Ferroelectric Phase Transformation Research Articles

Phase equilibria in the system BaO–TiO2

AbstractThe system BaO–TiO2 is technically important because it contains multiple dielectric and ferroelectric phases, including the important BaTiO3, which is one of the most widely studied dielectric perovskites owing to its dual piezoelectric and ferroelectric properties. The present work revises the subsolidus phase equilibria data by synthesizing previous phase equilibria data and new experimental results using high‐temperature (600°–1300°C) and long‐term (≤336 h) equilibration, coupled with analytical work based principally on room‐temperature X‐ray diffraction. The resultant phase diagram is given in both mole and weight percents, extending from the liquidus surface (not investigated) to absolute zero temperature (for inclusion of the previously excluded crystallographic and ferroelectric phase transformations). The major features include (1) correction of four eutectoid and three peritectoid reactions and corresponding temperatures, (2) indication of inferred partial solid solubilities, (3) clarification of the BaTiO3 solid solubility homogeneity regions, and (4) specification of some invariant point compositions on the liquidus surface.

Development of ferroelectricity with crystallographic phase transformation in Hf0.5Zr0.5O2 thin films upon initial stimulation of an electric field exceeding the coercive field

This study demonstrates a drastic transformation of ferroelectricity and crystallographic phase in Hf0.5Zr0.5O2 (HZO) thin films through the first stimulation of an electric field larger than the coercive field in metal-ferroelectric-metal (MFM) capacitors. Initially, capacitance–voltage (C–V) measurements in fresh MFM capacitors with voltage sweep smaller than the coercive field indicated constant capacitance value without hysteresis. Applying the electric field exceeding the coercive field subsequently, the C–V behavior changed to a typical dual-peak ferroelectric feature in positive and negative sweeps. X-ray diffraction analysis of the HZO layers before and after a single electric-field application revealed small-angle shifts in diffraction peaks, confirming a crystallographic phase transformation induced by the single electric-field stimulation exceeding the coercive field. These results suggest a possibility that the first electric field apply initiates development of ferroelectric phase transformation from a non-ferroelectric phase.

The mechanism of ferroelectric phase transformation in Gd2O3 modified BCZT ceramics: Experimental studies and first-principles calculations

Lead-free (Ba0.85Ca0.15)(Ti0.90Zr0.10)O3 (BCZT)-based piezoelectric ceramics have attracted considerable interest due to their excellent piezoelectric properties and abundant phase structures. However, there is a serious lack in the theoretical calculations for the ferroelectric phase transition behavior. Here, the experimental and first-principles calculations were utilized to analyze the ferroelectric phase transition process of (Ba0.85Ca0.15)(Ti0.90Zr0.10)O3-xGd2O3(BCZT-xGd, x = 0, 0.02, 0.04, and 0.05) ceramics. The incorporation of Gd2O3 has induced a transformation from tetragonal to rhombohedral phase due to the decrease in the dislocation energy with A-site cations and the attenuation of the bonding energy between B-site cations and the planar O atoms. Moreover, the hybridization between the d orbitals of B-site atoms and the O 2p orbitals, coupled with the reduction of the polarization vector along the [001] axis, leads to enhanced weak coupling relaxation. This work provides a theoretical basis for the ferroelectric phase transition behavior of other piezoelectric systems.

Sharp Transformation across Morphotropic Phase Boundary in Sub-6nm Wake-Up-Free Ferroelectric Films by Atomic Layer Technology.

Atomic layer engineering is investigated to tailor the morphotropic phase boundary (MPB) between antiferroelectric, ferroelectric, and paraelectric phases. By increasing the HfO2 seeding layer with only 2 monolayers, the overlying ZrO2 layer experiences the dramatic phase transition across the MPB. Conspicuous ferroelectric properties including record-high remanent polarization (2Pr ≈ 60 µC cm-2 ), wake-up-free operation, and high compatibility with advanced semiconductor technology nodes, are achieved in the sub-6nm thin film. The prominent antiferroelectric to ferroelectric phase transformation is ascribed to the in-plane tensile stress introduced into ZrO2 by the HfO2 seeding layer. Based on the high-resolution and high-contrast images of surface grains extracted precisely by helium ion microscopy, the evolution of the MPB between tetragonal, orthorhombic, and monoclinic phases with grain size is demonstrated for the first time. The result indicates that a decrease in the average grain size drives the crystallization from the tetragonal to polar orthorhombic phases.

