Class Of Ferroelectrics Research Articles

Superfine Nanodomain Engineering Unleashing Ferroelectricity in Incipient Ferroelectrics.

Incipient ferroelectrics have emerged as an attractive class of functional materials owing to their potential to be engineered for exotic ferroelectric behavior, holding great promise for expanding the ferroelectric family. However, thus far, their artificially engineered ferroelectricity has fallen far short of rivaling classic ferroelectrics. In this study, we address this challenge by developing a superfine nanodomain engineering strategy. By applying this approach to representative incipient ferroelectric of SrTiO3-based films, we achieve unprecedentedly strong ferroelectricity, not only surpassing previous records for incipient ferroelectrics but also being comparable to classic ferroelectrics. The remanent polarization of the thin film reaches up to 17.0 μC cm-2 with an ultrahigh Curie temperature of 973 K. Atomic-scale investigations elucidate the origin of this robust ferroelectricity in the emergent high-density superfine nanodomains spanning merely 3-10 unit cells. Combining experimental results with theoretical assessments, we unveil the underlying mechanism, where the intentionally introduced diluted foreign Fe element creates a deeper Landau energy well and promotes a short-range ordering of polarization. Our developed strategy significantly streamlines the design of unconventional ferroelectrics, providing a versatile pathway for exploring new and superior ferroelectric materials.

Field-Induced Antiferroelectric-Ferroelectric Transformation in Organometallic Perovskite Displaying Giant Negative Electrocaloric Effect.

Antiferroelectric materials with an electrocaloric effect (ECE) have been developed as promising candidates for solid-state refrigeration. Despite the great advances in positive ECE, reports on negative ECE remain quite scarce because of its elusive physical mechanism. Here, a giant negative ECE (maximum ΔS ∼ -33.3 J kg-1 K-1 with ΔT ∼ -11.7 K) is demonstrated near room temperature in organometallic perovskite, iBA2EA2Pb3I10 (1, where iBA = isobutylammonium and EA = ethylammonium), which is comparable to the greatest ECE effects reported so far. Moreover, the ECE efficiency ΔS/ΔE (∼1.85 J cm kg-1 K-1 kV-1) and ΔT/ΔE (∼0.65 K cm kV-1) are almost 2 orders of magnitude higher than those of classical inorganic ceramic ferroelectrics and organic polymers, such as BaTiO3, SrBi2Ta2O9, Hf1/2Zr1/2O2, and P(VDF-TrFE). As far as we know, this is the first report on negative ECE in organometallic hybrid perovskite ferroelectric. Our experimental measurement combined with the first-principles calculations reveals that electric field-induced antipolar to polar structural transformation results in a large change in dipolar ordering (from 6.5 to 45 μC/cm2 under the ΔE of 18 kV/cm) that is closely related to the entropy change, which plays a key role in generating such giant negative ECE. This discovery of field-induced negative ECE is unprecedented in organometallic perovskite, which sheds light on the exploration of next-generation refrigeration devices with high cooling efficiency.

Thermally Induced Pulsed Processes in Strontium Barium Niobate Single Crystals

A brief analytical review of the literature data on the jump switching processes in classical ferroelectrics and new results of the experimental study of the thermally induced pulsed processes in the strontium barium niobate relaxor ferroelectric crystals are presented. The mechanisms of their occurrence in different temperature ranges are discussed based on the data of spectral analysis of the parameters of pulsed processes.

Near-electrode effects of ferroelectric nanocomposites filled with pristine and oxidized multiwalled carbon nanotubes at low frequencies

To fill a gap of previous studies, the present work considers possible effects near electrodes for nanocomposites based on classical ferroelectrics (triglycine sulfate and potassium dihydrogen phosphate) filled with pristine and oxidized multiwalled carbon nanotubes by analyzing the spectra of electric impedance at low frequencies (10−3–106 Hz). FTIR technique was utilized to explore composite structures. The results indicated that using the oxidized carbon nanotubes helped to partially suppress the near-electrode effects due to the poor electrical conductivity of OH groups appeared after oxidization. Besides, the frequency region in which the effects existed was expanded with increasing the filler content.

Confinement-Driven Inverse Domain Scaling in Polycrystalline ErMnO3.

