The switching dynamics of ferroelectric materials is a crucial intrinsic property which directly affects the operation and performance of ferroelectric devices. In conventional ferroelectric materials, the typical ferroelectric switching mechanism is governed by a universal process of domain wall motion. However, recent experiments indicate that Van der Waals ferroelectric CuInP2S6 possesses anomalous polarization switching dynamics under an electric field. It is important to understand the switching dynamics, but it remains theoretically unexplored in CuInP2S6 due to the lack of description of its order-disorder phase transition characteristics by density functional theory. Here, we employ a machine-learning potential trained from the first principles density functional theory dataset to conduct the large-scale atomistic simulations of temperature-driven order-disorder ferroelectric phase transition in CuInP2S6. Most importantly, it is found that the electric field-driven polarization switching in CuInP2S6 is mediated by single Cu dipole flip, rather than conventional domain wall motion mechanism. This intrinsic unconventional switching behavior can be attributed to the competition between the energy barrier of domain wall motion and single dipole flip.
By means of magnetic, specific heat and pyroelectric measurements, we report on magnetic ferroelectricity in the quadruple perovskite \namno, characterized by a canted antiferromagnetic (AFM) CE structure. Surprisingly, ferroelectricity is concomitant to a dramatic broadening of the magnetic hysteresis loop, well below the AFM ordering temperature. This unconventional behavior shows that the formation of ferroelectric domains is induced by the symmetric exchange interaction in the local scale, e.g. at magnetic domain boundaries or defects. The value of electric polarization, $P = 0.027 μ$C cm$…
Deterministic polarization reversal in ferroelectric and multiferroic films is critical for their exploitation in nanoelectronic devices. While ferroelectricity has been studied for nearly a century, major discrepancies in the reported values of coercive fields and saturation polarization persist in literature for many materials. This raises questions about the atomic-scale mechanisms behind polarization reversal. Unconventional ferroelectric switching in $ε$-Fe2O3 films, a material that combines ferrimagnetism and ferroelectricity at room temperature, is reported here. High-resolution in-situ…
Integration of ferroelectric materials into novel technological applications requires low coercive field materials, and consequently, design strategies to reduce the ferroelectric switching barriers. In this first principles study, we show that biaxial strain, which has a strong effect on the ferroelectric ground states, can also be used to tune the switching barrier of hybrid improper ferroelectric Ruddlesden-Popper oxides. We identify the region of the strain -- tolerance factor phase diagram where this intrinsic barrier is suppressed, and show that it can be explained in relation to strain …
The improper ferroelectricity in YMnO$_3$ and other related multiferroic hexagonal manganites are known to cause topologically protected ferroelectric domains that give rise to rich and diverse physical phenomena. The local structure and structural coherence across the ferroelectric transition, however, were previously not well understood. Here we reveal the evolution of the local structure with temperature in YMnO$_3$ using neutron total scattering techniques, and interpret them with the help of first-principles calculations. The results show that, at room temperature, the local and average s…
The recently discovered ferroelectricity of van der Waals bilayers offers an unconventional route to improve the performance of devices. Key parameters such as switching field and speed depend on the static and dynamic properties of domain walls (DWs). Here we theoretically explore the properties of textures in stacking-engineered ferroelectrics from first principles. Employing a machine-learning potential model, we present results of large-scale atomistic simulations of stacking DWs and Moiré structure of boron nitride bilayers. We predict that the competition between the switching barrier of…
Understanding the polarization switching mechanisms at play in ferroelectric materials is crucial for their exploitation in electronic devices. The conventional centrosymmetric reference structure-based mechanism which accounts for ferroelectricity in most of the usual displacive ferroelectric materials is too energy-demanding for some newly diagnosed ferroelectric materials such as the Ga2-xFexO3 (0.8 < x < 1.4) compounds. Some alternative theoretical propositions have been made and need experimental confirmation. A dual-scale electron microscopy study is performed on thin films of the Ga0.6F…
Field-induced switching of ferroelectric domains with a topological vortex configuration is studied by atomic imaging and electrical biasing in an electron microscope, revealing the role of topological defects on the topologically-guided change of domain-wall pairs in a hexagonal manganite.
