High Spontaneous Polarization Research Articles

Enhancing piezoelectric properties of BiScO3-PbTiO3 ceramics via- incorporation of Bi(Zn1/2Ti1/2)O3 with high spontaneous polarization

High-performance piezoelectric materials are the core elements for the fabrication piezoelectric transducers and actuators. In recent years, there has been an increasing demand for piezoelectric materials with both high operational temperature and large piezoelectricity. However, the conventional approach of soft doping to enhance the piezoelectric response often results in a reduction in Curie temperature. To address this issue, we incorporated Bi(Zn1/2Ti1/2)O3 with a large spontaneous polarization (Ps ∼ 100 µC/cm2) and high Curie temperature (Tc ∼ 1380 °C) into BiScO3-PbTiO3 ceramics to improve the piezoelectric response while maintaining high Tc. The newly developed 0.08Bi(Zn1/2Ti1/2)O3-0.335BiScO3-0.585PbTiO3 ceramic exhibits impressive properties including a high d33 value of 585 pC/N (increased by ∼ 33 % compared to the 0.36BiScO3-0.64PbTiO3 ceramics), an electromechanical coupling coefficient k33 of 0.75, a dielectric constant ε′ of 2380, a relatively high Tc of 421 °C. These remarkable improvements hold great promise for advancing high-temperature piezoelectric devices.

Evaporation Dynamics on a Lithium Niobate Surface.

Manipulating the water evaporation dynamics is a prerequisite in various modern-day applications like DNA stretching, rapid disease diagnostics, and inkjet printing. One method to affect the evaporation dynamics of droplets is to externally apply electric fields. However, surfaces that bear an intrinsic surface charge have not yet been investigated with respect to their evaporation behavior. In this study, we investigate water droplet evaporation on lithium niobate (LN), a ferroelectric material with a very high spontaneous polarization of 0.7 . Our results show that a droplet deposited on an LN surface evaporates in three stages: (i) constant contact radius (ii) mixed phase (iii) stick-slip, which is likely originating from the intrinsic surface charge. The influence of the polarization direction of the LN surface as well as the relative humidity of the environment on various evaporation characteristics were studied. The results suggest that the specific adsorption layers forming on charged surfaces, e. g. from the humidity of the surrounding air, play a key role in the evaporation process. Furthermore, compared to other materials with similar contact angles, LN demonstrated a significantly large evaporation rate. This property might also be attributed to the intrinsic surface charge and could be exploited in heat transfer applications.

Achieving Ultrahigh Electrocaloric Response in (Bi0.5Na0.5)TiO3-Based Ceramics through B-Site Defect Engineering.

Lead-free electrocaloric (EC) ferroelectrics are considered ideal for the next generation of environmentally friendly solid-state refrigeration materials. However, their inferior performance compared to lead-based materials significantly restricts their potential application. According to phase-field simulations, it is predicted that the pinning effect of a moderate number of defects can effectively enhance the reversible polarization response associated with the entropy change. Herein, sodium-bismuth titanate (BNT) ceramics with high spontaneous polarization are selected to construct B-site defects by introducing Li+ and Nb5+. Under an electric field of 6 kV mm-1, ultrahigh EC temperature changes of ΔTpos = 1.77 and ΔTneg = 1.49 K are achieved at 65 °C by direct measurement (ΔTneg > 1 K over 55-120 °C). Furthermore, ΔTneg remains above 0.70 K in the temperature range from 25 to 130 °C, exhibiting immense potential for practical applications. This study offers a promising direction for optimizing the EC response in defect systems.

Magnetron-Sputtered Lead Titanate Thin Films for Pyroelectric Applications: Part 2-Electrical Characteristics and Characterization Methods.

Pyroelectric materials are naturally electrically polarized and exhibits a built-in spontaneous polarization in their unit cell structure even in the absence of any externally applied electric field. These materials are regarded as one of the ideal detector elements for infrared applications because they have a fast response time and uniform sensitivity at room temperature across all wavelengths. Crystals of the perovskite lead titanate (PbTiO3) family show pyroelectric characteristics and undergo structural phase transitions. They have a high Curie temperature (the temperature at which the material changes from the ferroelectric (polar) to the paraelectric (nonpolar) phase), high pyroelectric coefficient, high spontaneous polarization, low dielectric constant, and constitute important component materials not only useful for infrared detection, but also with vast applications in electronic, optic, and MEMS devices. However, the preparation of large perfect and pure single crystals PbTiO3 is challenging. Additionally, difficulties arise in the application of such bulk crystals in terms of connection to processing circuits, large size, and high voltages required for their operation. In this part of the review paper, we explain the electrical behavior and characterization techniques commonly utilized to unravel the pyroelectric properties of lead titanate and its derivatives. Further, it explains how the material preparation techniques affect the electrical characteristics of resulting thin films. It also provides an in-depth discussion of the measurement of pyroelectric coefficients using different techniques.

Magnetron Sputtered Lead Titanates Thin Films for Pyroelectric Applications: Part 1: Epitaxial Growth, Material Characterization.

