Peculiarities of Ferro-Antiferroelectric Phase Transitions 9. Alternative for dipole-glass description of properties of substances with coexisting ferroelectric and antiferroelectric phases
It is demonstrated that the substances with small difference in the free energies of the ferroelectric and antiferroelectric phases possess a set of properties characteristic for the so-called "dipole glasses". Possible phase diagrams of the substances that can be misguidedly attributed to glasses are discussed. Main attention has been paid to the process of long-time relaxation of physical characteristics of these compounds after their state of thermodynamic equilibrium was disturbed by external influences. The long-time relaxation along with the pronounced frequency dependence of parameters (for example, dependence of dielectric or magnetic characteristics on the frequency of measuring field) is considered as main features due to which these systems are classified as dipole glasses. Our main purpose is to call attention to the fact that one has to be cautious during the interpretation of experimental results in substances with inhomogeneous states of coexisting domains of ferroelectric and antiferroelectric phases.
Comprehensive review of investigations of substances with a small difference in the energies of the ferroelectric and antiferroelectric types of dipole ordering is presented. Detailed analysis of the stability of homogeneous phases and conditions for existence of the inhomogeneous state of the substance containing domains of the coexisting ferroelectric and antiferroelectric phases is presented. It is shown that the interaction of locally separated domains of the ferroelectric and antiferroelectric phases stabilizes an inhomogeneous state of these materials. The analysis of physical phenomena …
Results of detailed investigations of stability of phases in substances with the small difference in the energies of the ferroelectric and the antiferroelectric types of dipole ordering are presented. It is shown that interaction of locally separated domains of the ferroelectric and antiferroelectric phases stabilizes a nonuniform state of the samples. The analysis of physical phenomena caused by the presence of domains of coexisting ferroelectric and antiferroelectric phases in different dipole ordered substances is presented. The consideration of peculiarities of behavior of systems with non…
A new definition of a dipole glass parameter for ferro-antiferroelectric solid mixtures is suggested. It is constructed on the nearest neighbours pair correlation functions for interacting dipole momenta. The behaviour of the dipole glass parameter is calculated and discussed.
In this paper, we present a microscopic model for heterogeneous ferroelectric and an order parameter for relaxor phase. We write a Landau theory based on this model and its application to ferroelectric PbFe$_{1/2}$Ta$_{1/2}$O$_3$ (PFT) and antiferroelectric NaNbO$_3$:Gd. We later discuss the coupling between soft mode and domain walls, soft mode and quasi-local vibration and resulting susceptibility function.
Phase diagram of solid solutions of antiferroelectric and ferroelectric materials like PbZr$_{1-x}$Ti$_x$O$_3$ (PZT), Rb$_x$(NH$_4$)$_{1-x}$H$_2$PO$% _4$ (RADP) is calculated at the region $x\leq 0.1$. Antiferroelectric and ferroelectric order parameters (which correspond respectively to the difference and sum of two sublattices ions shifts) were introduced for antiferroelectric host lattice. Small admixture of ferroelectric component was considered as a random electric field source. The influence of this field on both aforementioned order parameters was calculated. Self consistent averaging w…
Molecular dynamics simulations predict a giant electrocaloric effect at the ferroelectric-antiferroelectric phase boundary in PZT (PbTiO$_3$-PbZrO$_3$). These large-scale simulations also give insights into the atomistic mechanisms of the electrocaloric effect in PZT materials. Studying a range of ferroelectric (FE) and antiferroelectric (AFE) PZT materials we found positive electrocaloric effect in FE composites, but AFE ones exhibit a positive-to-negative crossover. At the AFE-FE phase boundary we find complex domain patterns. We demonstrate that the origin of giant electrocaloric change of …
Physical effects caused by the presence of interfaces between the domains of coexisting ferroelectric and antiferroelectric phases in solid solutions with small difference in free energies of the ferroelectric and antiferroelectric states are discussed in this review. There exist a number of solid solutions in which the two-phase state of domains of the coexisting phases may occur under certain conditions. We present here results of investigations of some effects directly caused by the presence of the interfaces between the domains of the coexisting ferroelectric and antiferroelectric phases. …