We carry out first-principles density-functional-theory calculations to elucidate the polarization switching mechanism in charge-ordering-induced ferroelectrics based on the prototypical case of the (SrVO$_3$)$_1$(LaVO$_3$)$_1$ superlattice. We find that lattice relaxation for a specific charge ordering state can "lock" that state in, making non-adiabatic switching to a different CO variant energetically prohibitive, and in some cases, even making the energy barrier for adiabatic switching prohibitively large. We classify charge-ordering materials into two types, polyhedral breathing and off-c…
Ferroelectric switching at edge dislocations in BaTiO$_3$ modelled at the atomic scale
Interdisciplinary Centre for Advanced Materials Simulation (ICAMS), Ruhr-University Bochum（波鸿鲁尔大学先进材料模拟跨学科中心）；Center for Interface-Dominated High Performance Materials (ZGH), Ruhr-University Bochum（波鸿鲁尔大学界面主导高性能材料中心）；Faculty of Physics and Astronomy, Ruhr-University Bochum（波鸿鲁尔大学物理与天文学系）；Univ. Lille, CNRS, INRAE, Centrale Lille, UMR 8207 - UMET - Unité Matériaux et Transformations（里尔大学、法国国家科学研究中心、法国国家农业食品与环境研究院、里尔中央理工学院、UMR 8207 材料与转化单元）
We have proposed the phenomenological description of polarization switching peculiarities in ferroelectric semiconductors with charged defects and prevailing extrinsic conductivity. Exactly we have modified Landau-Ginsburg approach shown that the macroscopic state of the aforementioned inhomogeneous system can be described by three coupled equations for three order parameters. Both the experimentally observed coercive field values well below the thermodynamic one and the various hysteresis loop deformations (minor, constricted and double loops) have been obtained in the framework of our model.…
Decoupling effects of the resistive-switching behavior on the polarization reversal in ultrathin ferroelectric Hf0.5Zr0.5O2 films
Harbin Institute of Technology, Shenzhen（哈尔滨工业大学（深圳））；Quantum Science Center of Guangdong-Hong Kong-Macao Greater Bay Area（粤港澳大湾区量子科学中心）；Westlake University（西湖大学）；Indian Institute of Science（印度科学学院）；University of Science and Technology Beijing（北京科技大学）
Pressure-induced polarization switching in ferroelectric thin films has emerged as a powerful method for domain patterning, allowing to create predefined domain patterns on free surfaces and under thin conductive top electrodes. However, the mechanisms for pressure induced polarization switching in ferroelectrics remain highly controversial, with flexoelectricity, polarization rotation and suppression, and bulk and surface electrochemical processes all being potentially relevant. Here we classify possible pressure induced switching mechanisms, perform elementary estimates, and study in depth u…
We propose a tunneling heterostructure by replacing one of the metal electrodes in a metal/ferroelectric/metal ferroelectric tunnel junction with a heavily doped semiconductor. In this metal/ferroelectric/semiconductor tunnel diode, both the height and the width of the tunneling barrier can be electrically modulated due to the ferroelectric field effect, leading to a colossal tunneling electroresistance. This idea is implemented in Pt/BaTiO3/Nb:SrTiO3 heterostructures, in which an ON/OFF conductance ratio above 10$^4$ can be readily achieved at room temperature. The colossal tunneling electror…
A stochastic model for polarization switching in tetragonal ferroelectric ceramics is introduced, which includes sequential 90°- and parallel 180°-switching processes and accounts for the dispersion of characteristic switching times due to a nonuniform spatial distribution of the applied field. It presents merging of the recent multistep stochastic mechanism (MSM) with the earlier nucleation limited switching (NLS) and inhomogeneous field mechanism (IFM) models. The new model provides a much better description of simultaneous polarization and strain responses over a wide time window and a deep…
Hafnium dioxide (HfO2) is a promising ferroelectric (FE) material for achieving high-density nonvolatile memory and neuromorphic computing, due to its compatibility with the mainstream integrated circuit technology and the surprisingly enhanced ferroelectricity by reduced thickness. The FE switching dynamics is essential to the device performance, but the complexity of HfO2 atomic structure causes unknown of various FE switching paths and domain wall configurations. Here, we demonstrate that its low-barrier paths and domain walls can be comprehensively found and understood from a perspective o…
