Softening and hardening transitions in ferroelectric Pb(Zr,Ti)O3 ceramics

Hysteretic and nonlinear dielectric behaviour in ferroelectric ceramics has been of interest since 1950s, when these materials found application in various electronic devices. Presently, these phenomena concern with important areas of science, technology and engineering. In particular, nonlinearity and hysteresis are the key factors in performance, precision and accuracy of modern devices. Many theoretical and experimental studies have been aimed at understanding the origins of hysteresis and nonlinearity in ferroelectrics. Nowadays, there are several models that describe major contributions to nonlinearity and hysteresis on phenomenological, microscopical or statistical levels. These models have a limited area of applicability due to the complexity of physical processes occurring in real materials. Empirically, hysteresis and nonlinearity in ferroelectrics can be controlled by softening and hardening of the material. This is the case of most widely used ferroelectric, lead zirconate titanate (PZT). The soft compositions possess large electro-mechanical coefficients but also large hysteresis and nonlinearity while the opposite is true for the hard compositions. After fifty years since introduction of these materials, the mechanisms of softening and hardening remain poorly understood. The present study is aimed at a better understanding of the processes leading to hardening and softening of Pb(Zr,Ti)O3 ceramics in order to verify the key principles required for a more universal physical model of hysteresis and nonlinearity. Based on the present state of knowledge, such model should consider domain wall contribution to nonlinear and hysteretic polarization response and at the same time account for hardening and softening of the ferroelectric. For this purpose the well known lead zirconate titanate (PZT) ceramics doped with various concentrations of niobium (soft materials) or iron (hard materials) are chosen as a prototype of the ferroelectric system. The starting hypothesis of the thesis' approach is that the softening and hardening are a result of electrostatic arrangement of charged defects in the ceramic bulk: the hard materials are characterized by the ordered and the soft by disordered defects. The thesis then develops in detail the idea that hardening-softening transitions in a ferroelectric system may occur under the influence of (i) dopants, depending on their type and concentration, (ii) a cyclically applied electric field, (iii) a thermal treatment, and (iv) time. The transition from microscopic order to microscopic disorder is confirmed experimentally using carefully analyzed phenomenological parameters of the macroscopic hysteresis and nonlinearity. Among the nonlinear and hysteretic parameters characterizing the polarization response of a ferroelectric material, some (e.g., third harmonic of polarization) are shown to be particularly sensitive to the softness and hardness of ferroelectric system and thus may serve as the characteristics of ferroelectric hardening-softening transitions. Contribution of domain walls to hysteresis and nonlinearity is analyzed in terms of domain wall energy potential and degree of ordering of pinning centres. It is shown that two existing models characterizing hard (V-potential) and soft (random potential) materials are ideal, limiting cases and that some real materials are described by an intermediary case, which can evolve with time and under influence of external factors. The dielectric characterization performed at wide range of frequencies has revealed an increase of the apparent frequency dispersion of the dielectric permittivity with the transition from the hard to soft state in PZT ceramics. The investigation of dielectric response over a wide temperature range has revealed the profound presence of hopping conductivity in iron doped PZT ceramics below the Curie temperatures and its absence in niobium doped PZT ceramics. The role of hopping charged species in ferroelectric hardening – softening transitions is analyzed and discussed. The thesis is organized in the following way. A brief introduction (Chapter 1) and a literature review of the theoretical description of domain wall contribution to dielectric nonlinearity and hysteresis in ferroelectrics (Chapter 2) is followed by the thesis outline and discussion of a unified model of hysteresis and nonlinearity in ferroelectrics with ordered and disordered states of domain wall pinning centres (Chapter 3). Processing of ceramics is described in Chapter 4 and mathematical and experimental background for the dielectric spectroscopy study in Chapter 5. The results and discussion of detailed experimental studies of polarization response in ferroelectric PZT ceramics under subswitching and switching conditions are given in Chapters 6 and 7. The summary of the main results and conclusions are given in the last thesis section.

