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

Thin film piezoelectric materials offer a number of advantages in microelectromechanical systems (MEMS), due to the large motions that can be generated, often with low hysteresis, the high available energy densities, as well as high sensitivity sensors with wide dynamic ranges, and low power requirements This paper reviews the literature in this field, with an emphasis on the factors that impact the magnitude of the available piezoelectric response For non-ferroelectric piezoelectrics such as ZnO and AlN, the importance of film orientation is discussed The high available electrical resistivity in AlN, its compatibility with CMOS processing, and its high frequency constant make it especially attractive in resonator applications The higher piezoelectric response available in ferroelectric films enables lower voltage operation of actuators, as well as high sensitivity sensors Among ferroelectric films, the majority of the MEMS sensors and actuators developed have utilized lead zirconate titanate (PZT) films as the transducer Randomly oriented PZT films show piezoelectric e(31, f) coefficients of about - 7 C/m(2) at the morphotropic phase boundary In PZT films, orientation, composition, grain size, defect chemistry, and mechanical boundary conditions all impact the observed piezoelectric coefficients The highest achievable piezoelectric responses can be observed in {001} oriented rhombohedrally-distorted perovskites For a variety of such films, e(31,f) coefficients of - 12 to - 27 C/m(2) have been reported

Thin Film Piezoelectrics for MEMS

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

Recent development in lead-free perovskite piezoelectric bulk materials

▪ Abstract This paper reviews the literature on size effects in ferroelectric materials, with an emphasis on thin film perovskite ferroelectrics. The roles of boundary conditions, defect chemistry, electrode interfaces, surface layers, and microstructure in controlling the measured properties of ferroelectric films, as well as the observed deviation from bulk properties are discussed. Examples of the manifestation of size effects in terms of the low and high field dielectric properties, the piezoelectric effect, and the leakage behavior of films are given.

The Properties of Ferroelectric Films at Small Dimensions

Low‐field piezoelectric coefficient and strain were investigated in Ca‐modified PbTiO3 thin films by means of optical interferometry. A remanent piezoelectric coefficient of 70 pm/V was observed that agrees well with the values previously reported for the bulk ceramics of the same composition. The efficient poling of the films can be achieved at room temperature under the field of 300 kV/cm. Electrically induced strains as high as 0.8% were observed using a bipolar driving field of 1 MV/cm. Strain response under a unipolar driving field exhibited a good linearity and small hysteresis. These properties combined with the low dielectric constant and high dielectric strength are shown to be attractive for micromechanical applications.

Piezoelectric properties of Ca‐modified PbTiO3 thin films

Phases, domain configuration, and properties of 0.65Pb(Mg1∕3Nb2∕3)O3–0.35PbTiO3 ceramics with grain sizes of 4 and 0.15μm have been studied. The average phase is monoclinic Pm in coexistence with tetragonal. An evolution from micron-sized lamellar domains towards submicron/nanometer sized crosshatched domains is found with the decrease in size, which results in electrical relaxor type behavior and hindered switching. This is proposed to be associated with the slowing down of the relaxor to ferroelectric transition that causes the long time presence of an intermediate domain configuration. Nevertheless, a high sensitivity piezoelectric submicron-structured material is obtained under tailored poling (d33∼300pCN−1).

Size effect in morphotropic phase boundary Pb(Mg1∕3Nb2∕3)O3–PbTiO3

On the effects of stresses in ferroelectric (Pb,Ca)Tio3 thin films

We have investigated the occurrence of phase-change functional responses in the BiFeO3-PbTiO3 perovskite solid solution, analogous to those anticipated by a recent first-principles study of BiFeO3-BiCoO3. Like the former system, BiFeO3-PbTiO3 shows a morphotropic phase boundary (MPB) between multiferroic polymorphs of rhombohedral and tetragonal symmetries. MPB BiFeO3-PbTiO3 is a high temperature ferroelectric with the phase transition around 900 K, and a room temperature square-shape hysteresis loop with remnant polarization as high as 62 μC cm−2. Strain under the electric field was studied, and a phase-change response was found. Analogous magnetoelectric effects are expected from the multiferroic nature of this MPB.

Very high remnant polarization and phase-change electromechanical response of BiFeO3-PbTiO3 at the multiferroic morphotropic phase boundary

Lead-free (1 − x)Bi0.5Na0.5TiO3–xBi0.5K0.5TiO3 [(BNKTx); x = 0.18, 0.20, 0.22, 0.24] piezoelectric ceramics were prepared via conventional solid-state reactions. Phase characterization using x-ray diffraction showed coexistence of perovskite rhombohedral and tetragonal polymorphs as anticipated for compositions across the morphotropic phase boundary (MPB). Electrical and electromechanical properties were studied as a function of x. Permittivity and polarization figures were comparable to the best values previously reported. Largest piezoelectric and high field electromechanical responses were obtained for BNKT0.20 samples, considered to have optimum MPB phases. This material exhibited giant field-induced strains of 0.13% and 0.38% under electric fields of 1 and 2.4 kV mm−1 at room temperature by a phase-change mechanism. Figures are comparable to those reported for other BNT-based systems, but under significantly lower driving fields, which is a clear advantage for actuation.

Pablo Ramos

Papers

Piezoelectric properties of Ca‐modified PbTiO3 thin films

Size effect in morphotropic phase boundary Pb(Mg1∕3Nb2∕3)O3–PbTiO3

On the effects of stresses in ferroelectric (Pb,Ca)Tio3 thin films

Very high remnant polarization and phase-change electromechanical response of BiFeO3-PbTiO3 at the multiferroic morphotropic phase boundary

High-field electromechanical response of Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3 across its morphotropic phase boundary