The elastic response of BaTiO$_3$ single crystals during electric field cycling at room temperature has been studied using in-situ Resonant Ultrasound Spectroscopy (RUS), which allows monitoring of both the elastic and anelastic changes caused by ferroelectric polarization switching. We find that the first ferroelectric switching of a virgin single crystal is dominated by ferroelastic 90° switching. In subsequent ferroelectric switching, ferroelastic switching is reduced by domain pinning and by the predominance of 180° ferroelectric domains, as confirmed by polarized light microscopy. RUS und…
The temperature evolution of the crystal and magnetic structures of ferroelectric sulfide AgCrS2 have been investigated by means of neutron scattering. AgCrS2 undergoes at TN = 41.6 K a first-order phase transition, from a paramagnetic rhombohedral R3m to an antiferromagnetic monoclinic structure with a polar Cm space group. In addition to being ferroelectric below TN, the low temperature phase of AgCrS2 exhibits an unconventional collinear magnetic structure that can be described as double ferromagnetic stripes coupled antiferromagnetically, with the magnetic moment of Cr+3 oriented along b w…
General energy approaches have been applied to study the single-domain polarization reversal induced by the voltage-modulated Atomic Force Microscopy (AFM) in ferroelectric single crystals and thin films. Topographic analysis of energy surfaces in the subspace of domain dimensions is performed, and energy evolutions under an external bias are elucidated. This has let to successfully describe all stages of the AFM switching, including formations of a reversed domain, its growth in a bulk, domain contact instabilities near an electrode, and pure sidewise expansions in a film.
We classify the switching kinetics of ferroelectrics including both epitaxial/polycrystalline thin films and single-crystalline/ceramic bulks at various applied fields into four categories, depending on whether the depolarization field and/or the polarization reversal induced by the switching promotion effect between adjacent parts can be neglected. We show that our statistical model developed very recently [Journal of Physics: Condensed Matter 21, 012207 (2009)] in its generalized form applies to all these four categories. Finally we make the comparison between our model and the conventional …
Ferroelectric polarization switching is one common example of a process that occurs via nucleation and growth, and understanding switching kinetics is crucial for applications such as ferroelectric memory. Here we describe and interpret anomalous switching dynamics in the wurtzite nitride thin film ferroelectrics Al0.7Sc0.3N and Al0.94B0.06N using a general model that can be directly applied to other abrupt transitions that proceed via nucleation and growth. When substantial growth and impingement occur while nucleation rate is increasing, such as in these wurtzite ferroelectrics under high el…
Hybrid improper ferroelectricity, where an electrical polarization can be induced via a trilinear coupling to two non-polar structural distortions of different symmetry, has recently been experimentally demonstrated for the first time in the $n$=2 Ruddlesden-Popper compound Ca$_3$Ti$_2$O$_7$. In this paper we use group theoretic methods and first-principles calculations to identify possible ferroelectric switching pathways in Ca$_3$Ti$_2$O$_7$. We identify low-energy paths that reverse the polarization direction by switching via an orthorhombic twin domain, or via an antipolar structure. We al…
Statistical distribution of switching times is a key information necessary to describe the dynamic response of a polycrystalline bulk ferroelectric to an applied electric field. The Inhomogeneous Field Mechanism (IFM) model offers a useful tool which allows extraction of this information from polarization switching measurements over a large time window. In this paper, the model was further developed to account for the presence of non-switchable regions in fatigued materials. Application of the IFM- analysis to bipolar electric cycling induced fatigue process of various lead-based and lead-free…
We describe ferroelectric thin films with circular electrodes and develop a thermodynamic theory that explains previously mysterious experiments. It is found to be especially useful for restricted geometries such as microstructures for which boundary conditions are well known to play an important role in ferroelectric properties. We have explored a new switching mechanism, which consists of an inhomogeneous rotational motion of the polarization and leads to an extended vortex state. The vortex appearance exhibits characteristic properties of a first-order field-induced phase transition: three …
