Ferroelectric, dielectric and piezoelectric properties of ferroelectric thin films and ceramics are reviewed with the aim of providing an insight into different processes which may affect the behaviour of ferroelectric devices, such as ferroelectric memories and micro-electro-mechanical systems. Taking into consideration recent advances in this field, topics such as polarization switching, polarization fatigue, effects of defects, depletion layers, and depolarization fields on hysteresis loop behaviour, and contributions of domain-wall displacement to dielectric and piezoelectric properties are discussed. An introduction into dielectric, pyroelectric, piezoelectric and elastic properties of ferroelectric materials, symmetry considerations, coupling of electro-mechanical and thermal properties, and definitions of relevant ferroelectric phenomena are provided.

https://iopscience.iop.org/article/10.1088/0034-4885/61/9/002/pdf

Ferroelectric, dielectric and piezoelectric properties of ferroelectric thin films and ceramics

Domains in ferroelectrics were considered to be well understood by the middle of the last century: They were generally rectilinear, and their walls were Ising-like. Their simplicity stood in stark contrast to the more complex Bloch walls or N\'eel walls in magnets. Only within the past decade and with the introduction of atomic-resolution studies via transmission electron microscopy, electron holography, and atomic force microscopy with polarization sensitivity has their real complexity been revealed. Additional phenomena appear in recent studies, especially of magnetoelectric materials, where functional properties inside domain walls are being directly measured. In this paper these studies are reviewed, focusing attention on ferroelectrics and multiferroics but making comparisons where possible with magnetic domains and domain walls. An important part of this review will concern device applications, with the spotlight on a new paradigm of ferroic devices where the domain walls, rather than the domains, are the active element. Here magnetic wall microelectronics is already in full swing, owing largely to the work of Cowburn and of Parkin and their colleagues. These devices exploit the high domain wall mobilities in magnets and their resulting high velocities, which can be supersonic, as shown by Kreines' and co-workers 30 years ago. By comparison, nanoelectronic devices employing ferroelectric domain walls often have slower domain wall speeds, but may exploit their smaller size as well as their different functional properties. These include domain wall conductivity (metallic or even superconducting in bulk insulating or semiconducting oxides) and the fact that domain walls can be ferromagnetic while the surrounding domains are not.

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Domain wall nanoelectronics

Due to the nature of domains, ferroics, including ferromagnetic, ferroelectric, and ferroelastic materials, exhibit hysteresis phenomena with respect to external driving fields (magnetic field, electric field, or stress). In principle, every ferroic material has its own hysteresis loop, like a fingerprint, which contains information related to its properties and structures. For ferroelectrics, many characteristic parameters, such as coercive field, spontaneous, and remnant polarizations can be directly extracted from the hysteresis loops. Furthermore, many impact factors, including the effect of materials (grain size and grain boundary, phase and phase boundary, doping, anisotropy, thickness), aging (with and without poling), and measurement conditions (applied field amplitude, fatigue, frequency, temperature, stress), can affect the hysteretic behaviors of the ferroelectrics. In this feature article, we will first give the background of the ferroic materials and multiferroics, with an emphasis on ferroelectrics. Then it is followed by an introduction of the characterizing techniques for the loops, including the polarization–electric field loops and strain–electric field curves. A caution is made to avoid misinterpretation of the loops due to the existence of conductivity. Based on their morphologic features, the hysteresis loops are categorized to four groups and the corresponding material usages are introduced. The impact factors on the hysteresis loops are discussed based on recent developments in ferroelectric and related materials. It is suggested that decoding the fingerprint of loops in ferroelectrics is feasible and the comprehension of the material properties and structures through the hysteresis loops is established.

Decoding the Fingerprint of Ferroelectric Loops: Comprehension of the Material Properties and Structures

We present a critical review that encompasses the fundamentals and state-of-the-art knowledge of barium titanate-based piezoelectrics. First, the essential crystallography, thermodynamic relations, and concepts necessary to understand piezoelectricity and ferroelectricity in barium titanate are discussed. Strategies to optimize piezoelectric properties through microstructure control and chemical modification are also introduced. Thereafter, we systematically review the synthesis, microstructure, and phase diagrams of barium titanate-based piezoelectrics and provide a detailed compilation of their functional and mechanical properties. The most salient materials treated include the (Ba,Ca)(Zr,Ti)O3, (Ba,Ca)(Sn,Ti)O3, and (Ba,Ca)(Hf,Ti)O3 solid solution systems. The technological relevance of barium titanate-based piezoelectrics is also discussed and some potential market indicators are outlined. Finally, perspectives on productive lines of future research and promising areas for the applications of these ma...

BaTiO3-based piezoelectrics: Fundamentals, current status, and perspectives

Predictions are made based on an analysis of a new nonlinear theory of martensitic transformations introduced by the authors The crystal is modelled as a nonlinear elastic material, with a free-energy function that is invariant with respect to both rigid-body rotations and the appropriate crystallographic symmetries The predictions concern primarily the two-well problem, that of determining all possible energy-minimizing deformations that can be obtained with two coherent and macroscopically unstressed variants of martensite The set of possible macroscopic deformations obtained is completely determined by the lattice parameters of the material For certain boundary conditions the total free energy does not attain a minimum, and the finer and finer oscillations of minimizing sequences are interpreted as corresponding to microstructure The predictions are amenable to experimental tests The proposed tests involve the comparison of the theoretical predictions with the mechanical response of properly oriented plates subject to simple shear Additional crystallographic background is given for the model, and the theory is compared with the `linearized' model of Khachaturyan, Roitburd and Shatalov There are some similarities in the predictions of the two theories, but also some major discrepancies

Proposed experimental tests of a theory of fine microstructure and the two-well problem

The regular twinning in ceramics and metals below the temperature of a ferroelastic or ferroelectric structural phase transition is a result of energy minimization. Here homogeneous elastic energy is reduced at the expense of twin wall energy. The twin density depends on the gram sizeg; under homogeneous stress the total elastic energy of a grain increases ∝g
3. Any kind of twin wall, however, increases ∝g
2. Below the intersection of these two curves, stress reduction by twinning cannot lower the total energy. Thus there is a critical grain size below which twinning should not occur. Above this limit the width of the twin lamellae increases ∝g
1/2. The shape of the grain then adjusts to the surroundings in two dimensions only. Above another larger critical grain size more complex interfaces with higher surface energy are created, which allow stress relief in the third dimension. A semi-quantitative model is developed with the example of BaTiO3 ceramic, of which the domain patterns are well known. It is representative for many ceramics. The highT
c superconductor YBa2Cu3O7−δ also twins according to the same law. For three-dimensional adjustment here a proper interface is missing.

G. Arlt

Papers

Twinning in ferroelectric and ferroelastic ceramics: stress relief