铁电陶瓷中电畴翻转研究进展

电畴为铁电陶瓷固有的独特微观组织特征之一,铁电陶瓷的许多性能均与其密切有关.综述了铁电陶瓷中的电畴结构,系统介绍了电场、机械作用引起的电畴翻转,概述了电畴翻转对铁电陶瓷断裂韧性的影响及其研究进展.     

Effect of composition on rate dependence of ferroelastic/ferroelectric switching in perovskite ceramics

Abstract

The process of ferroelectric/ferroelastic switching is rate dependent as evidenced by the frequency dependence of the coercive field/stress in polarisation/strain–electric field/stress loops. The rate dependence of domain switching has been investigated in different compositions of ferroelectric/ferroelastic perovskites by studying their stress–strain hysteresis loops. Stress–strain loops were generated by applying a static compressive load and then superimposing cyclic compressive loads of different amplitudes and frequencies. The stress–strain loops were fitted using a Rayleigh type relationship, whose parameters characterise the intrinsic and extrinsic contributions to the strain. Using these parameters, the rate dependence of the extrinsic domain wall contribution was investigated.     

Structural visualization of polarization fatigue in epitaxial ferroelectric oxide devices

Ferroelectric oxides, such as Pb(Zr,Ti)O(3), are useful for electronic and photonic devices because of their ability to retain two stable polarization states, which can form the basis for memory and logic circuitry. Requirements for long-term operation of practical devices such as non-volatile RAM (random access memory) include consistent polarization switching over many (more than 10(12)) cycles of the applied electric field, which represents a major challenge. As switching is largely controlled by the motion and pinning of domain walls, it is necessary to develop suitable tools that can directly probe the ferroelectric domain structures in operating devices-thin-film structures with electrical contacts. A recently developed synchrotron X-ray microdiffraction technique complements existing microscopic probes, and allows us to visualize directly the evolution of polarization domains in ferroelectric devices, through metal or oxide electrodes, and with submicrometre spatial resolution. The images reveal two regimes of fatigue, depending on the magnitude of the electric field pulses driving the device: a low-field regime in which fatigue can be reversed with higher electric field pulses, and a regime at very high electric fields in which there is a non-reversible crystallographic relaxation of the epitaxial ferroelectric film.     

Nanoscale insight into the statics and dynamics of polarization behavior in thin film ferroelectric capacitors

In this study, we review recent advances in PFM studies of micrometer scale ferroelectric capacitors, summarize the experimental PFM-based approach to investigation of fast switching processes, illustrate what information can be obtained from PFM experiments on domains kinetics, and delineate the scaling effect on polarization reversal mechanism. Particular attention is given to PFM studies of mechanical stress effect on polarization stability.     

Nucleation and growth of domains near crack tips in single crystal ferroelectrics

The nucleation and growth of domains is investigated near a stationary crack tip in a single crystal of ferroelectric material. The phase-field approach, applying the material polarization as the order parameter, is used as the theoretical modeling framework and the finite element method is used for the numerical solution technique. The electromechanical form of the J-integral is appropriately modified to account for the polarization gradient energy terms, and analyzed to illustrate the amount of shielding, or lack thereof, due to domain switching at the crack tip. It is shown that the nucleation of domains near the crack tip due to applied electric field is affected by applied stress. However, the crack-tip energy release rate can change significantly between the instant of domain nucleation and the final equilibrium domain configuration. Implications of these results for ferroelectric single crystal fracture criteria are discussed.     