In-situ structural investigations of ferroelasticity in soft and hard rhombohedral and tetragonal PZT

Dragan Damjanovic

Despite the technological importance of hard and soft PZT, Pb(Zr,Ti)O3, ceramics, the mechanisms of ferroelectric hardening and softening remain widely discussed in the literature. The hardening and softening phenomena have traditionally been investigated in relation with dielectric manifestations such as aging of the dielectric susceptibility and constriction of the polarization electric field hysteresis loop. Here, we present a systematic investigation of the ferroelectric and ferroelastic properties of soft and hard PZT in both the tetragonal and rhombohedral phases. A particular focus has been devoted to ferroelastic domain switching by characterizing the macroscopic mechanical constitutive behavior and in-situ synchrotron X-ray diffraction during compression. It is demonstrated that variation of the ordering state of point defects in PZT ceramics affects the switching behavior of both ferroelectric and ferroelastic domains under mechanical or electrical fields. Softening of the mechanical and electrical properties of originally hard PZT ceramics was conferred by quenching the materials from above the Curie temperature. The present findings are discussed with respect to the current understanding of hardening-softening transitions in ferroelectric materials.

American Institute of Physics2015

Experimental and first-principles study of point defects, domain walls, and point-defect/domain-wall interactions in ferroelectric oxides

Anand Chandrasekaran

Ferroelectric oxides, such as lead zirconate titanate, have proved invaluable due to their excellent dielectric and piezoelectric properties. These classes of materials possess a large electric polarization below the Curie temperature. Regions of the crystal lattice having different directions of polarization are separated by nano-scale interfaces known as domain walls. These interfaces, which can be moved by electric and mechanical fields, are not only important for electromechanical properties but they also exhibit unique structural and electronic properties that may be exploited through novel application in nanoelectronics and photovoltaics. The mobility of domain walls is strongly dependent on the defect chemistry of the material due to defect-domain wall interactions. Indeed, aliovalent doping of these materials has been used to tune the properties of ferroelectric oxides for specific applications. In this work, we investigate the origin of the so-called âhardâ and âsoftâ behavior in lead zirconate titanate. Experimental evidence suggests that small concentrations of donor dopants (such as niobium) results in enhanced domain wall motion while doping with acceptor dopants (such as iron) leads to an inhibited domain wall response. The microscopic origin of this phenomena is best investigated using first-principles simulations of the atomistic properties of defects and domain wall in these materials to bring to light novel structural and electronic properties. First, we show that polar defect complexes are likely to exist in both acceptor-doped and undoped PbTiO3 . These defects and defect associates are attracted to 180o domain walls and cause pinning of such interfaces. Donor- doped materials, on the other hand, do not show the presence of polar defect complexes. A closer investigation of the 180o domain wall in PbTiO3 reveals the presence of a âBlochâ component of polarization at the domain wall. In other words, due to polarization rotation, there exists a ferroelectric phase within the domain wall itself. We characterize the strain dependence of this phenomena and calculate the piezoelectric properties of such domain walls. A complete study of domain walls in PbTiO3 also entails looking closer at the properties of the ferroelastic âhead-to-tailâ 90o domain boundary. We show the presence of an asymmetry in the variation of the lattice parameter across the domain wall. This asymmetry is verified using high resolution aberration corrected electron microscopy. We look at the energy landscape of oxygen vacancies in the vicinity of these walls to explain the pinning effect in terms of random-bond and random-field defects. Next we look at the electronic properties of the recently discovered charged domain walls. We characterize the band bending phenomena in 90o head-to-head and tail-to-tail domain wall in PbTiO3 . We then look at the long range effects of clusters of oxygen vacancies in BaTiO3; especially in terms of the formation of 180o tail-to-tail domain wall. In parallel to the first priciples work, we also prepared high quality samples of PZT 50/50 with different concentrations of donor dopant. We characterized the microstructure and hysteresis loops as a function of donor dopant concentration. Based on experimental observations and ab initio calculations we propose ideas on the origins of hardening and softening in PZT.

