Thermodynamic and Phase-field Analysis of Domain Structures and Switching Kinetics of Bismuth Ferrite Thin Films


Book Description

In this study, thermodynamic analysis and phase-field simulation are utilized to study the polarization, phase transitions, and phase coexistence in BFO thin films. The effect of temperature, substrate strain, and electrical bias on the phase stability and the phase transformation pathways were studied. Existing thermodynamic analysis methods are supplemented by a phase de-strain model, which determines free energy minima as a function of biaxial strain and the fractions of BFO's ferroelectric phases in a thin film. The results of this methodology are compared with phase-field modeling. The phase de-strain model shows reasonable accuracy in determining boundaries at which BFO's phase mixtures and morphotropic phase boundaries can form. Increasing temperature is shown to favor phases that occur at lower strains, and increase the strain required to induce formation of high-strain phases of BFO. Thermodynamic analysis and phase-field modeling are further used to predict the coercive field and its dependence on the biaxial strain, and temperature. Both models show reasonable agreement. As temperature increases, the coercive field required to induce electrical switching decreases under given substrate strain. Depending on the relative stability of phases at a given strain, the phase transformation can occur as a part of the electrical switching process.




Phase-field Simulations of Topological Structures and Topological Phase Transitions in Ferroelectric Oxide Heterostructures


Book Description

Ferroelectrics are materials that exhibit spontaneous electric polarization which can be switched between energy-degenerated states by external stimuli (e.g., mechanical force and electric field) that exceeds a critical value. They have wide potential applications in memories, capacitors, piezoelectric and pyroelectric sensors, and nanomechanical systems. Topological structures and topological phase transitions have been introduced to the condensed matter physics in the past few decades and have attracted broad attentions in various disciplines due to the rich physical insights and broad potential applications. Ferromagnetic topological structures such as vortex and skyrmion are known to be stabilized by the antisymmetric chiral interaction (e.g., Dzyaloshinskii-Moriya interaction). Without such interaction, ferroelectric topological structures (i.e., vortex, flux-closure, skyrmions, and merons) have been studied only recently with other designing strategies, such as reducing the dimension of the ferroelectrics. The overarching goal of this dissertation is to investigate the topological structures in ferroelectric oxide perovskites as well as the topological phase transitions under external applied forces.Pb(Zr,Ti)O3 (PZT) with morphotropic phase boundary is widely explored for high piezoelectric and dielectric properties. The domain structure of PZT tetragonal/rhombohedral (T/R) bilayer is investigated. Strong interfacial coupling is shown, with large polarization rotation to a lower symmetry phase near the T/R interface. Interlayer domain growth can also be captured, with T-domains in the R layer and R-domains in the T layer. For thin PZT bilayer with 5nm of T-layer and 20 nm of R-layer, the a1/a2 twin domain structure is formed in the top T layer, which could be fully switched to R domains under applied bias. While a unique flux-closure pattern is observed both theoretically and experimentally in the thick bilayer film with 50 nm of thickness for both T and R layers. It is revealed that the bilayer system could facilitate the motion of the ferroelastic a-domain in the top T-layer since the a-domain is not directly embedded in the substrate with high density of defects which can pin the domain wall. Excellent dielectric and piezoelectric responses are demonstrated due to the large polarization rotation and the highly mobile domain walls in both the thick and thin bilayer systems.The long-range ordered polar vortex array is observed in the (PbTiO3)n/(SrTiO3)n (PTOn/STOn with n=10~20) superlattices with combined experimental and theoretical studies. Phase-field simulations reveal the three-dimensional textures of the polar vortex arrays. The neighboring vortices rotate in the opposite directions, which extended into tube-like vortex lines perpendicular to the vortex plane. The thickness-dependent phase diagram is predicted and verified by experimental observations. The energetics (the contributions from elastic, electrostatic, gradient and Landau chemical energies) accompanying the phase transitions are analyzed in details. The dominating depolarization energy at short periodicity (n10) favors a1/ a2 twin domain, while the large elastic relaxation and Landau energy reduction at large periodicity (n20) leads to the formation of flux-closure domain with both 90o a/c domain walls and 180o c+/c- domain walls, counterbalancing of the individual energies at intermediate periodicities (n=10~20) gives rise to the formation of exotic vortex structure with continuous polarization rotation surrounding a singularity-like vortex core. Analytical calculations are performed, showing that the stability of the polar vortex structure is directly related to the length of Pi times bulk domain wall width, where vortex structure can be expected when the geometric length scale of the ferroelectrics is close to this value. The role of insulating STO is further revealed, which shows that a rich phase diagram can be formed by simply tuning the thickness of this layer. Wave-like polar spiral phase is simulated by substituting part of the PTO with BiFeO3 (BFO) in the PTO/STO superlattice (i.e., in a (PTO)4/(BFO)4/(PTO)4/(STO)12 tricolor system) which has demonstrate ordered polar vortex lattice. This spiral phase is made up of semi-vortex cores that are floating up-down in the ferroelectric PTO layers, giving rise to a net in-plane polarization. An increase of Curie temperature and topological to regular domain transition temperature (over 200 K) is observed, due to the higher Curie temperature and larger spontaneous polarization in BFO layers. This unidirectional spiral state can be reversibly switched by experimentally feasible in-plane field, which evolves into a metastable vortex structure in-between two spiral phases with opposite in-plane directions.The switching of polar vortex lattice under capacitor field for the (PTO)16/(STO)16 superlattice is studied, which reveals the existence of polar skyrmion state at intermediate applied bias. This is akin to the Rayleigh-Plateau instability in the fluid mechanics. A similar phenomenon is experimentally observed in the ferromagnetic system recently. The skyrmion-like structure will shrink with the further increasing of applied bias after saturation and eventually disappear given sufficiently large bias, leading to the formation of ferroelectric/ferroelastic twin domains with distinct 90o domain walls. Dimensionality cross-over is demonstrated, where a 1-D vortex core structure can be switched to the 2-D domain wall by the joint of two vortices with opposite curls. Electric-field phase diagram is plotted, showing a wide electric field region which could stabilize the metastable polar skyrmion state. This could serve as a road map for the experimental observation of the ferroelectric skyrmion state.