Normal ferroelectric to ferroelectric relaxor conversion in fluorinated polymers and the relaxor dynamics

To elucidate the molecular origin of the polarization dynamics in the ferroelectric relaxor poly(vinylidene fluoride—trifluoroethylene-chlorofluoroethylene) (P(VDF-TrFE-CFE)) terpolymer, a broadband dielectric study was carried out in the frequency range from 0.01 Hz to 10 MHz and temperatures from −150°C to 120°C for the terpolymer and a normal ferroelectric P(VDF-TrFE) copolymer. The relaxation processes were also studied using dynamic mechanical analysis. It was shown that in the terpolymer, which was completely converted to a ferroelectric relaxor, there is no sign of the relaxation process associated with the ferroelectric-paraelectric transition which occurs in the P(VDF-TrFE) copolymer. In the copolymer, three additional relaxation processes have been observed. It was found that the relaxation process β_a, which was commonly believed to be associated with the glass transition in the amorphous phase, in fact, contains significant contribution from chain segment motions such as domain boundary motions in the crystalline region. In the temperature range studied, the terpolymer exhibits the latter three relaxation processes with the one (termed β_r) near the temperature range of β_a significantly enhanced. This is consistent with the observation that in conversion from the normal ferroelectric to a ferroelectric relaxor, the macro-polar domains are replaced by nano-polar-clusters and the boundary motions as well as the reorientation of these nano-clusters generate the high dielectric response. The experimental data also reveal a broad relaxation time distribution related for the β_r process whose distribution width increases with reduced temperature, reflecting the molecular level heterogeneity in the crystalline phase due to the random introduction of the CFE monomer in the otherwise ordered macro-polar domains. The random interaction among the nano-clusters as well as the presence of the random fields produces ferroelectric relaxor behavior in the terpolymer.     

An application of polarized domains in ferroelectric thin films using scanning probe microscope

The feasibility of utilizing PZT films as future data storage media was investigated using a modified AFM. Applying voltages between a conductive AFM tip and the PZT films causes the switching of ferroelectric domains. The domains are observed using an EFM imaging technique. The experimental results and calculations revealed that the electrostatic force generated between the polarized area and the tip is a main contributor for the imaging of the polarized domains. The written features on ferroelectric films were less than 100 nm in diameter, implying the possibility of realizing data storage devices with ultra-high area density. The disappearance of the polarized images without any applied voltage was observed, which is a drawback in this application of PZT thin films.     

溶胶-凝胶法制备PbTiO3铁电玻璃陶瓷的高频晶粒尺寸效应

首次报道了用溶胶－凝胶法制备的钛酸铅铁电玻璃陶瓷的晶粒尺寸对其高频介电性能的影响。研究表明,铁电玻璃陶瓷的高频介电弛豫主要是由材料内部的畴壁共振引起的。晶粒尺寸增加,畴壁宽度增大,介电弛豫向低频移动;反之,晶粒尺寸减小,畴壁宽度变小,介电弛豫向高频移动,弛豫频率提高,介电损耗变小。     

Mechanical and electrical switching of local ferroelectric domains of K<Subscript>0.5</Subscript>Bi<Subscript>4.5</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> film

Ferroelectric/Piezoelectric K_0.5Bi_4.5Ti₄O₁₅ (KBT) film was fabricated by pulsed laser deposition method and confirmed by ferroelectric, dielectric measurements and local butterfly-type piezoresponse hysteresis loops. Importantly, ferroelectric domain switching by both electrical field and mechanical force in KBT film was demonstrated. The dark and bright contrast represents the PFM response of the up and down polarized domains, which can be written by a dc bias of ±12 V or a mechanical force of 40–50 nN. The successful demonstration of mechanical force switching of ferroelectric domain in KBT film other than electric field provides a novel mean for information storage and sensors.     

Constitutive law for ferroelectric and ferroelastic single crystals: a micromechanical approach

This paper examines the switching process occuring in ferroelectric and ferroelastic single crystals under electro-mechanical loadings. Ferroelectrics undergoing a cubic to tetragonal phase transition are considered. The single crystal energy has three origins: elastic, electric and the incompatibilities of the spontaneous strain and electric displacement fieds between domains. The stress and electric fields fluctuate and present jumps at the domain walls. As a consequence, they induce electro-elastic interaction energy. Thus, it involves dissipation that the present work aims to capture through a micromechanical approach.     

