Theory of switching of multiaxial ferroelectrics (Initial stage)

The classical theory of nucleation and growth is used to study the thermodynamics and kinetics of switching of multiaxial ferroelectrics. The initial stage of 180°-and 90°-domain switching is studied in the tetragonal, orthorhombic, and trigonal phases. The multidimensional kinetic theory of first-order phase transitions is applied to describe the initial stage of switching of ferroelectric crystals in the general case where three-dimensional growth (along the radius and height) of repolarized domains occurs. The energy of nucleus formation is calculated in the vicinity of the saddle point of an activation barrier in the space of sizes and shapes, and the dependence of the critical domain size on the switching field is found. The two-dimensional Fokker-Planck kinetic equation is reduced to a one-dimensional Zel’dovich equation, and a stationary solution to the Zel’dovich equation is obtained. The diffusion coefficients are derived in the size space for the normal and layer-by-layer mechanisms of domain growth. The main characteristic of the initial switching stage, namely, the steadystate flux of repolarized domains, is found as a function of the applied field.

     

Polarization switching kinetics in ferroelectrics

The switching kinetics in ferroelectrics in the bulk polarization switching stage and in the final stage of the process are studied. Consideration is given to the specific case of switching of intrinsic ferroelectrics with 180° domains. A complete system of equations describing the switching processes and taking into account the change in repolarization in the course of a phase transformation is derived. The solution of this system is found. All the main characteristics of the switching process are calculated; namely, the evolution of the domain size distribution function is revealed and the time dependences of the domain density and flux are determined. An expression describing the variation in repolarization with time is obtained. The mechanisms of domain growth are studied. An equation for calculating the switching current and its variation with time is derived. A method is proposed for determining a number of constants for ferroelectric crystals by studying the switching current evolution.     

Polarization switching kinetics in ferroelectrics in the region of strong metastability

The thermodynamics and kinetics of polarization switching in ferroelectrics are studied in the framework of the field theory in the vicinity of the critical point of first-order phase transitions. The study is exemplified by the switching of intrinsic ferroelectrics with 180° domains. An expression describing the dependence of the domain critical size on the switching field is derived. The switching process is studied at high switching fields. Relationships for calculating the field dependence of the number of switched domains are obtained.     

Thermodynamics and kinetics of the initial stages of polarization switching in ferroelectrics

The thermodynamics and kinetics of polarization switching in ferroelectrics are studied in the specific case of switching in intrinsic ferroelectrics with 180° domains. The initial stage of the switching in the region of weak metastability is analyzed. An expression relating the critical domain size to the switching field is derived. An equation describing the evolution of the size distribution function of the switched domains is obtained. Expressions for calculating the number of polarization switching nuclei as a function of the switching field are derived.     

Processing effects on the microstructure and ferroelectric properties of strontium bismuth tantalate thin films

Ferroelectric thin films of strontium bismuth tantalate compositions with Bi/Sr ratios of 2.75 and 2.50 have been produced by deposition of solutions derived from sol-gels followed by crystallization using rapid thermal processing (RTP) at 650 °C. Single-step and two-step processes have been used for the RTP crystallization of the films. Both the composition and the heating process used affect the grain size, grain shape and compositional heterogeneity of the films, acting on their ferroelectric switching behaviour and dielectric properties. Larger and more elongated grains are obtained by crystallization using a single-step process. These films exhibit less slanted hysteresis loops. The combination of the study of the pure-ferroelectric-switching loop and the lambda curves through the application of a Curie–Weiss-like model gives a deeper insight into the influence of film heterogeneity on its ferroelectric properties. The observation of net polarisation without poling in all the films is attributed to the effects of 180° ferroelectric domains. Received: 16 May 2001 / Accepted: 27 October 2001 / Published online: 20 March 2002     

Field-induced phase transitions and reversible field-induced inversion of chirality in tilted smectic phases of bent-core mesogens

Three homologous achiral five-ring bent-core mesogens are presented where 4-chlororesorcinol is the central core and the aromatic rings are linked by ester groups. These compounds form smectic phases with a tilted arrangement of the molecules (tilt angle ≈ 45^°). On cooling the isotropic liquid this phase adopts a fan-like texture which shows for two homologues at relatively high electric fields ( 25-35V μm^-1) an antiferroelectric electro-optical response based on the collective rotation of the molecules around their long axes. At lower temperature the application of a sufficiently high electric field leads to a continuous transition into a non-birefringent texture which exhibits randomly distributed domains of opposite handedness. These domains can be reversibly switched into a state of opposite chirality by reversal of the field polarity. This switching is bistable and shows a current response typical for a ferroelectric ground state. The possible mechanism of the field-induced phase transition, of the ferroelectric switching and of the field-induced inversion of the chirality is discussed on the base of XRD, ¹³C- and ¹H-NMR investigations, dielectric and electro-optical measurements.     

