Yuri A. Genenko

Drift of charged defects in local fields as aging mechanism in ferroelectrics

Point defect migration is considered as a mechanism for aging in ferroelectrics. Numerical results are given for the coupled problems of point defect migration and electrostatic energy relaxation in a two-dimensional domain configuration. The peak values of the clamping pressure at domain walls are in the range of 106 Pa, which corresponds to macroscopically observed coercive stresses in perovskite ferroelectrics. The effect is compared to mechanisms involving orientational reordering of defect dipoles in the bulk of domains. Domain clamping is significantly stronger in the drift mechanism than in the orientational picture for the same material parameters.

Aging of poled ferroelectric ceramics due to relaxation of random depolarization fields by space-charge accumulation near grain boundaries

Migration of charged point defects triggered by the local random depolarization field is shown to plausibly explain aging of poled ferroelectric ceramics providing reasonable time and acceptor concentration dependences of the emerging internal bias field. The theory is based on the evaluation of the energy of the local depolarization field caused by mismatch of the polarizations of neighbor grains. The kinetics of charge migration assumes presence of mobile oxygen vacancies in the material due to the intentional or unintentional acceptor doping. Satisfactory agreement of the theory with experiment on the Fe-doped lead zirconate titanate is demonstrated.

Space-charge mechanism of aging in ferroelectrics: An analytically solvable two-dimensional model

A mechanism of point defect migration triggered by local depolarization fields is shown to explain some still inexplicable features of aging in acceptor-doped ferroelectrics. A drift-diffusion model of the coupled charged defect transport and electrostatic field relaxation within a two-dimensional domain configuration is treated numerically and analytically. Numerical results are given for the emerging internal bias field of about 1 kV/mm which levels off at dopant concentrations well below 1 mol %; the fact, long ago known experimentally but still not explained. For higher defect concentrations a closed solution of the model equations in the drift approximation as well as an explicit formula for the internal bias field is derived revealing the plausible time, temperature, and concentration dependencies of aging. The results are compared to those due to the mechanism of orientational reordering of defect dipoles.

Experimental and theoretical investigation on polarization reversal in unfatigued lead-zirconate-titanate ceramic

The dynamics of polarization switching in a soft lead-zirconate-titanate ceramic has been studied over a broad time window ranging from 10−6–106 for applied fields between 0.5 and 2.5 kV/mm. The classical Kolmogorov–Avrami–Ishibashi model of the polarization reversal was not able to satisfactory explain the obtained results. Therefore, a new concept for the polarization dynamics of ferroelectric ceramics has been suggested, which is based on two principal assumptions, (1) a strong dependence of the polarization switching time on the local electric field and (2) a random distribution of the local switching times caused by an intrinsic randomness in the field distribution within the system. Thereby the switching volume is composed as an ensemble of many regions with independent dynamics governed by local field exclusively. Such random field distribution could be well adjusted by a Gaussian distribution around the mean value of the field applied. A total polarization dependence on time and applied field was ...

Polarization dynamics across the morphotropic phase boundary in Ba(Zr0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3 ferroelectrics

Analysis of polarization switching dynamics by means of the inhomogeneous field mechanism model allows insight into the microscopic mechanism of reversed polarization domain nucleation. For all chemical compositions studied, two distinct field regions of nucleation are established. In the high-field region, the activation energy barrier is found to be inversely proportional to the local field according to the Merz law. In contrast, the barriers in the low-field region exhibit a linear field dependence with a minimum in the compositional region of phase instability, which can explain the corresponding peak ferroelectric properties.

Effect of bipolar electric fatigue on polarization switching in lead-zirconate-titanate ceramics

From comparison of experimental results on polarization switching in fresh and electrically fatigued lead-zirconate-titanate (PZT) over a wide range of applied fields and switching times it is concluded that fatigue alters the local field distribution inside the sample due to the generation of discrete defects, such as voids and cracks. Such defects have a strong influence on the overall electric field distribution by their shape and dielectric permittivity. On this hypothesis, a new phenomenological model of polarization switching in fatigued PZT is proposed. The model assumes that the fatigued sample can be composed of different local regions which exhibit different field strengths but otherwise can be considered as unfatigued. Consequently the temporal response of a fatigued sample is assumed to be the superposition of the field-dependent temporal responses of unfatigued samples weighted by their respective volume fraction. A certain part of the volume is excluded from the overall switching process due to the domain pinning even at earlier stages of fatigue, which can be recovered by annealing. Suitability of the proposed model is demonstrated by a good correlation between experimental and calculated data for differently fatigued samples. Plausible cause of the formation of such regions is the generation of defects such as microcracks and the change in electrical properties at imperfections such as pores or voids.