Dielectric and Ferroelectric Properties of Complex Perovskite Ceramics Under Compressive Stress

Dielectric and ferroelectric properties of complex perovskite PZT-PZN ceramic system were investigated under the influence of the compressive stress. The results showed that the dielectric properties, i.e. dielectric constant ( εr ) and dielectric loss ( tan δ), and the ferroelectric characteristics, i.e. the area of the ferroelectric hysteresis loops, the saturation polarization ( P(sat) ), and the remnant polarization (Pr) changed significantly with increasing compressive stress. These changes depended strongly on the ceramic compositions. The experimental results on the dielectric properties could be explained by both intrinsic and extrinsic domain-related mechanisms involving domain wall motions, as well as the de-aging phenomenon. The stress-induced domain wall motion suppression and non-180° ferroelectric domain switching processes were responsible for the changes observed in the ferroelectric parameters. In addition,a significant decrease in those parameters after a cycle of stress was observed and attributed to the stress induced decrease in switchable part of spontaneous polarization. This study clearly show that the applied stress had significant influence on the electrical properties of complex perovskite ceramics.     

Electro-optical investigations of holographic-polymer-dispersed ferroelectric liquid crystals

Uniform alignment of ferroelectric liquid-crystal domains encapsulated by a polymer binder was established through a holographic exposure process. The refractive index modulation in these thin films is modeled as a phase grating that can be electrically addressed to erase the optical diffractive properties. A phenomenological model is developed to take into account a distribution of domain sizes and an effective field that stabilizes the ferroelectric liquid-crystal domains. A diffraction model successfully predicts changes in normalized intensities for first-order diffraction with applied field. These gratings demonstrate microsecond-scale response and relaxation times for various grating pitch sizes between approximately 3 and approximately 12 microm.     

Numerical analysis of ferroelectric/ferroelastic domain switching in ferroelectric ceramics

A numerical approach predicting the behavior of ferroelectric ceramics under electric field and mechanical loading is proposed in this paper. In the model, macroscopic properties of ferroelectric ceramics are determined by microscopic structures. Ferroelectric ceramics are seen to be composed of many domains with different orientations, and domain switching is the source of the nonlinear constitutive behavior of the ferroelectric ceramics. Numerical calculations based on the model were carried out, and the computational results are compared with the experimental results, which shows the two sets of results consist with each other. The calculation approach can provide a guidance for the ceramics component design.     

Normally distributed free energy model and creep behavior of ferroelectric polycrystals at room and high temperatures

A constitutive model that can be used to predict creep behavior of ferroelectric polycrystals at room and high temperatures is proposed. The model consists of the Gibbs free energy function with normal distribution and a switching evolution law with critical driving force. Linear moduli in the free energy function and switching parameters in the switching law are assumed to be linearly dependent on temperature. A ferroelectric polycrystal is modeled by an agglomerate of 210 single crystallites. Compressive stress and electric field-induced creep behavior as well as polarization hysteresis and strain butterfly responses of the model are calculated and compared with experimental observations.     

Light‐Induced Reversible Control of Ferroelectric Polarization in BiFeO3

Manipulation of ferroic order parameters, namely (anti‐)ferromagnetic, ferroelectric, and ferroelastic, by light at room temperature is a fascinating topic in modern solid‐state physics due to potential cross‐fertilization in research fields that are largely decoupled. Here, full optical control, that is, reversible switching, of the ferroelectric/ferroelastic domains in BiFeO₃ thin films at room temperature by the mediation of the tip‐enhanced photovoltaic effect is demonstrated. The enhanced short‐circuit photocurrent density at the tip contact area generates a local electric field well exceeding the coercive field, enabling ferroelectric polarization switching. Interestingly, by tailoring the photocurrent direction, via either tuning the illumination geometry or simply rotating the light polarization, full control of the ferroelectric polarization is achieved. The finding offers a new insight into the interactions between light and ferroic orders, enabling fully optical control of all the ferroic orders at room temperature and providing guidance to design novel optoferroic devices for data storage and sensing.     