The combination of antiferroelectricity (AFE) and ferromagnetism (FM) in one structure would allow the development of new type of multiferroic candidates, which be applicable not only in magnetoelectric memories but also in novel energy storage devices. Here we propose a novel type of multiferroic candidate LaxSr1-xFe12O19, whose room temperature state could betuned from ferroelectrics (FE) to antiferroelectrics by changing x from 0 to 0.5. The emphasis of this paper will be focused on the La0.5Sr0.5Fe12O19 system, in which full AFE and FM coexist. The pure antiferroelectric behavior in La0.5S…
Neutron diffraction studies using powder samples have been used to understand the complex sequence of low temperature phase transitions of NaNbO3 in the temperature range from 12 K-350 K. Detailed Rietveld analysis of the diffraction data reveal that the antiferroelectric to ferroelectric phase transition occurs on cooling around 73 K while the reverse ferroelectric to antiferroelectric transition occurs on heating at 245 K. However, the former transformation is not complete till down to 12 K and there is unambiguous evidence for the presence of the ferroelectric R3c phase coexisting with an a…
The results of the first investigations of the process of local decomposition of lead-lanthanum zirconate-titanate solid solution in the vicinity of the interphase boundaries separating domains of coexisting ferroelectric and antiferroelectric phases are presented. The solid solution with the composition: 6 at% of La, 73 at% of Zr, and 27 at% of Ti is considered. The kinetics of the local decomposition of this solid solution in the process of aging of samples quenched down to room temperature from the paraelectric phase is studied. The mechanisms that define the kinetics of the process of esta…
Recently, a layered ferroelectric CuInP2Se6 was shown to exhibit domain walls with locally enhanced piezoresponse - a striking departure from the observations of nominally zero piezoresponse in most ferroelectrics. Although it was proposed that such "bright" domain walls are phase-boundaries between ferri- and antiferroelectrically ordered regions of the materials, the physical mechanisms behind the existence and response of these boundaries remain to be understood. Here, using Landau-Ginzburg-Devonshire phenomenology combined with four sub-lattices model, we describe quantitatively the bright…
We report a first-principles study of (BaTiO${_3}$)$_m$/(BaO)$_n$ superlattices for a wide range of periodicities $m/n$. We show that such a system develops a polar zone-center instability for sufficiently large \textit{m}/\textit{n} ratio, which can be understood, at least qualitatively, from a simple electrostatic model and should lead to a ferroelectric ground-state. However, the analysis of the phonon dispersion curves also points out the appearance of stronger antiferroelectric instabilities at the zone boundaries around $m=4$, before the critical ratio for ferroelectricity is reached and…
Coexistence of ferroelectric and ferrielectric phases in ultrathin antiferroelectric PbZrO3 thin films
Catalan Institute of Nanoscience and Nanotechnology (ICN2)（加泰罗尼亚纳米科学和技术研究所）；School of Aerospace, Mechanical and Mechatronic Engineering, The University of Sydney（悉尼大学航空航天、机械与机电工程学院）；Institut Català de Recerca i Estudis Avançats (ICREA)（加泰罗尼亚研究与高级研究学院）
We show how van der Waals (vdW) forces outcompete covalent and ionic forces to control ferroelectric ordering in CuInP2S6 nanoflakes as well as in CuInP2S6 and CuBiP2Se6 crystals. While the self-assembly of these 2D layered materials is clearly controlled by vdW effects, this result indicates that the internal layer structure is also similarly controlled. Using up to 14 first-principles computational methods, we predict that the bilayers of both materials should be antiferroelectric. However, antiferroelectric nanoflakes and bulk materials are shown to embody two fundamentally different types …
This paper contains results of investigations of inhomogeneous states caused by the coexistence of ferroelectric and antiferroelectric phases in lead-zirconate-titanate based solid solutions. The domains of ferroelectric and antiferroelectric phases with sizes of the order of 20 to 30 nm coexist in the bulk of the samples due to a small difference in the free energies of the phases. The coherent character of interphase boundaries leads to the concentration of elastic stresses along these boundaries. Elastic stresses cause the local decomposition of the solid solution due to the circumstance th…
The traditional derivation of the elastic anomalies associated with ferroelectric (FE) phase transitions in the framework of the Landau theory is combined with the piezoelectric constitutive relations instead of being explicitly carried out with a definite expression of the FE part of the free energy. In this manner it is shown that the softening within the FE phase is of electrostrictive and hence piezoelectric origin. Such a piezoelectric softening may be canceled by the better known piezoelectric stiffening, when the piezoelectric charges formed during the vibration are accompanied by the d…