The research on topological phenomena in ferroelectric materials has revolutionized the way people understand polar order. Intriguing examples are polar skyrmions, vortex/anti-vortex structures, and ferroelectric incommensurabilties, which promote emergent physical properties ranging from electric-field-controllable chirality to negative capacitance effects. Here, the impact of topologically protected vortices on the domain formation in improper ferroelectric ErMnO3 polycrystals is studied, demonstrating inverted domain scaling behavior compared to classical ferroelectrics. It is observed that as the grain size increases, smaller domains are formed. Phase field simulations reveal that elastic strain fields drive the annihilation of vortex/anti-vortex pairs within the grains and individual vortices at the grain boundaries. The inversion of the domain scaling behavior has far-reaching implications, providing fundamentally new opportunities for topology-based domain engineering and the tuning of the electromechanical and dielectric performance of ferroelectrics in general.

A Landau–Devonshire analysis of strain effects on ferroelectric Al1−xScxN

We present a thermodynamic analysis of the recently discovered nitride ferroelectric materials using the classic Landau–Devonshire approach. Electrostrictive and dielectric stiffness coefficients of Al1−xScxN with a wurtzite structure (6 mm) are determined using a free energy density function assuming a hexagonal parent phase (6/mmm), with the first-order phase transition based on the dielectric stiffness relationships. The results of this analysis show that the strain sensitivity of the energy barrier is one order of magnitude larger than that of the spontaneous polarization in these wurtzite ferroelectrics, yet both are less sensitive to strain compared to classic perovskite ferroelectrics. These analysis results reported here explain experimentally reported sensitivity of the coercive field to elastic strain/stress in Al1−xScxN films and would enable further thermodynamic analysis via phase field simulation and related methods.

Differences of the temperatures of ferroelectric and magnetic phase transitions of perovskites

Binary and ternary AB′0.5 B″0.5O3 oxides with a complex perovskite structure, possessing the consecutive ferroelectric or antiferroelectric phase transitions at T C and ferromagnetic, antiferromagnetic, or ferrimagnetic phase transitions at T N, are considered together with classical ferroelectrics and antiferroelectrics. The common correlations between these temperatures, their differences T С-T N and interatomic bond A-O (δ AO) or B-O (δ BO) strains are revealed. Some common correlations between their temperatures T С, T N, T С-T N differences, and δ AO or δ BO are revealed. It is established that these differences for multiferroics are in common dependences with classical ferroelectrics and antiferroelectrics.

Nanoscale Doping and Its Impact on the Ferroelectric and Piezoelectric Properties of Hf0.5Zr0.5O2.

Ferroelectric hafnium oxide thin films—the most promising materials in microelectronics’ non-volatile memory—exhibit both unconventional ferroelectricity and unconventional piezoelectricity. Their exact origin remains controversial, and the relationship between ferroelectric and piezoelectric properties remains unclear. We introduce a new method to investigate this issue, which consists in a local controlled modification of the ferroelectric and piezoelectric properties within a single Hf0.5Zr0.5O2 capacitor device through local doping and a further comparative nanoscopic analysis of the modified regions. By comparing the ferroelectric properties of Ga-doped Hf0.5Zr0.5O2 thin films with the results of piezoresponse force microscopy and their simulation, as well as with the results of in situ synchrotron X-ray microdiffractometry, we demonstrate that, depending on the doping concentration, ferroelectric Hf0.5Zr0.5O2 has either a negative or a positive longitudinal piezoelectric coefficient, and its maximal value is −0.3 pm/V. This is several hundreds or thousands of times less than those of classical ferroelectrics. These changes in piezoelectric properties are accompanied by either improved or decreased remnant polarization, as well as partial or complete domain switching. We conclude that various ferroelectric and piezoelectric properties, and the relationships between them, can be designed for Hf0.5Zr0.5O2 via oxygen vacancies and mechanical-strain engineering, e.g., by doping ferroelectric films.

An Epitaxial Ferroelectric ScAlN/GaN Heterostructure Memory

AbstractElectrically switchable bistable conductance that occurs in ferroelectric materials has attracted growing interest due to its promising applications in data storage and in‐memory computing. Sc‐alloyed III‐nitrides have emerged as a new class of ferroelectrics, which not only enable seamless integration with III‐nitride technology but also provide an alternative solution for CMOS back end of line integration. In this paper, the resistive switching behavior and memory effect in an ultrawide‐bandgap, high Curie temperature, fully epitaxial ferroelectric ScAlN/GaN heterostructure is reported for the first time. The structure exhibits robust ON and OFF states that last for months at room temperature with rectifying ratios of 60–210, and further shows stable operation at high temperatures (≈670 K) that are close to or even above the Curie temperature of most conventional ferroelectrics. Detailed studies suggest that the underlying mechanism is directly related to a ferroelectric field effect induced charge reconstruction at the hetero‐interface. The robust resistive switching landscape and the electrical polarization engineering capability in the polar heterostructure, together with the promise to integrate with both silicon and GaN technologies, can pave the way for next‐generation memristors and further enable a broad range of multifunctional and cross‐field applications.