Dynamic behaviour of domains during poling by acoustic emission measurements in La-modified PbTiO3 ferroelectric ceramics

In order to study the dynamic behaviour of domains during poling, the acoustic emission (AE) characteristics of two La-modified PbTiO3 ferroelectric ceramics in which 90° and 180° domains were respectively dominant have been investigated. One sample was a 15 mol% La-doped ceramic with a high tetragonality ratio (c/a=1.021) and the other was a 24 mol% La-doped ceramic where the tetragonality ratio was close to unity (c/a=1.007). The acoustic emission behaviour of the former sample consisted of both burst as well as continuous emission, with the latter sample mainly showing continuous emission. Energy distributions made it possible to distinguish between the AE signals resulting from 90° and 180° domain switching. From the observed results, it was confirmed that most of the AE occurred due to 90° domain switching. By introducing an alternative switching behaviour for the 90° domains, the behaviour of the AE generation during poling could be explained.     

压电材料中缺陷偶极子特性的研究进展

压电材料通过受主掺杂或烧结挥发等可以形成缺陷偶极子, 缺陷偶极子对材料的性能有显著的影响。本文综述了压电材料中缺陷偶极子的产生及其在外场下的响应机理, 同时, 从缺陷偶极子运动的角度分析了压电材料中老化、电滞回线异常及电致形状记忆效应等现象的起源, 简要分析了偶极子弛豫现象, 并对未来发展高可靠性压电驱动器的研究作了展望。     

Unipolar resistive switching behavior of BiFeO3 thin films prepared by chemical solution deposition

Bismuth ferrite (BiFeO₃, BFO) thin films were spin-coated on Pt/Ti/SiO₂/Si substrates by a chemical solution deposition method. The ferroelectric BFO films annealed at 500 °C and 550 °C were found to possess unipolar resistive switching behaviors. The resistance ratio of the high resistance state (HRS) to the low resistance state (LRS) of the unipolar resistance switching is about 10³ for the ferroelectric BFO films. The conduction mechanisms are concluded to be space charge-limited conduction for the initial state and Ohmic conduction for the LRS. As for the HRS, the Poole-Frenkel emission fits well in the whole voltage region. Traps composed of oxygen vacancies are considered to play a key role in forming conducting paths. The relaxation time of electronic carriers is much shorter than that of ionic oxygen vacancies; therefore, the resistance switching is considered more probably due to carrier injection and emission through the Poole-Frenkel model after forming.     

The influence of fabrication processing on domain structure and polarization switching in PZN-based ferroelectric ceramics

Lead zinc niobate (Pb(Zn_1/3Nb_2/3)O₃, PZN) based ceramics are prepared by using conventional mixing oxide and complex phase reaction-sintering ceramic techniques. From the results of X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), it is clear that these two fabrication processing routes produce different microstructures and ferroelectric domains in the same Pb(Zn_1/3Nb_2/3)O₃–BaTiO₃–Pb(Zr_0.4Ti_0.6)O₃ composition. Furthermore, different phase transitions are observed for the temperature dependence of the dielectric permittivity that can be confirmed by differential scanning calorimetry (DSC). Different polarization switching characteristics are also examined by using high field-induced strain and ferroelectric hysteresis loop. It is suggested that the distribution of the inner stress and domain configuration should be related with the fabrication processing of ferroelectric ceramics.     

粗大晶粒PZT陶瓷中电畴的结构

应用扫描力显微镜(SFM)的压电响应模式观测未经抛光处理的PZT陶瓷片的电畴结构,用纵向压电响应信号和侧向压电响应信号获得PZT陶瓷材料三维电畴结构.结果表明,将样品晶粒的微形貌与SFM的纵向和侧向压电响应信号相结合,能准确表征粗大晶粒样品的三维电畴结构.用SFM可观测表面不经任何处理的陶瓷样品的电畴,不会引入表面应力等影响因素,能得到样品的原生畴结构.对原生畴结构的观察表明,对于受应力较大的晶粒,成畴的主要原因是降低应变能,而受应力较小的晶粒成畴的主要原因是降低退极化能.