EPFL2016

High coupling materials for thin film bulk acoustic wave resonators

Janine Conde

Radio frequency (RF) filters based on bulk acoustic wave resonances in piezoelectric thin films have become indispensable components in mobile communications. The currently used material, AlN, exhibits many excellent properties for this purpose. However, its bandwidth is often a limiting factor. In addition, no tuning is possible with AlN. Ferroelectrics would offer both larger coupling to achieve larger bandwidths, and tunability. However, their acoustic properties are not well known, especially in the thin film case. The goal of this thesis is to investigate the potential and identify the limitations of ferroelectric thin films for thickness mode resonators in the 0.5 - 2 GHz range. The Pb(Zrx,Ti1-x)O3 (PZT) solid solution system is the main candidate, since it is known for its large piezoelectric constants and its growth is already well studied. As a main test vehicle, free standing thin film bulk acoustic resonator (TFBAR) structures with Pt/PZT/Pt/SiO2 membranes were successfully fabricated using silicon micro-machining techniques. The main drawback of ferroelectrics is the damping of acoustic waves by domain wall motion both in the RF electric field and in the pressure wave. For this reason films with varying orientations and compositions were investigated. From the device structures the electro-mechanical coupling constants kt2, the quality factors (Q-factors) and several materials parameters have been obtained. High coupling constants have been found for sol-gel Pb(Zr0.53,Ti0.47)O3 films with a {100} texture, kt2 is found to be 0.4 for a 1 µm thick film and 0.8 for a 3.8 µm thick film. However, the Q-factors of these films are low, 18 for the first film and 3 for the second film. The increase of kt2 and the decrease of the Q-factor with frequency indicates that the domains present in these films contribute to these characteristic parameters. It was generally observed that high coupling constant are associated to low Q-factors. This became evident when comparing films with 53/47 composition, where both tetragonal and rhombohedral phases are present, to tetragonal films as well as when comparing {100} textures with (111) textures. Both for the 53/47 composition and for the {100} texture, ferroelastic domain walls are thought to play a bigger role than for tetragonal compositions and (111) textures. The highest figure of merit (FOM) of about 15 was found when combining the composition leading to a high coupling constant (53/47) and the orientation leading to lower losses (111). However the losses even in this film are too high for RF-filter applications. On the other hand, films with low Q-factors but high coupling could prove very useful as transducers for ultrasonic imaging applications, where low Q-factors are desired. The stiffness coefficients of the studied PZT films were shown to be higher than expected from ceramics data. Most likely the stiffness of ceramics always contains domain contributions leading to softening. In contrast, in textured films the variety of domain orientation is very much reduced. In order to reduce losses due the presence of ferroelastic domains three different potential solutions were explored. The first idea was to manipulate the domain populations of the films deposited on silicon by using heat and vacuum treatments. Silicon substrates are known from previous works to be unfavourable for high c-domain fractions. It was discovered that an anneal in vacuum at 550 °C lead to a significant reduction of c-domains in tetragonal 30/70 PZT ({100}). On the contrary, if the sample was subjected to a compressive stress during cooling, the c-domain fraction could be increased. Analysis of the film stress versus temperature curves revealed a trend consistent with theoretical predictions, i.e. a phase boundary between the c/a/c/a and the a1/a2/a1/a2 domain patterns between room temperature and the Curie temperature θC. However, even though this method reveals interesting results, it can not be exploited as a method to achieve a sufficient c-domain population. The second idea explored was the implementation of a high thermal expansion material as a substrate. PZT films deposited on MgO are known to be compressive due to the difference in thermal expansion of the two materials. The compressive stress leads to highly c-axis oriented PZT films. Devices using MgO substrates were fabricated, however difficulties in the micro-machining of the MgO substrate inhibited a complete liberation of the membrane. Nevertheless, preliminary measurements indicate these devices could lead to both high coupling and high Q-factors, suggesting that further detailed study of this method is worthwhile. As a third method for avoiding ferroelastic domains, the uniaxial ferroelectric potassium lithium niobate (KLN) was explored. The unique ferroelectric axis in this material means that only 180° domain walls are present, which can theoretically be removed by poling. This material has been deposited in thin film form using pulsed laser deposition (PLD). KLN thin films with a {001} texture were deposited successfully on Pt/Si substrates. The films were piezoelectric with a d33,f value of around 10 pm/V and a dielectric constant of 250. This is the first time that piezoelectric properties were measured on KLN thin films. A columnar structure has been observed, however the small grain size and the rough surface currently make it difficult to apply this material to TFBAR's.