A possibility of use of the controlled decomposition of solid solutions of oxides with perovskite structure in the state of coexisting domains of the antiferroelectric (AFE) and ferroelectric (FE) phases for manufacturing of materials with negative refractive index is demonstrated. The lead zirconate titanate based solid solutions are considered as an example of substances suitable for creation of such materials. Manufactured composites constitute a dielectric matrix with a structure of conducting interphase boundaries separating domains of the FE and AFE phases. The electric conductivity of i…
We investigate the microstructural evolution in a ferroelectric to antiferroelectric phase transition at the morphotropic phase boundary in the Bi(1-x)SmxFeO3 system. Continuous Sm3+ substitution on the A-site induces short-range anti-parallel cation displacements as verified by the appearance of localized 1/4(110) weak spots in selected area electron diffraction patterns for 0.1<x<0.14 samples, and thus onset of antiferroelectricity. Kinetic Monte Carlo simulations confirm that increasing the strength of the anti-parallel interactions (i.e. increasing x) induces a ferroelectric to antiferroel…
Antiferroelectrics have potential applications in energy conversion and storage, but are scarce, particularly among oxides that otherwise display rich ferroic behaviours. Are we overlooking potential antiferroelectrics, simply because we have not discovered their corresponding ferroelectric phase yet? Here we report a first-principles study suggesting this is the case of a family ABO$_3$ pyroxene-like materials, characterized by chains of corner-sharing BO$_4$ tetrahedra, a well-known member being KVO$_3$. The irregular tetrahedra have an electric dipole associated to them. In the most stable …
The influence of the B-site ion substitutions in (1-x)(Bi1/2Na1/2)TiO3-xBaTiO3 system of solid solutions on the relative stability of the ferroelectric and antiferroelectric phases has been studied. The ions of zirconium, tin, along with (In0.5Nb0.5), (Fe0.5Nb0.5), (Al0.5V0.5) ion complexes have been used as substituting elements. An increase in the concentration of the substituting ion results in a near linear variation in the size of the crystal lattice cell. Along with the cell size variation a change in the relative stability of the ferroelectric and antiferroelectric phases takes place ac…
Low-dimensional ferroelectricity and polar materials have attracted considerable attentions for their fascinating physics and potential applications. Based on first-principles calculations, here we investigate the stacking modes and polar properties of a typical series of quasi-one-dimensional ferroelectrics: double-chain oxyhalides NbO$X_3$ ($X$=Cl, Br, I). The geometry of their double-chains allows both the interchain/intrachain permutation. Thus, different stacking modes of double-chains lead to a variety of ferroelectric and antiferroelectric phases in both the tetragonal and monoclinic cr…
Ferroelectric tunnel junctions (FTJs), which consist of two metal electrodes separated by a thin ferroelectric barrier, have recently aroused significant interest for technological applications as nanoscale resistive switching devices. So far, most of existing FTJs have been based on perovskite-oxide barrier layers. The recent discovery of the two-dimensional (2D) van der Waals ferroelectric materials opens a new route to realize tunnel junctions with new functionalities and nm-scale dimensions. Due to the weak coupling between the atomic layers in these materials, the relative dipole alignmen…
The switching behavior of antiferroelectric domain structures under the applied electric field is not fully understood. In this work, by using the phase field simulation, we have studied the polarization switching property of antiferroelectric domains. Our results indicate that the ferroelectric domains nucleate preferably at the boundaries of the antiferroelectric domains, and antiferroelectrics with larger initial domain sizes possess a higher coercive electric field as demonstrated by hysteresis loops. Moreover, we introduced charge defects into the sample and numerically investigated their…
Bulk chalcogenide perovskite BaZrS3 (BZS), with a direct band gap in visible region, is an important photovoltaic material, albeit with limited applicability owing to its antiferroelectric (AF) nature. Presently, ferroelectric (FE) perovskite-based photovoltaics are attracting enormous attention for environmental stability and better energy conversion efficiency through enhanced charge separation, owing to loss of center of inversion symmetry. We report on antiferroelectric-ferroelectric (AF-FE) phases of BZS thin film, grown with chemical vapor deposition (CVD), using temperature-dependent Ra…
Ferroic transition metal oxides, which exhibit spontaneous elastic, electrical, magnetic or toroidal order, exhibit functional properties that find use in ultrastable solid-state memories to sensors and medical imaging technologies. To realize multifunctional behavior, where one order parameter can be coupled to the conjugate field of another order parameter, however, requires a common microscopic origin for the long-range order. Here, we formulate a complete theory for a novel form of ferroelectricity, whereby a spontaneous and switchable polarization emerges from the destruction of an antife…
