Ferroelectric Phase Transition Research Articles

Design of polar boundaries enhancing negative electrocaloric performance by antiferroelectric phase-field simulations

Electrocaloric refrigeration which is environmentally benign has attracted considerable attention. In distinction to ferroelectric materials, which exhibit an extremely high positive electrocaloric effect near the Curie temperature, antiferroelectric materials represented by PbZrO3 have a specific negative electrocaloric effect, i.e., electric field decreases the temperature of the materials. However, the explanation of the microscopic mechanism of the negative electrocaloric effect is still unclear, and further research is still needed to provide a theoretical basis for the negative electrocaloric effect enhancement. Herein, the antiferroelectric phase-field model has been proposed to design polar boundaries enhancing antiferroelectric negative electrocaloric performance in PbZrO3-based materials. Based on this, we have simulated the polarization response and domain switching process of the temperature and electric field-induced antiferroelectric—ferroelectric phase transition. It is shown that the temperature range tends to increase as the density of polar boundaries increases from the antiferroelectric stripe domain, polymorphic domain to the nanodomain. Among them, the peak adiabatic temperature change of antiferroelectric nanodomains can reach −13.05 K at 84 kV/cm, and a wide temperature range of about 75 K can be realized at 42 kV/cm. We expect these discoveries to spur further interest in the potential applications of antiferroelectric materials for next-generation refrigeration devices.

Field-induced effects and ferroelectric critical endpoint in (K0.95Li0.05)(Nb1–x Ta x )O3 single crystals

Abstract Dielectric permittivities under dc biasing fields in the temperature range between –169 and 75°C have been investigated in (K0.95Li0.05)(Nb1–x Ta x )O3 (KLNT–x, x = 71 and 74%). Field-induced ferroelectric phase transitions in KLNT–x have been clarified in the dc field applied along the [001]c direction (in the cubic coordinate). The ferroelectric critical endpoints in KLNT–71% and KLNT–74% have been determined to be 43.5°C, 3.0 kV/cm, and 30.3°C, 2.0 kV/cm, respectively. The tricritical point at which the first-order phase transition changes to the second-order phase transition has been estimated at 10.4℃ and x = 77.4% in the temperature–concentration phase diagram. The field-induced phase transitions and dielectric tunabilities have been discussed on the basis of the Landau-type free energy density.

Accelerating ferroelectric materials discovery through high-throughput first-principles screening and experimental validation

Abstract We conducted high-throughput screening of ferroelectrics using first-principles calculations based on an existing crystal structure database. We focused on nonpolar structures with polar instability, to efficiently screen materials for their potential to undergo ferroelectric phase transitions from oxide materials in crystal structure databases. Our screening criteria included computational feasibility (excluding partial occupation), the absence of hazardous elements, and a maximum of 250 atoms in the conventional cell. Through this screening, we identified 47 ferroelectric candidates, 8 of which have already been reported as ferroelectrics. To validate our screening approach, we synthesized and evaluated several candidate materials with Dion-Jacobson-type structures and measured their dielectric and ferroelectric properties. Although the ferroelectric behavior was not initially identified in these materials, our experiments confirmed their properties. 
Finally, we discovered a new ferroelectric material, CsCa2Nb3O10, which exhibited a ferroelectric phase transition at 28 K, clearly demonstrating the effectiveness of our screening strategy.

Accelerating ferroelectric materials discovery through high-throughput first-principles screening and experimental validation

Abstract We conducted high-throughput screening of ferroelectrics using first-principles calculations based on an existing crystal structure database. We focused on nonpolar structures with polar instability, to efficiently screen materials for their potential to undergo ferroelectric phase transitions from oxide materials in crystal structure databases. Our screening criteria included computational feasibility (excluding partial occupation), the absence of hazardous elements, and a maximum of 250 atoms in the conventional cell. Through this screening, we identified 47 ferroelectric candidates, 8 of which have already been reported as ferroelectrics. To validate our screening approach, we synthesized and evaluated several candidate materials with Dion-Jacobson-type structures and measured their dielectric and ferroelectric properties. Although the ferroelectric behavior was not initially identified in these materials, our experiments confirmed their properties. 
Finally, we discovered a new ferroelectric material, CsCa2Nb3O10, which exhibited a ferroelectric phase transition at 28 K, clearly demonstrating the effectiveness of our screening strategy.