The Physics of Structural Phase Transitions


Book Description

Phase transitions in which crystalline solids undergo structural changes present an interesting problem in the interplay between the crystal structure and the ordering process. This text, intended for readers with some prior knowledge of condensed-matter physics, emphasizes the basic physics behind such spontaneous structural changes in crystals. Starting with the relevant thermodynamic principles, the book discusses the nature of order variables and their collective motion in a crystal lattice; in a structural phase transition a singularity in such a collective mode is responsible for the lattice instability, as revealed by soft phonons. This mechanism is analogous to the interplay of a charge-density wave and a periodically deformed lattice in low-dimensional conductors. The text also describes experimental methods for modulated crystal structures and gives examples of structural changes in representative systems. The book is divided into two parts. The first, theoretical, part includes such topics as: the Landau theory of phase transitions; statistics, correlations and the mean-field approximation; pseudospins and their collective modes; soft lattice modes and pseudospin condensates; lattice imperfections and their role in the phase transitions of real crystals. The second part discusses experimental studies of modulated crystals using x-ray diffraction, neutron inelastic scattering, light scattering, dielectric measurements, and magnetic resonance spectroscopy.




Continuum Scale Simulation of Engineering Materials


Book Description

This book fills a gap by presenting our current knowledge and understanding of continuum-based concepts behind computational methods used for microstructure and process simulation of engineering materials above the atomic scale. The volume provides an excellent overview on the different methods, comparing the different methods in terms of their respective particular weaknesses and advantages. This trains readers to identify appropriate approaches to the new challenges that emerge every day in this exciting domain. Divided into three main parts, the first is a basic overview covering fundamental key methods in the field of continuum scale materials simulation. The second one then goes on to look at applications of these methods to the prediction of microstructures, dealing with explicit simulation examples, while the third part discusses example applications in the field of process simulation. By presenting a spectrum of different computational approaches to materials, the book aims to initiate the development of corresponding virtual laboratories in the industry in which these methods are exploited. As such, it addresses graduates and undergraduates, lecturers, materials scientists and engineers, physicists, biologists, chemists, mathematicians, and mechanical engineers.