The effect of annealing temperature on the morphology and piezoelectric characteristics of BaTiO3 nanofibers and domain switching under different temperatures

Effects of annealing temperature (600–750 °C) on crystalline structure, the morphology and piezoresponse hysteresis loops of BaTiO₃ nanofibers prepared by electrospinning are characterized by X-ray diffraction, scanning electronic microscopy, transmission electron microscope and piezoresponse force microscope. When the annealing temperature is 700 °C, the nanofibers become smoother and have a diameter of 100–300 nm. Meanwhile the typical butterfly-shaped amplitude loop and 180°phase change represents the best ferroelectric and piezoelectric properties at 700 °C. So the 700 °C was found to be optimum for good piezoelectric characteristics at annealing temperature of 600 °C–750 °C. In order to give more clear evolution of domain states at different external fields, the three dimensional topographic and phase images of the nanofiber at different temperatures are observed by piezoresponse force microscope. The 90° domain switching is observed during heating from room temperature to 125 °C and the domain switching tends to be stable when the temperature exceeds a critical value. The thermal stress due to the high temperatures is responsible for switching mechanism from the perspective of equilibrium state free energy. This work suggests that the temperature variation should be considered while designing the ferroelectric devices based on one dimensional material.     

Electroluminescence and internal screening of domains upon polarization switching of ferroelectric ceramics in a pulsed self-consistent field

This paper reports on the results of investigations into the electroluminescence induced by polarization switching of a ferroelectric ceramic material in an electric field with a rapidly increasing strength. A correlation between the polarization switching and luminescence kinetics is revealed. It is demonstrated that tunneling of electrons to the conduction band and impact ionization in field concentrators are the main mechanisms of generation of free charge carriers responsible for the electroluminescence and internal screening of switching domains.     

Equations for domain walls in a coordinate system of the ferroelectric phase

Two methods are suggested for writing equations for domain walls in a coordinate system of the ferroelectric phase in ferroelastics and multiaxial ferroelectrics. The equations for domain walls in ferroelectric barium titanate and ferroelastic lead orthophosphate are derived. It is shown that suborientation states are possible in these crystals. The suggested methods make it possible to find the matrices of the transformation from the coordinate system of the paraelectric phase to a coordinate system of the ferroelectric phase for each orientation state.     

Switching of partially switched KNbO3 single crystals containing cooperatively ordered impurity dipoles

Switching studies have been carried out in partially switched KNbO₃ single crystals by observing switching transients and hysteresis loops. The crystals used contained ordered impurity dipoles that are active in nucleating domains around them. Partial initial switching was obtained by applying known compressive stress to the crystal by means of a spring. The partially switched nature was determined by recording the photograph of the crystal surface. The changed domain structure on the surface gave a clear idea of the extent of partial switching. As the compressive stress was gradually increased, the crystal showed increased initial mechanical switching through the mechanism of evaporation of domain walls associated with ordered impurity dipoles. The dipoles then switch systematically converting 90° domains with polar axes in the plane of plate into 60° domains with polar axes in the perpendicular pseudocubic {001} planes. The initial switching condition changes the switching characteristics as determined by hysteresis loops and switching transients. The results are interpreted in terms of domains in the crystal. If the dipole density is quite high, the effect of the dipoles becomes negligible, and the switching behaviour approximates that of a normal ferroelectric. The switching transients and the hysteresis loops in the crystals containing cooperatively ordered dipoles are basically different from the ones observed in normal ferroelectrics. The anomalous behaviour is detrimental to the use of material in device applications. Hence, it is shown that the switching transients and hysteresis loops provide a ready means of detecting the presence of these ordered impurity dipoles.     