Materials undergoing antiferroelectric/ferroelectric (AFE/FE) transitions are studied for possible applications that exploit the large volume, charge and entropy differences between the two states, such as electrocaloric cooling, energy storage, electromechanical actuators. Though certain compositions of PZT codoped with La and Sn may withstand millions of electrically induced AFE/FE cycles, in other cases few thermally induced cycles and room temperature aging may cause noticeable changes in the material properties. This is particularly evident in the elastic moduli, which at room temperature…
Relaxation approach to quantum-mechanical modeling of ferroelectric and antiferroelectric phase transitions
University of South Florida（南佛罗里达大学）；Georgia Institute of Technology（佐治亚理工学院）；Trinity College Dublin（都柏林三一学院）；Centre for Research on Adaptive Nanostructures and Nanodevices (CRANN)（自适应纳米结构与纳米器件研究中心）；Queen’s University Belfast（贝尔法斯特女王大学）；Advanced Research Institute, Georgia Institute of Technology（佐治亚理工学院先进研究院）；G.W. Woodruff School of Mechanical Engineering, School of Materials Science and Engineering, Georgia Institute of Technology（佐治亚理工学院G.W.伍德鲁夫机械工程学院与材料科学与工程学院）
At variance with structural ferroic phase transitions which give rise to macroscopic tensors coupled to macroscopic fields, criteria defining antiferroelectric (AFE) phase transitions are still under discussion due to the absence of specific symmetry properties characterizing their existence. They are recognized by the proximity of a ferroelectric (FE) phase induced under applied electric field, with a double hysteresis loop relating the induced polarization to the electric field and a typical anomaly of the dielectric permittivity. Here, we show that there exist indeed symmetry criteria defin…
The polarization response of antiferroelectrics to electric fields is such that the materials can store large energy densities, which makes them promising candidates for energy storage applications in pulsed-power technologies. However, relatively few materials of this kind are known. Here we consider ferroelectric/paraelectric superlattices as artificial electrostatically-engineered antiferroelectrics. Specifically, using high-throughput second-principles calculations, we engineer PbTiO$_{3}$/SrTiO$_{3}$ superlattices to optimize their energy-storage performance at room temperature (to maximi…
The alkali-trihalogeno-germanates AGeX$_3$ with A a large single positive ion such as Rb, Cs, or organic radicals such as methyl ammonium (MA), and X a halogen (I, Br, Cl, F) along with the corresponding stannates (ASnX$_3$) and plumbates (APbX$_3$) exhibit a large variety of crystal structures, some of which are of the perovskite type. These materials, better known as "halide perovskites'' have recently gained worldwide attention as promising photovoltaic and more broadly opto-electronic materials. But their stability problems relative to the non-perovskite phases is a major issue. Here we sh…
This letter reports microwave dielectric measurements performed in the antiferroelectric phase of NaNbO3 ceramics from 100 to 450 K. Remarkable dielectric relaxations were found within the antiferroelectric phase and in the vicinity of ferroelectric-antiferroelectric phase transition. Such dielectric relaxation process was associated with relaxations of polar nanoregions with strong relaxor-like characteristic. In addition, the microwave dielectric measurements also revealed an unexpected and unusual anomaly in the relaxation strength, which was related to a disruption of the antiferroelectric…
Using the previously developed model we study the electrocaloric effect (ECE) in antiferroelectric crystals of squaric acid. At low temperatures, the polarization reorientation by the electric field applied along the crystallographic $a$ axis of these crystals is predicted to be a two-stage process, with one of the sublattice polarizations switched twice, by 90$^\circ$ each time. The $T$-$E$ landscapes of the model polarization and entropy are explored. The ECE, characterized by the introduced electric Grüneisen parameter, is found to be negative in the antiferroelectric phase. In the intermed…
A pseudospin model for description of the influence of the electric field, confined to the plane of sublattice polarization, on the two-dimensional squaric acid antiferroelectrics is developed. The system behavior is analyzed in terms of the parameters of ferroelectric and antiferroelectric ordering, as well as the non-collinearity angle $θ$, which is the angle between sublattice polarizations. The temperature-electric field $T-E_1$ phase diagram is constructed. Most of the field-induced transitions are found to be associated with polarization rotation. The observed phases include the collinea…