Biodegradable Ferroelectric Molecular Plastic Crystal HOCH2(CF2)7CH2OH Structurally Inspired by Polyvinylidene Fluoride.

Ferroelectric materials, traditionally comprising inorganic ceramics and polymers, are commonly used in medical implantable devices. However, their nondegradable nature often necessitates secondary surgeries for removal. In contrast, ferroelectric molecular crystals have the advantages of easy solution processing, lightweight, and good biocompatibility, which are promising candidates for transient (short-term) implantable devices. Despite these benefits, the discovered biodegradable ferroelectric materials remain limited due to the absence of efficient design strategies. Here, inspired by the polar structure of polyvinylidene fluoride (PVDF), a ferroelectric molecular crystal 1H,1H,9H,9H-perfluoro-1,9-nonanediol (PFND), which undergoes a cubic-to-monoclinic ferroelectric plastic phase transition at 339 K, is discovered. This transition is facilitated by a 2D hydrogen bond network formed through O-H···O interactions among the oriented PFND molecules, which is crucial for the manifestation of ferroelectric properties. In this sense, by reducing the number of -CF2- groups from ≈5000 in PVDF to seven in PFND, it is demonstrated that this ferroelectric compound only needs simple solution processing while maintaining excellent biosafety, biocompatibility, and biodegradability. This work illuminates the path toward the development of new biodegradable ferroelectric molecular crystals, offering promising avenues for biomedical applications.

Tadpole-Like Polar Molecule Encapsulated in a Two-in-One Supramolecular Cage: Molecular Motion, Phase Transition and Ferroelectricity.

Molecule-inclusive closed cage compounds present a unique platform for molecular motion in an isolated environment. This study showcases the incorporation of a tadpole-like polar molecule (1-propyl-1H-imidazole, PIm) into a supramolecular cage formed by duad semicage p-tert-butylcalix[4]arene. The ferroelectric phase transition as well as the cage-confined motion of encapsulated PIm was studied in detail. The unusual quadrastable state of the PIm in the paraelectric phase allows for the modulation of dipolar polarization over a broad temperature/frequency range. This compound represents the first example of a clathrate molecular ferroelectric featuring a molecule-inclusive supramolecular cage, and it also contributes to the understanding of cage-confined molecular dynamics.

Molecular orbital breaking in photo-mediated organosilicon Schiff base ferroelectric crystals

Ferroelectric materials, whose electrical polarization can be switched under external stimuli, have been widely used in sensors, data storage, and energy conversion. Molecular orbital breaking can result in switchable structural and physical bistability in ferroelectric materials as traditional spatial symmetry breaking does. Differently, molecular orbital breaking interprets the phase transition mechanism from the perspective of electronics and sheds new light on manipulating the physical properties of ferroelectrics. Here, we synthesize a pair of organosilicon Schiff base ferroelectric crystals, (R)- and (S)-N-(3,5-di-tert-butylbenzylidene)-1-((triphenylsilyl)oxy)ethanamine, which show optically controlled phase transition accompanying the molecular orbital breaking. The molecular orbital breaking is manifested as the breaking and reformation of covalent bonds during the phase transition process, that is, the conversion between C = N and C–O in the enol form and C–N and C = O in the keto form. This process brings about photo-mediated bistability with multiple physical channels such as dielectric, second-harmonic generation, and ferroelectric polarization. This work further explores this newly developed mechanism of ferroelectric phase transition and highlights the significance of photo-mediated ferroelectric materials for photo-controlled smart devices and bio-sensors.