We investigate theoretically the polarization switching kinetics in ferroelectric thin films. In such substances, the domain walls are pinned by (usually dipole) defects, which are present also in ordered samples as technologically unavoidable impurities. This random interaction with dipole pinning centers results, in particular, in exponentially broad distribution of switching times. Under supposition of low pinning centers concentration, we derive the distribution function of switching times showing that it is not simply Lorentzian (as it was first suggested by Tagantsev et al [\prb, {\bf 66…
Piezoresponse Force Spectroscopy (PFS) is a powerful method widely used for measuring the nanoscale ferroelectric responses of the materials. However, it is found that certain non-ferroelectric materials can also generate similar responses from the PFS measurements due to many other factors, hence, it is believed that PFS alone is not sufficient to differentiate the ferroelectric and non-ferroelectric materials. On the other hands, this work shows that there are distinct differences in contact resonance frequency variation during the PFS measurements for ferroelectric and non-ferroelectric mat…
Ferroelectrics are multifunctional smart materials finding applications in sensor technology, micromechanical actuation, digital information storage etc. Their most fundamental property is the ability of polarization switching under applied electric field. In particular, understanding of switching kinetics is essential for digital information storage. In this regard, scaling properties of the temporal polarization response are well-known for 180°-switching processes in ferroelectrics characterized by a unique field-dependent local switching time. Unexpectedly, these properties were now observe…
Using metal-ferroelectric junctions as switchable diodes was proposed several decades ago. This was shown to actually work in PbZr(1-x)TixO3 (PZT) by Blom et al. [P.W. M. Blom et al., Phys. Rev. Lett. 73, 2107 (1994)], who reported switching in the rectification direction and changes of the current of about 2 orders of magnitude upon switching the polarization direction of the ferroelectric layer. This form of resistive switching enables the read out of a ferroelectric memory state at higher speed compared to the capacitive design, without destroying the information in each reading cycle. Rece…
The switching of electric polarization induced by electric fields -a fundamental functionality of ferroelectrics- is closely associated with the motions of the domain walls that separate regions with distinct polarization directions. Therefore, understanding domain-walls dynamics is of essential importance for advancing ferroelectric applications. In this Letter, we show that the topology of the multidomain structure can have an intrinsic impact on the degree of switchable polarization. Using a combination of polarization hysteresis measurements and piezoresponse force microscopy on a uniaxial…
Monitoring structural changes in ferroelectric thin films during electric field-induced polarization switching is important for a full microscopic understanding of the coupled motion of charges, atoms and domain walls. We combine standard ferroelectric test-cycles with time-resolved x-ray diffraction to investigate the response of a nanoscale ferroelectric oxide capacitor upon charging, discharging and switching. Piezoelectric strain develops during the electronic RC time constant and additionally during structural domain-wall creep. The complex atomic motion during ferroelectric polarization …
Investigating the Electromechanical Behavior of Unconventionally Ferroelectric $Hf_{0.5}Zr_{0.5}O_{2}$-based Capacitors Through Operando Nanobeam X-ray Diffraction
A stochastic model of electric field-driven polarization reversal in orthorhombic ferroelectrics is advanced, providing a description of their temporal electromechanical response. The theory accounts for all possible parallel and sequential switching events. Application of the model to the simultaneous measurements of polarization and strain kinetics in a lead-free orthorhombic (K,Na)NbO3-based ferroelectric ceramic over a wide timescale of 7 orders of magnitude allowed identification of preferable polarization switching paths, fractions of individual switching processes, and their activation …