Using the previously developed model we explore the processes of polarization rotation in antiferroelectric crystals of squaric acid by the electric fields directed arbitrarily within the $ac$ plane. Except for some particular directions of the field, the two-step polarization reorientation at low temperatures is predicted: first, to the noncollinear phase with perpendicular sublattice polarizations and then to the collinear ferroelectric phase. However, when the field is directed along the axis of spontaneous sublattice polarizations, the intermediate noncollinear phase is absent; when the fi…
In the paper we consider size effects of phase transitions and polar properties of the thin antiferroelectric films. We modified phenomenological approach proposed by Kittel. The Euler-Lagrange equations were solved by direct variational method. The free energy with renormalized coefficients depending on the film thickness has been derived. The approximate analytical expression for the coefficients dependence on film thickness, temperature, polarization gradient coefficient and extrapolation lengths were obtained. We have shown how the anti-ferroelectric double hysteresis loop transforms into …
Discovery of a new weberite-type antiferroelectric: La3NbO7
Thayer School of Engineering, Dartmouth College（达特茅斯学院泰勒工程学院）；Department of Materials Science and Engineering, University of California, Berkeley（加州大学伯克利分校材料科学与工程系）；Rice Advanced Materials Institute, Rice University（莱斯大学先进材料研究所）；Department of Materials Science and NanoEngineering, Rice University（莱斯大学材料科学与纳米工程系）；Department of Physics, University of California, Berkeley（加州大学伯克利分校物理系）；Materials Sciences Division, Lawrence Berkeley National Laboratory（劳伦斯伯克利国家实验室材料科学部）；Kavli Energy Nanosciences Institute, University of California, Berkeley（加州大学伯克利分校卡弗里能源纳米科学研究所）；Molecular Foundry, Lawrence Berkeley National Laboratory（劳伦斯伯克利国家实验室分子工厂）
Crystalline materials with broken inversion symmetry can exhibit a spontaneous electric polarization, which originates from a microscopic electric dipole moment. Long-range polar or anti-polar order of such permanent dipoles gives rise to ferroelectricity or antiferroelectricity, respectively. However, the recently discovered antiferroelectrics of fluorite structure (HfO$_2$ and ZrO$_2$) are different: A non-polar phase transforms into a polar phase by spontaneous inversion symmetry breaking upon the application of an electric field. Here, we show that this structural transition in antiferroel…
We propose an order-disorder type microscopic model for BaTiO$_3$-like Ferroelectric Substance. Our model has three phase transitions and four phases. The symmetry and directions of the polarizations of the ordered phases agree with the experimental results of BaTiO$_3$. The intermediate phases in our model are known as an incompletely ordered phase, which appears in a generalized clock model.
The physical nature of the ferroelectric (FE), ferrielectric (FEI) and antiferroelectric (AFE) phases, their coexistence and spatial distributions underpin the functionality of antiferrodistortive (AFD) multiferroics in the vicinity of morphotropic phase transitions. Using Landau-Ginzburg-Devonshire (LGD) phenomenology and a semi-microscopic four sublattice model (FSM), we explore the behavior of different AFE, FEI and FE long-range orderings and their coexistence at the morphotropic phase boundaries in FE-AFE-AFD multiferroics. These theoretical predictions are compared with the experimental …
Density functional calculations are performed to investigate the experimentally-reported field-induced phase transition in thin-film ZrO2 (J. Muller et al., Nano. Lett. 12, 4318). We find a small energy difference of ~ 1 meV/f.u. between the nonpolar tetragonal and polar orthorhombic structures, characteristic of antiferroelectricity. The requisite first-order transition between the two phases, which atypically for antiferroelectrics have a group-subgroup relation, results from coupling to other zone-boundary modes, as we show with a Landau-Devonshire model. Tetragonal ZrO2 is thus established…
Ferroelectric tungsten-based Aurivillius oxides are naturally stable superlattice structures, in which A-site deficient perovskite blocks [WnO3n+1]-2 (n = 1, 2, 3, ...) interleave with fluorite-like bismuth oxide layers [Bi2O2]+2 along the c -axis. In the n = 2 Bi2W2O9 phase, an in-plane antipolar distortion dominates but there has been controversy as to the ground state symmetry. Here we show, using a combination of first-principles density functional theory calculations and experiments, that the ground state is a non-polar phase of Pnab symmetry. We explore the energetics of metastable phase…
We report ferrielectricity in a single-phase crystal, TSCC -- tris-sarcosine calcium chloride [(CH3NHCH2COOH)3CaCl2]. Ferrielectricity is well known in smectic liquid crystals but almost unknown in true crystalline solids. Pulvari reported it in 1960 in mixtures of ferroelectrics and antiferroelectrics, but only at high fields. TSCC exhibits a second-order displacive phase transition near Tc = 130 K that can be lowered to a Quantum Critical Point at zero Kelvin via Br- or I-substitution, and phases predicted to be antiferroelectric at high pressure and low temperatures. Unusually, the size of …