Investigations of energy storage and thermal stability properties in eco-friendly B-site substituted Na0.5Bi0.5TiO3

In this work, (Mg1/3Nb2/3)4+ cationic substitution in lead-free polycrystalline Na0.5Bi0.5TiO3 (NBT) has been adopted to synthesize by the conventional solid-state reaction method. The cationic substitution was introduced into NBT through compositional modification, which significantly restricted grain growth and promoted a ferroelectric to relaxor ferroelectric phase transition. The substitution of (Mg1/3Nb2/3)4+ influenced the crystal structure, ferroelectric, dielectric properties, and micromorphology, which had been investigated systematically. The enhancement of relaxor nature is found with this substitution and further verified by dielectric curve, polarization (P) - electric field (E) hysteresis loop, and current (I)- electric field (E) curve. The recoverable energy density was determined to be 1.09 J/cm3 and 1.24 J/cm3 at 101 kV/cm and 114 kV/cm in the 10 mol% and 20 mol% of (Mg1/3Nb2/3)4+ substituted systems, respectively. Furthermore, over the 35 ˚C to 490 ˚C temperature range, the 30 mol% (Mg1/3Nb2/3)4+ substituted composition showed superior thermal stability in the permittivity. Therefore, this study concluded that these cationic substituted NBT compositions are appropriate materials for applications involving higher-temperature and energy storage in electronic devices.

Antiferroelectric Ceramics for Energy-Efficient Capacitors by Theory-Guided Discovery.

Antiferroelectric ceramics, via the electric-field-induced antiferroelectric (AFE)-ferroelectric (FE) phase transitions, show great promise for high-energy-density capacitors. Yet, currently, only 70-80% energy release is found during a charge-discharge cycle. Here, for PbZrO3-based oxides, geometric nonlinear theory of martensitic phase transitions is applied (first used to guide supercompatible shape-memory alloys) to predict the reversibility of the AFE-FE transition by using density-functional theory to assess AFE/FE interfacial lattice-mismatch strain that assures ultralow electric hysteresis and extended fatigue lifetime. A good correlation of mismatch strain with electric hysteresis, hence, with energy efficiency of AFE capacitors is observed. Guided by theory, high-throughput material search is conducted and AFE compositions with a near-perfect charge-discharge energy efficiency (98.2%), i.e., near-zero hysteresis are discovered. And the fatigue life of the capacitor reaches 79.5 million charge-discharge cycles, a factor of 80 enhancement over AFE ceramics with large electric hysteresis.

Interface engineering of composite systems: Focusing on the compatibility of reduced graphene oxide and Bi0.8La0.1Ba0.1Fe0.9Ti0.1O3 hybrid systems

The composite of reduced graphene oxide and perovskite-based ferroelectric materials offers exciting opportunities to enhance the optical performance of optoelectronic devices. The present work reporting rGO modified x(Bi0.8La0.1Ba0.1Fe0.9Ti0.1O3)-1-x(rGO) (La-BBFT/rGO) composite to investigate their structural, morphological, electrical, magnetic and optical properties by using robust solid-state and spun calcination method. X-Ray diffraction patterns confirm the rhombohedral crystal structure with space group (R3c) of both samples with the presence of rGO as second phase. The functional groups present in reduced graphene oxide (rGO) can act as nucleation sites for crystallization, leading to the formation of more grains and Grain boundaries. The ferroelectric phase transition was observed in La-BBFT/rGO composites at comparatively low temperature near 250 °C. The impedance spectroscopy confirms the non-Debye behaviour of relaxation process. The electric and magnetic remanence shows the compatibility of the switching state. Additionally, the optical band gap energy of both samples was evaluated and found to be in the range of 2.0 to 1.9eV. Incorporation of rGO in La-BBFT/rGO, were marginally improved, the dialectic, impedance, and optical properties, which could be beneficial for electronic and optical components in the opto-electronic industries.

