets in our simulations. Further investigation shows that it is a result of compromise between the ground state and the symmetry of the shape of the nanodot. Furthermore, based on the novel VDS, routes of controlling VDSs governed by homogeneous electric field and uniform stress are discussed. In particular, our results show the possibility of designing multi-states devices based on a single VDS. ~ 2017 The Authors. Published by Elsevier Ltd on behalf of The Chinese Society of Theoretical and Applied Mechanics.

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

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

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.

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.

Dehydration-triggered structural phase transition-associated ferroelectricity in a hybrid perovskite-type crystal

Since the appearance of Rochelle salt,ferroelectrics have received extensive attention from researchers due to they are playing an important role in sensors,memories,mechanical actuation,and so on.In recent years,with the rapid development of molecular ferroelectrics,high-performance molecular ferroelectrics have become effective complement to inorganic ferroelectrics.However,compared with inorganic ferroelectrics,the family of molecular ferroelectrics is relatively scarce,and exploring highperformance ferroelectric materials through new synthesis strategies has become the trend of molecular ferroelectrics.Here,we successfully transformed non-polar material 1(2-H_(2)PCA)_(2)(H_(2)O)CdCl_(6)(2-H_(2)PCA=2-picolylamine cation)into polar material 2(2-H_(2)PCA)2CdCl_(6)by single-crystal to single-crystal transformation(SCSCT).Meanwhile,2 exhibits clear ferroelectricity with a high-temperature Tc of 378 K,a Ps of 1.18μC/cm^(2)at 300 K.This work not only realizes the purpose of synthesizing ferroelectrics by forming polar structures by SCSCT,but also realizes the reversibility of SCSCT,which provides ideas for the construction and exploration of new molecular ferroelectrics.

Energy storage optimization of ferroelectric ceramics during phase-transition process of amorphous/nanocrystalline and polycrystalline by using a phaseffeld model for dielectric breakdown

Ferroelectric ceramics have the potential to be widely applied in the modern industry and military power systems due to their ultrafast charging/discharging speed and high energy density.Considering the structural design and electrical properties of ferroelectric capacitor,it is still a challenge to ffnd out the optimal energy storage of ferroelectric ceramics during the phase-transition process of amorphous/nanocrystalline and polycrystalline.In this work,a ffnite element model suitable for the multiphase ceramic system is constructed based on the phase ffeld breakdown theory.The nonlinear coupling relationship of multiple physical ffelds between multiphase ceramics was taken into account in this model.The basic structures of multiphase ceramics are generated by using the Voronoi diagram construction method.The speciffed structure of multiphase ceramics in the phase-transition process of amorphous/nanocrystalline and polycrystalline was further obtained through the grain boundary diffusion equation.The simulation results show that the multiphase ceramics have an optimal energy storage in the process of amorphous polycrystalline transformation,and the energy storage density reaches the maximum when the crystallinity is 13.96%and the volume fraction of grain is 2.08%.It provides a research plan and idea for revealing the correlation between microstructure and breakdown characteristics of multiphase ceramics.This simulation model realizes the nonlinear coupling of the multiphase ceramic mesoscopic structure and the phase ffeld breakdown.It provides a reference scheme for the structural design and performance optimization of ferroelectric ceramics.

Hybrid improper ferroelectricity and phase transition behavior of Li_(2)Nd_(2)Ti_(3)O_(10)ceramics with A-site ordered triple-layer Ruddlesden-Popper structure

Hybrid improper ferroelectricity has been extensively reported through theoretical prediction and experimental investigation in the oxides with Ruddlesden-Popper(R-P)structures.However,the experimentally reported ferroelectric materials based on triple-layer R-P structures are rare,and the weak ferroelectricity impedes its practical application.In the present work,the single-phase Li_(2)Nd_(2)Ti_(3)O_(10)ceramics with A-site cation ordered triple-layer R-P structure was obtained by spark plasma sintering technique,and the crystal structure of P2_(1)ab symmetry was revealed by neutron powder diffraction and transmission electron microscope analysis.Furthermore,the switchable ferroelectricity in Li_(2)Nd_(2)Ti_(3)O_(10)ceramics has been observed at room temperature,and the saturated polarization-electric field hysteresis loop was obtained with P_(r)=0.4μC/cm^(2)under the electric field of 250 kV/cm.The phase transition behavior of Li_(2)Nd_(2)Ti_(3)O_(10)oxides was revealed by the temperature-dependence Raman and dielectric spectra combined with the piezoelectric property.

Combined effect of the transition layer and interfacial coupling on the properties of ferroelectric bilayer film

Within the framework of modified Ginzburg Landau-Devonshire phenomenological theory, a ferroelectric bilayer film with a transition layer within each constituent film and an interfacial coupling between two materials has been studied. Properties including the Curie temperature and the spontaneous polarization of a bilayer film composed of two equally thick ferroelectric constituent films are discussed. The results show that the combined effect of the transition layer and the interracial coupling plays an important role in explaining the interesting behaviour of ferroelectric multilayer structures consisting of two ferroelectrie materials.

Phenomenological theory of surface effects in ferroelectrics and its relationship with transverse Ising model

The relationship between the transverse field Ising model and the Landau phenomenological theory for ferroelectrics is analyzed, and the Landau free energy expression for ferroelectrics having surfaces is derived. It is pointed out that the traditional expression in which the surface integral has only a term of the square polarization is valid only for special cases, in general a term of the polarization to the four should be included as well. By use of the newly derived free energy expression, the thickness-dependence of the spontaneous polarization and Curie temperature of ferroelectric films is calculated; thereby some experimental results incompatible with the traditional phenomenological theory are successfully explained.