Cross-coupling of ordering parameters in multiferroic materials by multiple external stimuli other than electric field and magnetic field is highly desirable from both practical application and fundamental study points of view. Recently, mechanical force has attracted great attention in switching of ferroic ordering parameters via electro-elastic coupling in ferroelectric materials. In this work, mechanical force induced polarization and magnetization switching were investigated in a polycrystalline multiferroic Bi0.9La0.1FeO3 thin film using a scanning probe microscopy system. The piezorespon…
Ferroelectric nanostructures can be formed by local switching of domains using techniques such as piezo-force microscopy (PFM). Understanding lateral size effects is important to determine the minimum feature size for writing ferroelectric nanostructures. To understand these lateral size effects, we use the time-dependent-Ginzburg-Landau equations to simulate localized switching of domains for a PFM type and parallel-plate capacitor configurations. Our investigations indicate that fringing electric fields lead to switching via 90 deg domain wedge nucleation for thicker films while at smaller t…
Consecutive stochastic 90° polarization switching events, clearly resolved in recent experiments, are described by a new nucleation and growth multi-step model. It extends the classical Kolmogorov-Avrami-Ishibashi approach and includes possible consecutive 90°- and parallel 180°-switching events. The model predicts the results of simultaneous time-resolved macroscopic measurements of polarization and strain, performed on a tetragonal Pb(Zr,Ti)O3 ceramic in a wide range of electric fields over a time domain of five orders of the magnitude. It allows the determination of the fractions of individ…
Domain-Wall Mediated Polarization Switching in Ferroelectric AlScN: Strain Relief and Field-Dependent Dynamics
Jilin University（吉林大学）；University of Arkansas（阿肯色大学）；Guangdong Technion – Israel Institute of Technology（广东以色列理工学院）；Technion – Israel Institute of Technology（以色列理工学院）
研究铁电AlScN中极化开关机制，发现域壁通过缓解应变导致场依赖的开关动力学，提出通过域工程调控 coercive field 的策略。
Phase-field simulation (PFS) have revolutionized the understanding of domain structure and switching behavior in ferroelectric thin films and ceramics. Generally, PFS is based on solution of a (set) of Ginzburg-Landau equations for a defined order parameter field(s) under physical boundary conditions (BCs) of fixed potential or charge. While well-matched to the interfaces in bulk materials and devices, these BCs are generally not applicable to free ferroelectric surfaces. Here, we developed a self-consistent phase-field model with boundary conditions based on electrochemical equilibria. We cho…
The comparative experimental analysis of polarization reversal kinetics in conventional homogeneous triglycine sulfate ((NH_{2}CH_{2}COOH)_{3} \cdot H_{2}SO_{4}; TGS) and relaxor strontium barium niobate (Sr_{0.61}Ba_{0.39}Nb_{2}O_{6}; SBN) crystals have been performed in a broad range of measurement conditions. The experimental data have been collected from microscopic observation of the domain structure, switching current and D-E hysteresis loop registration. The hysteresis loop and dielectric spectra have a strong link to the configuration of ferroelectric microdomains. The domain structure…
Switching kinetics in ultrathin epitaxial BaTiO3 films confirms the existence of the homogeneous switching (without domains) in ultrathin ferroelectric films. We suppose that the homogeneous switching in ultrathin films is a common phenomenon for all ferroelectric materials.
We use molecular dynamics simulations to understand the mechanisms of polarization switching in ferroelectric BaTiO$_3$ achieved with external electric field. For tetragonal and orthorhombic ferroelectric phases, we determine the switching paths, and show that polarization rotation through intermediate monoclinic phases (a) facilitates switching at low fields (b) is responsible for a sharp anisotropy in polarization switching. We develop understanding of this through determination of detailed electric field-temperature phase diagrams, that are fundamental to technological applications based on…
Ferroelectric hafnium zirconium oxide (HZO) thin films show significant promise for applications in ferroelectric random-access memory, ferroelectric field-effect transistors, and ferroelectric tunneling junctions. However, there are shortcomings in understanding ferroelectric switching, which is crucial in the operation of these devices. Here a computational model based on phase field method is developed to simulate the switching behavior of polycrystalline HZO thin films. Furthermore, we introduce a novel approach to optimize the effective Landau coefficients describing the free energy of HZ…