Multiscale Materials Modeling for Nanomechanics


Book Description

This book presents a unique combination of chapters that together provide a practical introduction to multiscale modeling applied to nanoscale materials mechanics. The goal of this book is to present a balanced treatment of both the theory of the methodology, as well as some practical aspects of conducting the simulations and models. The first half of the book covers some fundamental modeling and simulation techniques ranging from ab-inito methods to the continuum scale. Included in this set of methods are several different concurrent multiscale methods for bridging time and length scales applicable to mechanics at the nanoscale regime. The second half of the book presents a range of case studies from a varied selection of research groups focusing either on a the application of multiscale modeling to a specific nanomaterial, or novel analysis techniques aimed at exploring nanomechanics. Readers are also directed to helpful sites and other resources throughout the book where the simulation codes and methodologies discussed herein can be accessed. Emphasis on the practicality of the detailed techniques is especially felt in the latter half of the book, which is dedicated to specific examples to study nanomechanics and multiscale materials behavior. An instructive avenue for learning how to effectively apply these simulation tools to solve nanomechanics problems is to study previous endeavors. Therefore, each chapter is written by a unique team of experts who have used multiscale materials modeling to solve a practical nanomechanics problem. These chapters provide an extensive picture of the multiscale materials landscape from problem statement through the final results and outlook, providing readers with a roadmap for incorporating these techniques into their own research.




Formation of Ferroelectricity in Hafnium Oxide Based Thin Films


Book Description

In 2011, Böscke et al. reported the unexpected discovery of ferroelectric properties in hafnia based thin films, which has since initiated many further studies and revitalized research on the topic of ferroelectric memories. In spite of many efforts, the unveiling of the fundamentals behind this surprising discovery has proven rather challenging. In this work, the originally claimed Pca21 phase is experimentally proven to be the root of the ferroelectric properties and the nature of this ferroelectricity is classified in the frame of existing concepts of ferroelectric materials. Parameters to stabilize this polar phase are examined from a theoretical and fabrication point of view. With these very basic questions addressed, the application relevant electric field cycling behavior is studied. The results of first-order reversal curves, impedance spectroscopy, scanning transmission electron microscopy and piezoresponse force microscopy significantly advance the understanding of structural mechanisms underlying wake-up, fatigue and the novel phenomenon of split-up/merging of transient current peaks. The impact of field cycling behavior on applications like ferroelectric memories is highlighted and routes to optimize it are derived. These findings help to pave the road for a successful commercialization of hafnia based ferroelectrics.




Ferroelectric Thin Films


Book Description

Ferroelectric thin films continue to attract much attention due to their developing applications in memory devices, FeRAM, infrared sensors, piezoelectric sensors and actuators. This book, aimed at students, researchers and developers, gives detailed information about the basic properties of these materials and the associated device physics. The contributing authors are acknowledged experts in the field.




Comprehensive Nuclear Materials


Book Description

Materials in a nuclear environment are exposed to extreme conditions of radiation, temperature and/or corrosion, and in many cases the combination of these makes the material behavior very different from conventional materials. This is evident for the four major technological challenges the nuclear technology domain is facing currently: (i) long-term operation of existing Generation II nuclear power plants, (ii) the design of the next generation reactors (Generation IV), (iii) the construction of the ITER fusion reactor in Cadarache (France), (iv) and the intermediate and final disposal of nuclear waste. In order to address these challenges, engineers and designers need to know the properties of a wide variety of materials under these conditions and to understand the underlying processes affecting changes in their behavior, in order to assess their performance and to determine the limits of operation. Comprehensive Nuclear Materials, Second Edition, Seven Volume Set provides broad ranging, validated summaries of all the major topics in the field of nuclear material research for fission as well as fusion reactor systems. Attention is given to the fundamental scientific aspects of nuclear materials: fuel and structural materials for fission reactors, waste materials, and materials for fusion reactors. The articles are written at a level that allows undergraduate students to understand the material, while providing active researchers with a ready reference resource of information. Most of the chapters from the first Edition have been revised and updated and a significant number of new topics are covered in completely new material. During the ten years between the two editions, the challenge for applications of nuclear materials has been significantly impacted by world events, public awareness, and technological innovation. Materials play a key role as enablers of new technologies, and we trust that this new edition of Comprehensive Nuclear Materials has captured the key recent developments. Critically reviews the major classes and functions of materials, supporting the selection, assessment, validation and engineering of materials in extreme nuclear environments Comprehensive resource for up-to-date and authoritative information which is not always available elsewhere, even in journals Provides an in-depth treatment of materials modeling and simulation, with a specific focus on nuclear issues Serves as an excellent entry point for students and researchers new to the field