Thermodynamic prediction of ferroelectric mechanical to electrical energy harvesting capabilities utilizing phase dependent electromechanical coupling factors

Prediction of the mechanical to electrical energy harvesting capabilities in [011]C cut PIN-PMN-PT is presented as a function of thermodynamic analysis of hysteresis in the stress induced ferroelectric phase transformation, and phase dependency of the electromechanical coupling factors. Energy conversion rates vary from 0.528 for low transformation hysteresis to 0.432 for high transformation hysteresis. While these predicted values are lower than the experimentally determined value from literature (“approximately 60%”), differences are explained through limitations of the mechanical loading mechanism. This brings the predicted values into agreement with literature. Ferroelectric rhombohedral phase behavior is found to dominate energy harvesting capabilities.

B-site ion driven morphotropic phase transformation in NN-BT-ABO3 lead-free ceramics through chemical pressure

Forming morphotropic phase boundary (MPB) is crucial to improve the piezoelectric properties of lead-free NaNbO3-BaTiO3-xABO3 (NN-BT-xABO3) ceramics. In this work, four NN-BT-xABO3 systems (ABO3 = K0.5Bi0.5TiO3 (KBT), Bi0.5Na0.5TiO3 (BNT), K0.5Bi0.5ZrO3 (KBZ), and Bi0.5Na0.5ZrO3 (BNZ)) were constructed to analyze the relationship between ABO3 characteristic and phase transformation behavior. The results showed that the NN-BT-xKBT/xBNT systems underwent ferroelectric tetragonal (T)-relaxor ferroelectric T phase transformation with d33 ∼ 150 pC/N and kp ∼ 0.2 in NN-BT-0.11KBT and NN-BT-0.09BNT compositions, while the NN-BT-xKBZ/xBNZ systems underwent ferroelectric T- ferroelectric rhombohedral (R) morphotropic phase transformation with improved d33 ∼ 256 pC/N and kp ∼ 0.31 in NN-BT-0.04BNZ composition. The B-site ion radius was found to be a key factor in inducing phase transformation. The incorporation of small Ti4+ ions tends to break the long ordering of ferroelectrics, inducing the normal-relaxor ferroelectric phase transformation, however, the appearance of the R phase in NN-BT-xAZrO3 compositions was attributed to the chemical pressure caused by buckled Zr-O-Zr bonds as larger Zr4+ ions enter the NN-BT matrix lattices. This study will deepen the understanding of the ferroelectric phase transformation mechanism in the lead-free NaNbO3 material system and provide a guidance for designing morphotropic NN-based lead-free piezoelectric ceramics.

Superior Energy-Storage Properties in Bi0.5Na0.5TiO3-Based Lead-Free Ceramics via Simultaneously Manipulating Multiscale Structure and Field-Induced Structure Transition.

Pratical applications have put forward great challenges to the comprehensive energy-storage performance of ceramic material. Here, a novel route of simultaneously manipulating multiscale structure and the field-induced structural transformation in (Bi0.5Na0.5)TiO3-based ceramics is proposed to address the above concern. The multiscale structure of 0.88(Bi0.5Na0.5)TiO3-0.12BaTiO3 solid solutions such as grain and domain size, band gap, and phase structure can be adjusted by adding antiferroelectric NaNbO3. Simultaneously, a field-induced P4bm relaxor antiferroelectric to P4mm ferroelectric phase transformation can be obtained by constructing a P4mm-P4bm phase boundary, which is expected to require a lower energy barrier compared with the field-induced P4bm relaxor antiferroelectric to R3c ferroelectric transformation in other (Bi0.5Na0.5)TiO3-based ceramics. The optimized field-induced structural transformation behavior and the formation of nanodomains enables a minimized polarization hysteresis but an enhanced maximum polarization. Moreover, the decreased grain size together with increased band gap leads to a significantly improved breakdown strength. Accordingly, a giant energy density Wrec ∼ 8.0 J/cm3, a high efficiency η ∼ 86%, a short discharging time t0.9 ∼ 41 ns, and a good temperature stability (Wrec = 1.32 ± 0.12 J/cm3, η = 88.5% ± 2.5% @ 25-200 °C) are simultaneously obtained in 0.63(Bi0.5Na0.5)TiO3-0.12BaTiO3-0.25NaNbO3 relaxor antiferroelectric ceramics, demonstrating large potentials for the ceramic capacitor applications.

