A SIGNIFICANT fraction of the computer memory industry is at present involved in the manufacture of non-volatile memory devices1—that is, devices which retain information when power is interrupted. For such applications (and also for volatile memories), the use of capacitors constructed from ferroelectric thin films has stimulated much interest1. In such structures, information is stored in the polarization state of the ferroelectric material itself, which should in principle lead to lower power requirements, faster access time and potentially lower cost1. But the use of ferroelectrics is not without problems; the memories constructed to date have generally suffered from poor retention of stored information and degradation of performance ('fatigue') with use1–3. Here we describe the preparation and characterization of thin-film capacitors using ferroelectric materials from a large family of layered perovskite oxides, exemplified by SrBi2Ta2O9, SrBi2NbTaO9 and SrBi4Ta4O15. The structural flexibility of these materials allows their properties to be tailored so that many of the problems associated with previous ferroelectric memories are avoided. In particular, our capacitors do not show significant fatigue after 1012 switching cycles, and they exhibit good retention characteristics and low leakage currents even with films less than 100 nm thick.

Fatigue-free ferroelectric capacitors with platinum electrodes

This review covers important advances in recent years in the physics of thin-film ferroelectric oxides, the strongest emphasis being on those aspects particular to ferroelectrics in thin-film form. The authors introduce the current state of development in the application of ferroelectric thin films for electronic devices and discuss the physics relevant for the performance and failure of these devices. Following this the review covers the enormous progress that has been made in the first-principles computational approach to understanding ferroelectrics. The authors then discuss in detail the important role that strain plays in determining the properties of epitaxial thin ferroelectric films. Finally, this review ends with a look at the emerging possibilities for nanoscale ferroelectrics, with particular emphasis on ferroelectrics in nonconventional nanoscale geometries.

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Physics of thin-film ferroelectric oxides

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

Imagine you are in the last stages of typing your thesis, the year is 1980, and it's a hot, hazy summer afternoon, a thunderstorm brews on the horizon. Tense and tired, you have forgotten to save the document on your hard disk. Suddenly, lightning strikes! Your computer shuts down. Your final chapter is lost.

The Physics of Ferroelectric Memories

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

A theoretical model of fatigue in ferroelectric thin‐film memories based upon impact ionization (e.g., Ti+4 to Ti+3 conversion in PbZr1−xTixO3), resulting in dendritic growth of oxygen‐deficient filaments, is presented. The predictions of spontaneous polarization versus switching cycles Ps(N) are compared with both Monte Carlo simulations for a two‐dimensional Ising model and with experimental data on small‐grain (40 nm) sol‐gel PZT films. Excellent agreement between theory and experiment is obtained. In addition to modeling the Ps(N) curves, the theory developed explains the observed linear proportionality between switching time ts(N) and polarization Ps(N) during fatigue; other models of aging do not account for this. Earlier theories of switching are also extended to include finite grain sizes, surface nucleation, triangular drive pulses, and dipolar forces. Good agreement with sol‐gel PZT switching data is obtained.

Fatigue and switching in ferroelectric memories: Theory and experiment

We have measured electrical and spectroscopic properties of thin films (d = 75–500 nm) of ferroelectric ceramic potassium nitrate and developed a mean field theory which explicitly incorporates film thickness effects. Variations of Tc(d) are observed as are changes in the shape of Ps(T) with thickness. Comparisons with earlier work on TGS are made.

Properties of ceramic KNO3 thin-film memories☆

A model of ferroelectric switching that describes crystals composed of a large number of relatively small grains is presented. It is shown that, if the grain boundaries stop or significantly affect domain-wall growth, then the observed switching current transients will deviate from those predicted by the infinite-grain model of Ishibashi and Takagi. The model accounts for constant nucleation rate throughout the switching period and for constant domain-wall velocity. It is shown that at some time dependent only on the size of the grains and the domain-wall velocity, the switching-current transient changes from its small-time infinite-grain behavior to an exponential decay. The results are applied to two-dimensional Ising-model simulations.

Grain-size effects in ferroelectric switching

We present a model of ferroelectric switching which describes domain growth in crystals composed of a large number of relatively small grains. If the grain boundaries stop or significantly affect domain wall motion then the observed switching transients will deviate from those predicted by the infinite grain model of Ishibashi and Takagi. The model assumes a constant nucleation rate throughout the switching process and constant domain wall velocity. At a characteristic time dependent only on the size of the grains and the domain wall velocity the switching current transient changes from its early-time infinite-grain behavior to an exponential decay. The results are compared with Monte Carlo simulations of switching in the two-dimensional Ising model.

H. M. Duiker

Papers

Fatigue and switching in ferroelectric memories: Theory and experiment

Properties of ceramic KNO3 thin-film memories☆

Grain-size effects in ferroelectric switching

Grain-size effects in ferroelectric switching