Ferroelectric properties of vinylidene fluoride copolymers

Ferroelectric properties of copolymers of vinylidene fluoride with trifluoroethylene and tetrafluoroethylene are described with special interest in their polarization reversal and phase transition behavior. The ferroelectric phase consists of all-trans molecules packed in a parallel fashion while molecules adopt irregular TT, TG, T[Gbar] conformations in the paraelectric phase. In the ferroelectric phase, polarization reversal occurs at very high fields (> 100 MV/m) as a result of eventual 180° rotations of individual chain molecules around their axes. The switching time ranges from sec to nsec depending upon the strength of the applied field according to an exponential law with a particularly large activation field (～ 1 GV/m). The value of the observed remnant polarization is consistent with prediction from a simple dipole sum implying a minor contribution from the Coulomb interaction. The ferroelectric-to-paraelectric transition appears most clearly for copolymers containing 50-80 mol% vinylidene fluoride at temperatures from 70 to 140°C. The transition accompanies cooperative dipole motions associated with elementary trans-gauche transformations. Changes in various properties as well as in structures in the vicinity of the Curie point are consistent with an order-disorder transition of first order. Detailed characteristics specifying their ferroelectricity are summarized and discussed in relation to the molecular, crystalline, and higher-order structures inherent to ferroelectric polymers.     

Direct observation of ferroelectric domain switching in varying electric field regimes using in situ TEM

In situ Transmission Electron Microscopy (TEM) techniques can potentially fill in gaps in the current understanding interfacial phenomena in complex oxides. Select multiferroic oxide materials, such as BiFeO(3) (BFO), exhibit ferroelectric and magnetic order, and the two order parameters are coupled through a quantum-mechanical exchange interaction. The magneto-electric coupling in BFO allows control of the ferroelectric and magnetic domain structures via applied electric fields. Because of these unique properties, BFO and other magneto-electric multiferroics constitute a promising class of materials for incorporation into devices such as high-density ferroelectric and magnetoresistive memories, spin valves, and magnetic field sensors. The magneto-electric coupling in BFO is mediated by volatile ferroelastically switched domains that make it difficult to incorporate this material into devices. To facilitate device integration, an understanding of the microstructural factors that affect ferroelastic relaxation and ferroelectric domain switching must be developed. In this article, a method of viewing ferroelectric (and ferroelastic) domain dynamics using in situ biasing in TEM is presented. The evolution of ferroelastically switched ferroelectric domains in BFO thin films during many switching cycles is investigated. Evidence of partial domain nucleation, propagation, and switching even at applied electric fields below the estimated coercive field is revealed. Our observations indicate that the occurrence of ferroelastic relaxation in switched domains and the stability of these domains is influenced the applied field as well as the BFO microstructure. These biasing experiments provide a real time view of the complex dynamics of domain switching and complement scanning probe techniques. Quantitative information about domain switching under bias in ferroelectric and multiferroic materials can be extracted from in situ TEM to provide a predictive tool for future device development.     

Domain walls, magnetization, and magnetoelectric effect in bismuth ferrite films

The specific features of the antiferromagnetic domain structure, magnetization, and polarization induced by an inhomogeneous micromagnetic distribution in films of bismuth ferrite multiferroics have been investigated. It has been shown that the magnetic domain structure correlates with the ferroelectric domain structure, and the character of the rotation of the antiferromagnetic vector depends on the type of ferroelectric domain walls. An asymmetry in the distribution of the antiferromagnetic vector has been observed for the cases of 109° and 71° ferroelectric domain walls. It has been demonstrated that there are differences in the distributions of the polarization and magnetization in bismuth ferrite films with ferroelectric domains separated by 109° and 71° walls. The basic mechanisms responsible for the magnetization in domain walls in multiferroics have been considered.     

Electric Field Writing of Ferroelectric Nano‐Domains Near 71° Domain Walls with Switchable Interfacial Conductivity

Conducting ferroelectric domain walls attract a wide range of research interest due to their promising applications in nanoelectronics. In this study, we reveal an unexpected enhanced conductivity near the well‐aligned 71° nonpolar domain walls in BiFeO₃. Such an interfacial conductivity is induced by the creation of up‐polarized nano‐domains near the 71° domain walls, as revealed by the combination of the piezo‐response force microscopy (PFM) and conducting atomic force microscopy (c‐AFM) imaging techniques, as well as phase‐field simulations. The upward polarized domains are suggested to lower the Schottky barrier at the interface between the tip and sample surface, and then give rise to the enhanced interfacial conductivity. The result provides a new strategy to tune the local conductance in ferroelectric materials and opens up new opportunities to design novel nanoelectronic devices.     