Effect of capping layer on the ferroelectricity of hafnium oxide

In this work, we investigate the effect of a capping layer of aluminum oxide (AlOx) on dopant-free hafnium-oxide (HfO2) ferroelectric layer. According to our experimental results, the AlOx-capped HfO2 ferroelectric capacitor exhibits the significant improvement on ferroelectric polarization strength and also presents a comparable electrical stress resistance in comparison with control HfO2 ferroelectric capacitor with a very weak ferroelectric hysteresis. An additional nitrogen treatment on AlOx capping layer effectively alleviate the stress-induced generation of defect traps near the interface of tantalum nitride (TaN) electrode under negative-bias voltage stress. Therefore, the performance improvement can be ascribed to the introduction of AlOx capping layer and well-controlled nitrogen plasma treatment to improve interface traps and stabilize the ferroelectric phase transformation during high-temperature annealing process.

NaNbO3 modulated phase transition behavior and antiferroelectric stability evolution in 0.88(Bi0.5Na0.5)TiO3-0.12BaTiO3 lead-free ceramics

Giant strains in (Bi0.5Na0.5)TiO3 based ceramics are usually attributed to electric field induced nonpolar to polar phase transition. Whether it is an ergodic relaxor R3c/P4mm ferroelectric (FE) to long-range ordered FE phase transformation or a reversible P4bm antiferroelectric (AFE) to FE phase transition is still unclear. Herein, lead-free (0.88-x)(Bi0.5Na0.5)TiO3-0.12BaTiO3-xNaNbO3 ceramics exhibit a composition-modulated FE tetragonal P4mm to relaxor AFE tetragonal P4bm phase transition, in which double hysteresis loop, sprout-shaped S-E curves, near-zero quasi-static d33 together with a large volume change suggest the AFE characteristics of P4bm phase. An interesting finding is that the reversibility of field-induced AFE P4bm phase to FE P4mm phase transition strongly depends on the NN content, from being completely irreversible at x = 0.01–0.02, to partially reversible at x = 0.03–0.05, and finally to completely reversible at x = 0.06–0.08. It is indicated that the variation of reversibility should be attributed to the change of relative free energy caused by decreasing the FE to AFE phase transition temperature with increasing the NN content.

Uncovering the symmetry of the induced ferroelectric phase transformation in polycrystalline barium titanate

Microstructural design is a widespread approach to tailor the properties of functional materials with the size effect being an effective constraint that modifies physical phenomena. In this work, we investigate the grain size effect on the properties and the electric field induced phase transformation behavior in barium titanate. A broad range of unimodal average grain size distribution between 0.4 and 15 μm was successfully sintered avoiding abnormal grain growth. Samples with a grain size close to the range of 1–2 μm, balancing microstructural strain, presence, and mobility of domain walls to allow the field induced crystal phase transformation, showed optimal electromechanical and dielectric properties. By means of in situ high energy x-ray diffraction and a high-resolution multianalyzer detector, we distinguish and quantify a tetragonal–orthorhombic phase transformation induced by an electric field, providing unambiguous proof of this induced phase transformation. These results contribute to the understanding of fundamental questions about the piezoelectric effect in barium titanate and consequently other similar systems.

Twin-boundary engineering and thickness effect on strontium-barium niobate thin films on MgO substrate

The Sr0.5Ba0.5Nb2O6 (SBN50) films with different thicknesses synthesized by a high-current discharge rf-sputtering in an oxygen atmosphere. All synthesized films have the structure of tetragonal tungsten bronze. The dependence of the unit cell parameters of the film material demonstrates a size effect, the magnitude of which is comparable to the distortions resulting from the ferroelectric relaxor phase transformation of SBN crystals of the same composition. The twinning of the same type is observed in all films when the twinned film components are rotated relative to each other by 36.8 degrees around the fourth-order rotational axis. The orientation of the films relative to the substrate can be written as [001]SBN∥[001]MgO; [100]SBN+∥[310]MgO and [100]SBN−∥[31¯0]MgO, where the sign "+" and "–" marks the twin components. It is noteworthy that such an orientation of the film relative to the substrate corresponds to the maximum possible tensile stress of heteroepitaxial films acting from the MgO single crystal substrate. This type of twinning is not typical for SBN50 films on MgO grown by other synthesis methods. The appearance of this unusual type of twinning is associated with the peculiarities of synthesis. At the initial moment of sputtering, the substrate is additionally heated by the sputtered substance’s plasma. The substrate temperature can also be used in other synthesis methods to control twinning and strain in barium strontium niobate thin films.