Ferroelectric polymorphic phenomena in the layered antiferromagnet Cu(OH)2

Ferroic orders and their associated structural phase transitions are paramount in the understanding of a multitude of unconventional condensed matter phenomena. On this note, our investigation focuses on the polymorphic ferroelectric (FE) phase transitions of Copper(II) hydroxide, Cu(OH)2, considering an antiferromagnetic ground state. By employing the first-principles studies and group theory analysis, we have provided a systematic theoretical investigation of vibrational properties in the hypothetical Cmcm high-symmetry phase to unveil the symmetry-allowed ferroic phases. We identified a non-polar to polar ( Cmc21 ) phase transition, in which the displacive transformation is primarily responsible for the phase change induced by two B1u ( i.e. Γ2− ) phonon modes within the centrosymmetric phase. We also observed the existence of two polar structures with the same space group and different degrees of polarization ( i.e. Ps = 3.06 µC·cm−2 and Ps = 42.41 µC·cm−2), emerging from the high symmetry non-polar structure. According to the structural analysis the FE order, of a geometric nature, is driven by the Γ2− mode in which the O- and H-sites displacements lead the polar distortion with a minor contribution from the Cu-sites. Interestingly, the 3d 9:Cu2+ Jahn–Teller distortion coupled with the orientational shifts of O–H atoms enhances the polarization.

Voltage-assisted 3D printing of polymer composite dielectric films with low energy loss and high energy storage density

PVDF-based polymers have garnered significant attention in the field of high-power density electrostatic capacitors due to their exceptional dielectric strength. However, their practical applications are constrained by low charge-discharge efficiency (η) and energy storage density (Ue), which stem from high ferroelectric relaxation and low breakdown strength (Eb). Here, a hydrogenated glassy polymer poly(styrene-methyl methacrylate-methylallyl alcohol) (PSMA) is designed and synthesized to be homogeneously distributed in PVDF through voltage-assisted 3D printing-hot pressing, resulting in a flexible composite film. The findings demonstrate that PSMA, rich in hydrogen bonds and high modulus strength, effectively mitigates the ferroelectric phase transition of PVDF to enhance η. Additionally, the voltage-assisted 3D printing process induces an entropy gain mechanism, facilitating the uniform distribution of the two phases and enhancing the interfacial properties for enhancing Eb. Remarkably, the study achieves prominent growth in energy storage performance, with Ue and η reaching 18.1 J/cm3 and 80 % at 525 MV/m, respectively. These remarkable results highlight the potential of 3D printing technology in enhancing the energy storage performance of PVDF-based dielectrics.

Giant piezoelectricity driven by Thouless pump in conjugated polymers

Piezoelectricity of organic polymers has attracted increasing interest because of several advantages they exhibit over traditional inorganic ceramics. While most organic piezoelectrics rely on the presence of intrinsic local dipoles, a highly nonlocal electronic polarisation can be foreseen in conjugated polymers, characterised by delocalised and highly responsive π-electrons. These 1D systems represent a physical realisation of a Thouless pump, a mechanism of adiabatic charge transport of a topological nature which results, as shown in this work, in anomalously large dynamical effective charges, inversely proportional to the bandgap energy. A structural (ferroelectric) phase transition further contributes to an enhancement of the piezoelectric response reminiscent of that observed in piezoelectric perovskites close to morphotropic phase boundaries. First-principles density functional theory (DFT) calculations performed in two representative conjugated polymers using hybrid functionals, show that state-of-the-art organic piezoelectric are outperformed by piezoelectric conjugated polymers, mostly thanks to strongly anomalous effective charges of carbon, larger than 5e—ordinary values being of the order of 1e—and reaching the giant value of 30e for band gaps of the order of 1 eV.

Giant energy storage and power density negative capacitance superlattices.