Growth of tungsten bronze phase out of niobate perovskite phase for opto‐ferroelectric applications

AbstractEngineering the optical bandgaps of classic ferroelectrics from the typical ultraviolet range down to the visible range is an emerging methodology of developing the next‐generation optoelectric and opto‐ferroelectric devices including ferroelectric solar cells, light‐driven transistors and modulators, and multi‐sensors/energy harvesters. Recently, a material interface comprised of a pseudo‐morphotropic phase boundary between the tungsten bronze and perovskite phases of the KNBNNO [(K,Na,Ba)x(Ni,Nb)yOz] has been reported to be an effective approach for bandgap engineering while retaining excellent ferroelectricity and piezoelectricity of the perovskite‐phased KNBNNO. However, this approach requires the compositions of the materials to be determined at the synthesis stage, leaving little room for any further modification of the microstructure and functional properties at the post‐processing stage. This paper presents a post‐processing method, that is, atmospheric annealing in N2 and O2, to grow the necessary tungsten bronze phase out of the perovskite phase in the KNBNNO. This method is advantageous over the previously reported because it enables to grow the tungsten bronze–perovskite interface region independent of the initial composition. The distinctive electrical properties and the giant tunability of photoconductivity of the tungsten bronze phase, the perovskite phase, and the interface are characterized in detail in this paper, supporting the exploitation of fabricating opto‐ferroelectric devices using the reported method which is compatible and comparable with some of the post‐processing methods applied in the silicon industry.

A Predictive Theory for Domain Walls in Oxide Ferroelectrics Based on Interatomic Interactions and its Implications for Collective Material Properties.

Domain walls separating regions of ferroelectric material with polarization oriented in different directions are crucial for applications of ferroelectrics. Rational design of ferroelectric materials requires the development of a theory describing how compositional and environmental changes affect domain walls. To model domain wall systems, a discrete microscopic Landau-Ginzburg-Devonshire (dmLGD) approach with A- and B-site cation displacements serving as order parameters is developed. Application of dmLGD to the classic BaTiO3 , KNbO3, and PbTiO3 ferroelectrics shows that A-B cation repulsion is the key interaction that couples the polarization in neighboring unit cells of the material. dmLGD decomposition of the total energy of the system into the contributions of the individual cations and their interactions enables the prediction of different properties for a wide range of ferroelectric perovskites based on the results obtained for BaTiO3 , KNbO3, and PbTiO3 only. It is found that the information necessary to estimate the structure and energy of domain-wall "defects" can be extracted from single-domain 5-atom first-principles calculations, and that "defect-like" domain walls offer a simple model system that sheds light on the relative stabilities of the ferroelectric, antiferroelectric, and paraelectric bulk phases. The dmLGD approach provides a general theoretical framework for understanding and designing ferroelectric perovskite oxides.

Piezoelectricity in hafnia

Because of its compatibility with semiconductor-based technologies, hafnia (HfO2) is today’s most promising ferroelectric material for applications in electronics. Yet, knowledge on the ferroic and electromechanical response properties of this all-important compound is still lacking. Interestingly, HfO2 has recently been predicted to display a negative longitudinal piezoelectric effect, which sets it apart from classic ferroelectrics (e.g., perovskite oxides like PbTiO3) and is reminiscent of the behavior of some organic compounds. The present work corroborates this behavior, by first-principles calculations and an experimental investigation of HfO2 thin films using piezoresponse force microscopy. Further, the simulations show how the chemical coordination of the active oxygen atoms is responsible for the negative longitudinal piezoelectric effect. Building on these insights, it is predicted that, by controlling the environment of such active oxygens (e.g., by means of an epitaxial strain), it is possible to change the sign of the piezoelectric response of the material.

Theory and application of the vector pair correlation function for real-space crystallographic analysis of order/disorder correlations from STEM images