Observation of mechanical fracture and corresponding domain structure changes of polycrystalline PbTiO3 nanotubes

PbTiO₃ (PTO) nanotubes (NTs) were synthesized at various temperatures by gas phase reaction between PbO gas and anatase TiO₂ NTs and characterized by piezoresponse force microscopy (PFM). PTO ferroelectric phase was synthesized at as low as 400 °C as evidenced by PFM domain images and piezoresponse hysteresis loop measurement. Furthermore, the PTO NTs fabricated at above 500 °C underwent mechanical fracture through development of nanocracks due to grain growth, leading to ferroelectric domains with larger size and lower aspect ratio. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

压应力场下PLZT铁电陶瓷的原位Raman观测

铁电陶瓷材料在外场加载下的畴变所引起的材料结构变化,是导致材料性能衰变和破坏的主要原因,Raman光谱技术是一种研究铁电材料畴变和微结构变化的无损伤性及原位微区的观测方法。采用传统固相法合成Zr/Ti原子比为53/478的掺镧锆钛酸铅(PLZT)铁电陶瓷材料 ,采用X射线衍射仪和扫描电子显微镜及Precision_LC铁电测试系统分别对试样进行结构形貌表征和铁电物理性能测试,利用自制的应力加载装置与Raman光谱仪联用,实现不同压应力场作用下试样的原位Raman谱测试,考察和分析Raman谱软模E(2TO)和E(3TO+2LO)+B1的峰强和峰位随散射偏振方向的变化规律。结果表明,不同压应力场下Raman软模E(2TO)和E(3TO+2LO)+B1的峰强均随散射偏振角度呈现正弦式的变化规律,在60°偏振角度上软模峰强最大,在150°偏振角度上软模峰强最小。随着压应力场的增加,在0°和60°偏振角度获得的软模峰强随应力场的增加呈现明显的下降趋势,而在90°和150°偏振角度获得的软模峰强基本不变。压应力场变化对PLZT陶瓷的Raman软模E(2TO)和E(3TO+2LO)+B1的峰位均不产生影响。     

The interactions between dislocations and ferroelectric domains in KNbO3 crystals

It is found that it is rather easy to introduce dislocations into KNbO₃. With transmission electron microscopy we have determined the slip plane to be (110) and the Burgers vector of dislocations to be [110]. Using hot stage in a JEM-200CX electron microscope, we have made in situ observations during phase transitions at 435°C (cubic-tetragonal) and 225°C (tetragonal-orthorhombic). We have found evidence indicating the interactions between dislocations and ferroelectric domains. Especially during phase transitions, the new ferroelectric phase first appear in the vicinity of dislocations showing that the stress field of dislocations may raise Curie point of the crystals.     

Effect of a weak external electric field on the kinetics of the ordering of ferroelectrics upon first-order phase transitions

The kinetics of the formation and growth of 180° domains in a weak quasi-stationary external electric field has been considered in the framework of the phenomenological Ginzburg–Landau model using the example of sodium nitrite (NaNO₂) crystals that undergo a first-order ferroelectric phase transition of the order–disorder type. The influence of the rate and temperature of quenching, as well as the strength of an external electric field, on the subsequent evolution of the system toward the thermodynamic equilibrium state has been analyzed. It has been shown that, by varying a weak external electric field applied to the ferroelectric crystal after quenching, it is possible to obtain both single-domain and multi-domain ordered structures. It has been established that the formation of nonequilibrium (“virtual”) multi-domain structures of the asymmetric type is possible for particular strengths of the electric field applied to the ferroelectric after quenching. A similar effect can be achieved by varying the depth of quenching of the sample. It has been found that, if the size of the order parameter inhomogeneities formed at the stage of quenching does not exceed a critical value, they can be reoriented partially or completely into domains of opposite sign. For this purpose, the relaxation after quenching should be performed in an external electric field of the appropriate sign.     

Microscopic simulation of the polarization switching at ferroelectric first-order phase transitions

Simulations of the kinetics of polarization switching at first-order ferroelectric phase transitions are carried out within the framework of Ishibashi dipole lattice model. We consider the influence of the dipole–dipole interaction between polar units on the polarization switching taking into account the existence of metastable states. We also examine the size effect on the switching kinetics. We calculate hysteresis loops and switching rates in the systems in which the continuum approximation is not valid. We show that in the case of hundreds of polar units our equations give the known analytical expressions for the switching rate.     

The dynamics of 180° domains in a ferroelectric in the process of polarization reversal and electron emission

A model is proposed to describe the evolution of 180° domains in a ferroelectric. Closed analytic expressions are obtained for the velocity of sideways motion of a 180° domain wall in an electric field and numerical calculations are performed. The connection between polarization reversal and electron emission is discussed.