Critical exponents of ferroelectric transitions in modulated SrTiO_3:Consequences of quantum fluctuations and quenched disorder

The ferroelectric transitions of several SrTiO3-based ferroelectrics are investigated experimentally and theoretically, with special attention to the critical scaling exponents associated with the phase transitions, in order to understand the competition among quantum fluctuations （QFs）, quenched disorder, and ferroelectric ordering. Two representative systems with sufficiently strong QFs and quenched disorders in competition with the ferroelectric ordering are investigated. We start from non-stoichiometric SrTiO3（STO） with the Sr/Ti ratio deviating slightly from one, which is believed to maintain strong QFs. Then, we address Ba/Ca co-doped Sr1-x（Ca0.6389Ba0.3611）xTiO3（SCBT） with the averaged Sr-site ionic radius identical to the Sr2＋ ionic radius, which is believed to offer remarkable quenched disorder associated with the Sr-site ionic mismatch. The critical exponents associated with polarization P and dielectric susceptibility ε, respectively, as functions of temperature T close to the critical point Tc, are evaluated. It is revealed that both non-stoichiometric SrTiO3 and SCBT exhibit much bigger critical exponents than the Landau mean-field theory predictions. These critical exponents then decrease gradually with increasing doping level or deviation of Sr/Ti ratio from one. A transverse Ising model applicable to the Sr-site doped STO （e.g., Sr1-xCaxTiO3） at low level is used to explain the observed experimental data. It is suggested that the serious deviation of these critical exponents from the Landau theory predictions in these STO-based systems is ascribed to the significant QFs and quenched disorder by partially suppressing the long-range spatial correlation of electric dipoles around the transitions. The present work thus sheds light on our understanding of the critical behaviors of ferroelectric transitions in STO in the presence of quantum fluctuations and quenched disorder, whose effects have been demonstrated to be remarkable.

BNT基铁电陶瓷的温度诱导高电致应变响应及其机理研究

近年来,钛酸铋钠(Bi_(0.5)Na_(0.5))TiO_(3)(BNT)基铁电材料因具有高电致应变响应而受到广泛关注,并在驱动器方面展现出巨大的应用潜力。本工作采用传统固相法工艺制备了(1-x)(Bi_(0.5)Na_(0.5))TiO_(3)-x(Ba_(0.90)Ca_(0.10))(Ti_(0.92)Sn_(0.08))O_(3)(BNT-x BCTS,x=0.04~0.07)铁电陶瓷,研究了BCTS含量对BNT陶瓷的相结构、介电性能及电致应变性能的影响。通过分析高温下材料铁电/应变性能的变化和高温原位XRD/拉曼测试结果,明确了温度诱导BNT基陶瓷高电致应变产生的机理。结果表明,BNT-x BCTS(x=0.04~0.07)陶瓷均具有三方-四方两相共存结构,且三方相/四方相的含量比随着BCTS含量的增大逐渐减小。BCTS的引入促使BNT材料的铁电-弛豫相变温度(T_(F-R))向低温方向移动,并提高了BNT陶瓷材料室温下的电致应变性能。此外,BNT-x BCTS体系具有温度诱导高电致应变特征,在其T_(F-R)附近,电致应变性能获得极大提升:BNT-0.05BCTS陶瓷在其T_(F-R)(150℃)附近的单向应变值S uni达到0.463%(70 kV/cm电场下,测试频率1 Hz),对应的大信号压电常数d_(33)*为661 pm/V。通过开展样品在室温和150℃下第一圈电滞回线/双向应变曲线测试,给出了材料在不同温度下电场诱导结构转变的具体演变过程,并证实了BNT基材料在其T_(F-R)温度附近的高电致应变来源于电场诱导的遍历性弛豫态到铁电态的可逆转变。

对巧克力相变迟滞现象的理论解释——朗道-德冯谢亚理论以及铁电相变理论

巧克力作为生活中常见的事物,其储存方法一直是食品科学界研究的重要课题,而由相变产生的巧克力凝固和融化等现象对巧克力的储存产生了决定性的影响;但由于巧克力的成分复杂且晶体结构多变,目前只在生活中实现了控制巧克力保持良好性状的储存,而鲜少有研究分析其背后存在的相变机理。研究中首先基于朗道-德冯谢亚理论,使用序参量描述了影响相变的相关因素,初步解释了巧克力相变当中存在的迟滞现象;而后进行了相关实验,提出了一种对朗道理论的修正来解释实验现象;最后,通过研究巧克力的主要成分可可脂晶体的铁电相变,对德冯谢亚理论中未作出解释的势垒产生做出了阐述。

P(VDF-TrFE)共聚物结晶性能研究进展

P(VDF-TrFE)凭借其柔性好、频率响应大、化学性能稳定和自发极化强度高,在柔性有机器件中具有广阔应用前景。聚合物的结晶性能直接决定其压电、铁电性能的强弱,本文综述了单体共聚比例、薄膜制备工艺条件及共混物类型与含量等因素对P(VDF-TrFE)共聚物结晶性能的影响,并简要阐述了各种因素对P(VDF-TrFE)结晶性能的影响机理。