Induced ferroelectric phase transformation in polycrystalline BaTiO3

Induced ferroelectric phase transformation in polycrystalline BaTiO₃

Evidence of ferroelectric HfO2 phase transformation induced by electric field cycling observed at a macroscopic scale

The phase transformation of ferroelectric (FE) HfO2 induced by electric field cycling was observed at a macroscopic scale using the conventional X-ray diffraction (XRD) technique. We confirmed that the increase in the switchable polarization (Psw) is the result of the phase transformation to increase the amount of the higher symmetric phase of HfO2, both observed at a macroscopic scale. During characterization, we found an anomalous shift difference between the in-plane and the out-of-plane interplanar spacing in every HfO2 film we fabricated. We speculate that this phenomenon is unique to HfO2 and may have played an important role in the phase transformation during the waking-up effect of FE-HfO2.

Accelerated ferroelectric phase transformation in HfO2/ZrO2 nanolaminates

Ferroelectric phase transformation was compared between the Hf0.5Zr0.5O2 solid solution films and the HfO2/ZrO2 nanolaminate films, prepared by sputter deposition without heat treatment and crystallized by following cap annealing. Physical analyses showed that nanolaminate structures and their interfaces were robust even after high-temperature annealing. Ferroelectricity appeared largely in the nanolaminate films than in the solid solution film, and the best performance was attained in the nanolaminate film with the cycle thickness of monolayer oxide (0.25 nm). Long period annealing cleared that the ferroelectric phase transformation is greatly accelerated in the nanolaminate films than in the solid solution films.

Emerging Fluorite‐ and Wurtzite‐Type Ferroelectrics: From (Hf,Zr)O2 to AlN and Related Materials

Emerging Fluorite‐ and Wurtzite‐Type Ferroelectrics: From (Hf,Zr)O₂ to AlN and Related Materials

Electric‐Field‐Induced Ferroelectricity in 5%Y‐doped Hf0.5Zr0.5O2: Transformation from the Paraelectric Tetragonal Phase to the Ferroelectric Orthorhombic Phase

The ferroelectric phase transformation from the tetragonal phase to the orthorhombic phase, induced by an electric field, is demonstrated in a 5%YO1.5‐doped Hf0.5Zr0.5O2 epitaxial film which is grown on Sn‐doped In2O3‐covered (111) yttria‐stabilized zirconia by the pulsed laser deposition method at room temperature and subsequent heat treatment. Although X‐ray diffraction shows the film to consist of a paraelectric tetragonal phase after the heat treatment, polarization–electric field (P–E) measurements reveal a hysteresis loop attributed to the ferroelectricity. To clarify the discrepancy between the crystal structure and electric characteristics, the crystal structure after electric field loading is determined by scanning transmission electron microscopy and synchrotron X‐ray diffraction measurements. Both structural characterizations clearly reveal that the application of an electric field promotes the phase transition from the paraelectric tetragonal phase to the ferroelectric orthorhombic phase. This ferroelectric transition is irreversible, as the ferroelectric phase remains after the removal of the electric field. These results facilitate the elucidation of the mechanism by which ferroelectricity is displayed in HfO2‐based fluorite ferroelectric materials and imply unimportance of the orthorhombic phase for as‐prepared films.