De-aging of Fe-doped lead-zirconate-titanate ceramics by electric field cycling: 180°- vs. non-180° domain wall processes

Acceptor-doped ferroelectrics tend to show pronounced aging behavior. The microscopic effects of aging are commonly related to oxygen vacancies, however, there are still open questions with respect to their impact on domain wall movements. To elucidate the latter, the reverse process of de-aging by electric field cycling is investigated here on Pb(Zr0.54Ti0.46)O3 doped with iron in different concentrations. Measurements of the hysteretic behavior of large-signal parameters, i.e., polarization and strain, as well as small-signal parameters, i.e., electrical permittivity and piezoelectric coefficient, are used to distinguish between reversible and irreversible movement of 180°- and non-180° domain walls. The results indicate that for low doping concentrations, the de-aging behavior of 180° domain wall motion is governed by irreversible domain wall motion and a coarsening of the domain structure, while for non-180° domain walls the change in reversible domain wall mobility is the dominant de-aging mechanism....

Surface potential at a ferroelectric grain due to asymmetric screening of depolarization fields

Nonlinear screening of electric depolarization fields, generated by a stripe domain structure in a ferroelectric grain of a polycrystalline material, is studied within a semiconductor model of ferroelectrics. It is shown that the maximum strength of local depolarization fields is rather determined by the electronic band gap than by the spontaneous polarization magnitude. Furthermore, field screening due to electronic band bending and due to presence of intrinsic defects leads to asymmetric space charge regions near the grain boundary, which produce an effective dipole layer at the surface of the grain. This results in the formation of a potential difference between the grain surface and its interior of the order of 1 V, which can be of either sign depending on defect transition levels and concentrations. Exemplary acceptor doping of BaTiO3 is shown to allow tuning of the said surface potential in the region between 0.1 and 1.3 V.

Magnetic cloaking by a paramagnet/superconductor cylindrical tube in the critical state

Cloaking of static magnetic fields by a finite thickness type-II superconductor tube being in the full critical state and surrounded by a coaxial paramagnet shell is studied. On the basis of exact solutions to the Maxwell equations, it is shown that, in addition to previous studies assuming the Meissner state of the superconductor constituent, perfect cloaking is still realizable at fields higher than the field of full flux penetration into the superconductor and for arbitrary geometrical parameters of both constituents. It is also proven that simultaneously the structure is fully undetectable under the cloaking conditions. Different from the case of the Meissner state, the cloaking properties in the application relevant critical state are realized, however, only at a certain field magnitude.

Flexocoupling impact on size effects of piezoresponse and conductance in mixed-type ferroelectric semiconductors under applied pressure

We explore the role of flexoelectric effect in functional properties of nanoscale ferroelectric films with mixed electronic-ionic conductivity. Using a coupled Ginzburg-Landau model, we calculate spontaneous polarization, effective piezoresponse, elastic strain and compliance, carrier concentration, and piezoconductance as a function of thickness and applied pressure. In the absence of flexoelectric coupling, the studied physical quantities manifest well-explored size-induced phase transitions, including transition to paraelectric phase below critical thickness. Similarly, in the absence of external pressure flexoelectric coupling affects properties of these films only weakly. However, the combined effect of flexoelectric coupling and external pressure induces polarizations at the film surfaces, which cause the electric built-in field that destroys the thickness-induced phase transition to paraelectric phase and induces the electretlike state with irreversible spontaneous polarization below critical thickness. Interestingly, the built-in field leads to noticeable increase of the average strain and elastic compliance in this thickness range. We further illustrate that the changes of the electron concentration by several orders of magnitude under positive or negative pressures can lead to the occurrence of high- or low-conductivity states, i.e., the nonvolatile piezoresistive switching, in which the swing can be controlled by the film thickness and flexoelectric coupling. The obtained theoretical results can be of fundamental interest for ferroic systems, and can provide a theoretical model for explanation of a set of recent experimental results on resistive switching and transient polar states in these systems.