Deviations of local structure and chemistry from the average crystalline unit cell are increasingly recognized to have a significant influence on the properties of many technologically important materials. Here, we present the vector pair correlation function (vPCF) as a new real-space crystallographic analysis method, which can be applied to atomic-resolution scanning transmission electron microscopy (STEM) images to quantify and analyze structural order/disorder correlations. Our STEM-based vPCFs have several advantages over radial PCFs and/or 3D pair distribution functions from x-ray total scattering: vPCFs explicitly retain crystallographic orientation information, are spatially resolved, can be applied directly on a sublattice basis, and are suitable for any material that can be imaged with STEM. To show the utility of our approach, we measure partial vPCFs in Ba5SmSn3Nb7O30 (BSSN), a tetragonal tungsten bronze (TTB) structured complex oxide. Many TTBs are known to be classical or relaxor ferroelectrics, and these properties have been correlated with the presence of superlattice ordering. BSSN, specifically, exhibits relaxor behavior and an incommensurate structural modulation. From the vPCF data, we observe that, of the cation sites, only the Ba (A2) sublattice is structurally modulated. We then infer the local modulation vector and reveal a marked anisotropy in its correlation length. Finally, short-range correlated polar displacements on the B2 cation sites are observed. This work introduces the vPCF as a powerful real-space crystallography technique, which enables direct, robust quantification of short-to-long range order on a sublattice-specific basis and is applicable to a wide range of complex material types.

Features of the Structure and Electrophysical Properties of Solid Solutions of the System (1-x-y) NaNbO3-xKNbO3-yCd0.5NbO3.

Ferroelectric ceramic materials based on the (1-x-y) NaNbO3-xKNbO3-yCd0.5NbO3 system (x = 0.05–0.65, y = 0.025–0.30, Δx = 0.05) were obtained by a two-stage solid-phase synthesis followed by sintering using conventional ceramic technology. It was found that the region of pure solid solutions extends to x = 0.70 at y = 0.05 and, with increasing y, it narrows down to x ≤ 0.10 at y = 0.25. Going out beyond the specified concentrations leads to the formation of a heterogeneous region. It is shown that the grain landscape of all studied ceramics is formed during recrystallization sintering in the presence of a liquid phase, the source of which is unreacted components (Na2CO3 with Tmelt. = 1126 K, K2CO3 with Tmelt. = 1164 K, KOH with Tmelt. = 677 K) and low-melting eutectics in niobate mixtures (NaNbO3, Tmelt. = 1260 K, KNbO3, Tmelt. = 1118 K). A study of the electrophysical properties at room temperature showed the nonmonotonic behavior of all dependences with extrema near symmetry transitions, which corresponds to the logic of changes in the electrophysical parameters in systems with morphotropic phase boundaries. An analysis of the evolution of dielectric spectra made it possible to distinguish three groups of solid solutions: classical ferroelectrics (y = 0.05–0.10), ferroelectrics with a diffuse phase transition (y = 0.30), and ferroelectrics relaxors (y = 0.15–0.25). A conclusion about the expediency of using the obtained data in the development of materials and devices based on such materials has been made.

Strong Room-Temperature Ferroelectricity in Strained SrTiO3 Homoepitaxial Film.

Although the discovery of exceptional ferroelectricity in paraelectrics offers great opportunities to enrich the diversity of the ferroelectric family and promote the development of novel functionalities, transformation of paraelectric phases into ferroelectric phases remains challenging. Herein, a method is presented for driving paraelectrics into ferroelectric states via the introduction of M/O-deficient (M for metal) perovskite nanoregions. Using this method, strong ferroelectricity, equivalent to that of classic ferroelectrics, is achieved in a prototype paraelectric strontium titanate (SrTiO3 ) homoepitaxial film embedded with Ti/O-deficient perovskite nanoregions. It is shown that these unique nanoregions impose large out-of-plane tensile strain and electron-doping effects on the matrix to form a tetragonal structure (tetragonality = 1.038), driving the off-center movements of Ti and Sr atoms. This leads to a significant room-temperature ferroelectric polarization (maximum polarization = 41.6 µC cm-2 and spontaneous polarization = 25.2 µC cm-2 at 1.60 MV cm-1 ) with a high thermal stability (Tstable ≈ 1098 K). The proposed approach can be applied to various paraelectrics for creating ferroelectricity and generating emergent physical properties, opening the door to a new realm of materials design.

Defects in ferroelectric HfO2.

The discovery of ferroelectricity in polycrystalline thin films of doped HfO2 has reignited the expectations of developing competitive ferroelectric non-volatile memory devices. To date, it is widely accepted that the performance of HfO2-based ferroelectric devices during their life cycle is critically dependent on the presence of point defects as well as structural phase polymorphism, which mainly originates from defects either. The purpose of this review article is to overview the impact of defects in ferroelectric HfO2 on its functional properties and the resulting performance of memory devices. Starting from the brief summary of defects in classical perovskite ferroelectrics, we then introduce the known types of point defects in dielectric HfO2 thin films. Further, we discuss main analytical techniques used to characterize the concentration and distribution of defects in doped ferroelectric HfO2 thin films as well as at their interfaces with electrodes. The main part of the review is devoted to the recent experimental studies reporting the impact of defects in ferroelectric HfO2 structures on the performance of different memory devices. We end up with the summary and perspectives of HfO2-based ferroelectric competitive non-volatile memory devices.