Electrospinning of multiferroic CoFe2O4@ Ba(Zr0.2Ti0.8)O3–0.5(Ba0.7Ca0.3)TiO3 nano-structured fibers via two different routes

Multiferroic composite materials have attracted a lot of attention for their excellent ferroelectric and ferromagnetic properties. For the first time one-dimensional core-shell structure of CoFe2O4/Ba(Zr0.2Ti0.8)O3–0.5(Ba0.7Ca0.3)TiO3 (CFO@BZCT) multiferroic composite was synthesized by electrospinning. The effect of electrospinning routes on the composite fibers properties was investigated. To do so, two different routes were utilized: the electrospinning of core and shell solutions using coaxial nozzle and the electrospinning of BZCT solution containing CFO fibers (with three different concentrations of 2, 4 and 8 g/100 ml solution). The fiber morphology was maintained for all samples in calcination temperatures up to 900 °C. Spinel cobalt ferrite and perovskite BZT-0.5BCT phases were crystallized for calcined composites. The nano and core-shell structure of composites were confirmed by the TEM analysis. Magnetoelectric coupling of CFO and BZCT phases was investigated by the temperature-dependent SQUID measurement, where a ferroelectric phase transformation at 100 °C induced magnetization changes. Low saturation magnetization and dielectric constant of 6.7 emu/g and 300 ± 10 were obtained for the sample synthesized by the first method while these values rose to 36.8 emu/g and 400 ± 30 respectively for the second method. A comparison of the two methods exhibited a larger fiber diameter, porous fibers and lower ferroic properties for the sample synthesized by the first method.

The complex structural mechanisms behind strain curves in bismuth sodium titanate–barium titanate

In this work, the lead-free composition (1-x)Bi0.5Na0.5TiO3–xBaTiO3 (BNT–BT) with x = 0.12 was investigated using in situ Synchrotron x-ray powder diffraction. With the applied electric field, the pseudo-cubic relaxor phase reversibly transforms to a ferroelectric state. The reversibility is still preserved after 104 bipolar electric field cycles. A Rietveld refinement with a structure, strain, and texture analysis using a model based on the atomic scale was applied for four frequencies from 10−4 to 101 Hz. The analysis allowed us to separately determine the two coexisting phases, their electric field dependent evolution, and the underlying strain mechanisms. For all the applied frequencies, we showed that domain switching is the only strain mechanism appearing in the tetragonal phase and the lattice strain is the only mechanism in the rhombohedral phase. The coercive field of the tetragonal phase (4 kV/mm) is found to be higher than that of the rhombohedral phase (3 kV/mm). This divergence has not been observed in previously investigated lead-containing materials and cannot be detected solely using macroscopic strain and polarization experiments. Moreover, the domain strain abruptly starts to occur only after a threshold field value and exhibits high hysteresis. The lattice strain, on the other hand, starts nearly from the beginning and increases more linearly during the bipolar field cycle. It could, therefore, be demonstrated that complex structural mechanisms underlie the apparent clear and continuous macroscopic strain curve. These findings are crucial for all actuator materials undergoing a relaxor to ferroelectric phase transformation and provide approaches and strategies to optimize lead-free materials for tailored applications.

X‐Ray Diffractive Imaging: Needle‐Like Ferroelastic Domains in Individual Ferroelectric Nanoparticles (Adv. Electron. Mater. 5/2020)

In article 1901300, Edwin Fohtung and co-workers demonstrate an X-ray Bragg coherent diffractive imaging technique to spatially resolve the evolution of nanoscopic ferroelastic needle-like domains in individual BaTiO3 nanocrystals under external pressure. This provides a new paradigm for domain-boundary engineering and potential for nanoscale functional devices aided by pressure-induce structural phase transitions and ferroelectric phase transformation.

Electric-Field-Induced Phase Transformation and Frequency-Dependent Behavior of Bismuth Sodium Titanate-Barium Titanate.

The electric field response of the lead-free solid solution (1−x)Bi0.53Na0.47TiO3–xBaTiO3 (BNT–BT) in the higher BT composition range with x = 0.12 was investigated using in situ synchrotron X-ray powder diffraction. An introduced Bi-excess non-stoichiometry caused an extended morphotropic phase boundary, leading to an unexpected fully reversible relaxor to ferroelectric (R–FE) phase transformation behavior. By varying the field frequency in a broad range from 10−4 up to 102 Hz, BNT–12BT showed a frequency-dependent gradual suppression of the field induced ferroelectric phase transformation in favor of the relaxor state. A frequency triggered self-heating within the sample was found and the temperature increase exponentially correlated with the field frequency. The effects of a lowered phase transformation temperature TR–FE, caused by the non-stoichiometric composition, were observed in the experimental setup of the freestanding sample. This frequency-dependent investigation of an R–FE phase transformation is unlike previous macroscopic studies, in which heat dissipating metal contacts are used.