Dielectric electrostatic capacitors1, because of their ultrafast charge-discharge, are desirable for high-power energy storage applications. Along with ultrafast operation, on-chip integration can enable miniaturized energy storage devices for emerging autonomous microelectronics and microsystems2-5. Moreover, state-of-the-art miniaturized electrochemical energy storage systems-microsupercapacitors and microbatteries-currently face safety, packaging, materials and microfabrication challenges preventing on-chip technological readiness2,3,6, leaving an opportunity for electrostatic microcapacitors. Here we report record-high electrostatic energy storage density (ESD) and power density, to our knowledge, in HfO2-ZrO2-based thin film microcapacitors integrated into silicon, through a three-pronged approach. First, to increase intrinsic energy storage, atomic-layer-deposited antiferroelectric HfO2-ZrO2 films are engineered near a field-driven ferroelectric phase transition to exhibit amplified charge storage by the negative capacitance effect7-12, which enhances volumetric ESD beyond the best-known back-end-of-the-line-compatible dielectrics (115 J cm-3) (ref. 13). Second, to increase total energy storage, antiferroelectric superlattice engineering14 scales the energy storage performance beyond the conventional thickness limitations of HfO2-ZrO2-based (anti)ferroelectricity15 (100-nm regime). Third, to increase the storage per footprint, the superlattices are conformally integrated into three-dimensional capacitors, which boosts the areal ESD nine times and the areal power density 170 times that of the best-known electrostatic capacitors: 80 mJ cm-2 and 300 kW cm-2, respectively. This simultaneous demonstration of ultrahigh energy density and power density overcomes the traditional capacity-speed trade-off across the electrostatic-electrochemical energy storage hierarchy1,16. Furthermore, the integration of ultrahigh-density and ultrafast-charging thin films within a back-end-of-the-line-compatible process enables monolithic integration of on-chip microcapacitors5, which can unlock substantial energy storage and power delivery performance for electronic microsystems17-19.

Design, synthesis and Characterization of a novel antiferroelectric solid solution (1-x)PbHfO3-xBiAlO3

Antiferroelectric (AFE) materials are potentially useful for energy storage applications. Lead hafnate (PbHfO3) is one of the prototypical AFE materials. However, its critical field (Ecr) which is needed to induce the AFE to ferroelectric phase transition is close to the dielectric breakdown strength. To reduce Ecr, we prepare the solid solutions of (1-x)PbHfO3–xBiAlO3 (x = 0.00–0.04) via solid state synthesis. The crystal structures, dielectric behaviour, ferroelectric properties, and energy storage properties are investigated. A temperature-composition phase diagram is established. At room temperature, the crystal symmetry of all compositions is orthorhombic with the Pbam space group. Upon heating, the transition to the AFE orthorhombic Imma phase is observed at the temperature TC1, which slightly decreases with increasing x, followed by the transition to the cubic phase at the temperature TC2, which does not depend on x. Distinct dielectric anomalies are observed at TC1 and TC2. It is found that BiAlO3 substitution reduces Ecr and the polarization–electric field relations display characteristic double hysteresis loops. For x = 0.04, at a comparatively small applied field of 130 kV/cm, the values of recoverable energy density (Wrec) and efficiency of 0.24 J/cm3 and 84 %, respectively, are obtained. At 190 °C, a Wrec = 0.75 J/cm3 and a very high efficiency of 92 % are obtained at the field of 50 kV/cm. Thus, the prepared material can potentially be used in high-temperature pulsed power capacitors for energy storage applications within the temperature range from room temperature up to 190 °C.