Polarization switching in thin doped HfO2 ferroelectric layers

The deployment of ferroelectrics in device concepts such as Ferroelectric Random Access Memory and Ferroelectric Field Effect Transistors requires a good understanding of the polarization switching mechanisms. While several reports already exist involving classical perovskite ferroelectrics, only recently has the switching dynamics in HfO2-based layers started to be addressed. In this work, the Kolmogorov–Avrami–Ishibashi (KAI), the Nucleation Limited Switching (NLS), the Landau–Khalatnikov (LK), and the Inhomogeneous Field Mechanism (IFM) models for polarization switching are surveyed and evaluated with the existing body of literature. Data concerning NLS and IFM are compared to experiments undertaken in this study. After excluding the KAI model because of considerations dealing with film morphology and domain wall energy, we conclude that the NLS, the LK, and the IFM models do not necessarily mutually exclude each other, but rather give a diverse perspective on the switching phenomenon based on thermodynamic, kinetic, statistic, microscopic, and/or macroscopic points of view.

Relaxation of competing electromechanical couplings in murine artery

Piezoelectricity and pyroelectricity in biological tissues, which originate from oriented fibrous proteins with a polar axis, have long been suggested to play important roles in physiological functions. The possible manipulation of their polarity by external mechanisms, however, remains unsettled. We revisit this problem here using piezoresponse force microscopy (PFM) as the tool and the intima layer of murine artery as a model system. By carefully examining first and second harmonic piezoresponses at both selected points and through spatial mapping, we establish that electromechanical coupling probed by PFM is predominantly piezoelectric in the intima layer, while the quadratic effect makes only minor contributions. More importantly, we observe competition between the linear and quadratic effects after removal of DC biases applied to the sample surface, revealing not only interesting relaxation dynamics, but also highly asymmetric piezoresponse. Positive DC rotates dipoles in tropoelastin monomers away with reduced alignment, while negative DC aligns dipoles more leading to enhanced piezoresponse. The electric manipulation of biological polarity is thus demonstrated, with the relaxation time constant determined on the order of 0.1 s, much slower than classical ferroelectrics.

Two-dimensional hybrid organic–inorganic perovskites as emergent ferroelectric materials

Hybrid organic–inorganic perovskite (HOIP) materials have attracted significant attention in photovoltaics, light emission, photodetection, etc. Based on the prototype metal halide perovskite crystal, there is a huge space for tuning the composition and crystal structure of this material, which would provide great potential to render multiple physical properties beyond the ongoing emphasis on the optoelectronic property. Recently, the two-dimensional (2D) HOIPs have emerged as a potential candidate for a new class of ferroelectrics with high Curie temperature and spontaneous polarization. Room-temperature solution-processability further makes HOIP a promising alternative to traditional oxide ferroelectrics such as BaTiO3 and PbTiO3. In this perspective, we focus on the molecular aspects of 2D HOIPs, their correlation with macroscopic properties, as well as the material design rules assisted by advanced simulation tools (e.g., machine learning and atomistic modeling techniques). The perspective provides a comprehensive discussion on the structural origin of ferroelectricity, current progress in the design of new materials, and potential opportunities and challenges with emerging materials. We expect that this perspective will provide inspiration for innovation in 2D HOIP ferroelectrics.

Origin of Structural Change Driven by A-Site Lanthanide Doping in ABO3-Type Perovskite Ferroelectrics

Lanthanide doping is widely employed to tune structural change temperature and electrical properties in ABO3-type perovskite ferroelectric materials. However, the reason that A-site lanthanide doping leads to the decrease of the Curie temperature is still not clear. Based on the reported Curie temperature of lanthanides (Ln) doped in two classic ferroelectrics PbTiO3 and BaTiO3 with A2+B4+O3-type perovskite structure, we discussed the relationship between the decrease rate of Curie temperature (ΔTC) and the bond strength variance of A-site cation (σ). For Nd ion doped Pb(Mg1/3Nb2/3)O3-PbTiO3 (Nd-PMNT) ferroelectric crystal as an example, the internal factors of the dramatic decline of the Curie temperature induced by A-site Nd doping were investigated under a systematic study. The strong covalent bonds of Ln-O play an important role in A-site Ln composition-induced structural change from ferroelectric to paraelectric phase, and it is responsible for the significant decrease in the Curie temperature. It is proposed that the cells become cubic around the Ln ions due to the strong covalent energy of Ln-O bonding in A-site Ln doped A2+B4+O3 perovskite ferroelectrics.