Effect of Intrinsic Ferroelectric Phase Transition on Hydrogen Evolution Electrocatalysis

AbstractHeterogeneous electrocatalysis closely relies on the electronic structure of the catalytic materials. The ferroelectric‐to‐paraelectric phase transition of the materials also involves a change in the state of electrons that could impact the electrocatalytic activity, but such correlation remains unexplored. Here, we demonstrate experimentally and theoretically that the intrinsic electrocatalytic activity could be regulated as exampled by hydrogen evolution reaction catalysis over two‐dimensional ferroelectric CuInP2S6. The obvious discontinuity in the overpotential and apparent activation energy values for CuInP2S6 electrode are illustrated during the ferroelectric‐to‐paraelectric phase transition caused by copper displacement around Tc point (318 K), revealing the ferroelectro‐catalytic effect on thermodynamics and kinetics of electrocatalysis. When loading Pt single atom on the CuInP2S6, the paraelectric phase one showed an improved hydrogen evolution activity with smaller apparent activation energy over the ferroelectric phase counterpart. This is attributed to the copper hopping between two sulfur planes, which alternate between strong and weak H adsorption at the Pt sites to simultaneously promote H+ reactant adsorption and H2 product desorption.

The role of local non-tetragonal polar displacements in the temperature- and pressure-induced phase transitions in PbTiO3-BiMeO3 ferroelectrics

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Highly reversible extrinsic electrocaloric effects over a wide temperature range in epitaxially strained SrTiO3 films

Electrocaloric effects have been experimentally studied in ferroelectrics and incipient ferroelectrics, but not incipient ferroelectrics driven ferroelectric using strain. Here we use optimally oriented interdigitated surface electrodes to investigate extrinsic electrocaloric effects in low-loss epitaxial SrTiO3 films near the broad second-order 243 K ferroelectric phase transition created by biaxial in-plane coherent tensile strain from DyScO3 substrates. Our extrinsic electrocaloric effects are an order of magnitude larger than the corresponding effects in bulk SrTiO3 over a wide range of temperatures including room temperature, and unlike electrocaloric effects associated with first-order transitions they are highly reversible in unipolar applied fields. Additionally, the canonical Landau description for strained SrTiO3 films works well if we set the low-temperature zero-field polarization along one of the in-plane pseudocubic <100> directions. In future, similar strain engineering could be exploited for other films, multilayers and bulk samples to increase the range of electrocaloric materials for energy efficient cooling.

Raman scattering evolution in temperature-induced ferroelectric phase transition of few-layer NbOCl2

NbOCl2 is an emerging layered ferroelectric (FE) material with unique photoelectric properties. However, the phonons and thermal properties of NbOCl2 have remained elusive. Here, we report measurements of Raman and second harmonic generation spectrum of NbOCl2 flakes as a function of temperature (80–500 K). All observed Raman modes exhibit temperature-dependent shift. The first-order temperature coefficients of P1, P2, P3, P4, and P5 modes are 0.001 58, −0.005 21, −0.006 44, −0.012 56, and 0.036 75 cm−1 K−1, respectively. Interestingly, the frequency of the P1 mode changes directly from 161 to 156 cm−1 with increasing temperature, which is attributed to the switching between two independent Raman modes (P1H and P1L). The P1H mode is mainly contributed by the FE phase, while the P1L mode is mainly contributed by the antiferroelectric phase. Our results provide a fundamental understanding and analysis of the thermal–phonon coupling properties of few-layer NbOCl2 and promote the deep exploration of the basic physical properties of few-layer NbOCl2, which is crucial for the design and application of NbOCl2-based thermal and optoelectronic devices in the future.

Electric, Dielectric, and Phonon Properties of Cu2OCl2

Investigating the multiferroic properties of , their temperature and magnetic‐field dependencies around the magnetic and ferroelectric phase transition temperatures and are analyzed using a microscopic model and Green's function technique. Near the Neel temperature , a kink in the specific heat and also in the phonon energy and damping due to strong anharmonic spin–phonon interaction is observed. The kink in disappears with increasing magnetic field h. The polarization shows also a small anomaly at and decreases with increasing magnetic field h. This behavior strongly suggests that exhibits multiferroic characteristics. A kink at can be seen in the real part of the dielectric constant , too. It should be noted that demonstrates a significant increase with increasing field strength h below , which is a pronounced magneto‐dielectric effect. These findings qualitatively agree with the experimental data.