Pyroelectric materials, are those materials with the property that in the absence of any externally applied electric field, develop a built-in spontaneous polarization in their unit cell structure. They are regarded as ideal detector elements for infrared applications because they can provide fast response time and uniform sensitivity at room temperature over all wavelengths. Crystals of the perovskite Lead Titanate (PbTiO3) family show pyroelectric characteristics and undergo structural phase transitions. They have a high Curie temperature (the temperature at which the material changes from the ferroelectric (polar) to the paraelectric (nonpolar) phase), high pyroelectric coefficient, high spontaneous polarization, low dielectric constant, and constitute important component materials not only useful for infrared detection, but also with vast applications in electronic, optic, and Micro-electromechanical systems (MEMS) devices. However, the preparation of large perfect, and pure single crystals of PbTiO3 is challenging. Additionally, difficulties arise in the application of such bulk crystals in terms of connection to processing circuits, large size, and high voltages required for their operation. A number of thin film fabrication techniques have been proposed to overcome these inadequacies, among which, magnetron sputtering has demonstrated many potentials. By addressing these aspects, the review article aims to contribute to the understanding of the challenges in the field of pyroelectric materials, highlight potential solutions, and showcase the advancements and potentials of pyroelectric perovskite series including PbZrTiO3 (PZT), PbxCa1-x (PZN-PT), etc. for which PbTiO3 is the end member. The review is presented in two parts. Part 1 focuses on material aspects, including preparation methods using magnetron sputtering and material characterization. We take a tutorial approach to discuss the progress made in epitaxial growth of lead titanate-based ceramics prepared by magnetron sputtering and examine how processing conditions may affect the crystalline quality of the growing film by linking to the properties of the substrate/buffer layer, growth substrate temperature, and the oxygen partial pressure in the gas mixture. Careful control and optimization of these parameters are crucial for achieving high-quality thin films with desired structural and morphological characteristics.

Stepwise-design activated high capacitive energy storage in lead-free NaNbO3-based relaxor antiferroelectric ceramics

Although comparable energy storage performance (ESP) has been realized in NaNbO3 (NN)-based antiferroelectric (AFE) ceramics, how to simultaneously realize large energy density (Wrec), large storage efficiency (η), and outstanding thermal stability still remains a remarkable challenge. Herein, by progressively substituting BiFeO3 (BF) and CaTiO3 (CT), we propose a stepwise-design strategy to activate comprehensive exceptional ESP in NN-based relaxor AFE ceramics. The substitution of BF with high spontaneous polarization and CT with high breakdown strength (Eb) into NN generates stabilized AFE R phase, strong tilt distortions of oxygen octahedron, ultrasmall and highly dynamic polar nanoregions, and refined grains, thus manifesting enhanced high-field polarizability, significantly delayed polarization saturation, and ultrahigh Eb macroscopically. With the deliberate stepwise-design route, we realize an optimal overall ESP in 0.6(0.96NN-0.04BF)-0.4CT relaxor AFE ceramics, featuring a high Wrec of 6.84 J/cm3, a large η of 81.5 %, along with super temperature/frequency/fatigue stabilities, which shows great performance merits compared with previous reports. This work demonstrates that stepwise-design engineering approach by manipulating the crucial structures exerts a positive size effect on the polarization and breakdown response of dielectrics, and can be exploited for designing more high-performance energy storage ceramics.

Interpretable Machine Learning to Discover Perovskites with High Spontaneous Polarization

Interpretable Machine Learning to Discover Perovskites with High Spontaneous Polarization

Nanostructured relaxor ferroelectric polymers enable full utilization of nickel-rich cathode at wide-temperature

The sluggish Li+ replenishment and surface structural transformation issues are major bottlenecks that limit the full utilization of Ni-rich cathodes (NLOs) in high-energy rechargeable batteries. Here, a relaxor ferroelectric poly(vinylidene fluoride-trifluoroethylene) (P(VDF + TrFE)) copolymer coated on commercial polypropylene (PP) separator is proposed to tackle these problems for NLO cathodes. It is discovered that the relaxor ferroelectric P(VDF + TrFE) nanostructures with high spontaneous polarization and high dielectric constant at ambient temperature, acts as an ion-selective pump to accelerate the migration of lithium ions and reduce the accumulation of anions at the coating/cathode interface, thereby significantly improving the lithium-ion utilization rate of the cathode, reducing the interfacial side reactions, and stabilizing the cathode structure. As a result, the NCM811/Li cell with the relaxor ferroelectric coating shows extraordinary rate performance and cycling durability at a wide-temperature range of −40 ∼ 55 ℃. This work sheds light on the possibility to improve the electrochemical performance of other intercalated electrode materials by engineering ferroelectric interlayers.

Bismuth layer-structured Bi4Ti3O12-CaBi4Ti4O15 intergrowth ferroelectric films for high-performance dielectric energy storage on Si substrate

Bismuth layer-structured ferroelectrics (BLSFs) have shown a great design capability for electrical energy storage, due to a highly anisotropic lattice and dielectric property. In this work, we add another notch to their qualifications as high energy density dielectrics, by demonstrating an ultrahigh recyclable energy density (Wrec ∼ 151.1 J/cm3 @ 4 MV/cm) and a good energy efficiency (η ∼ 72.0%) in Bi4Ti3O12-CaBi4Ti4O15 intergrowth ferroelectric films integrated on Si. This performance was achieved by the combination of a high spontaneous polarization (Ps) of the intergrown superlattice, and a polycrystalline nanograin microstructure. The high Ps is obtained through design of a special lattice, which determines the up limit of the energy density. On the other hand, the nanograin structure corresponds to a reduce remnant polarization, an intermediate dielectric constant and a delayed polarization saturation, all are ideal features for achieving a high recyclable energy density and energy efficiency. Such a structure is the consequence of a limited grain growth under the effect of a buffer layer. Lastly, a remarkable fatigue-resistance and an excellent charge-retaining ability were exhibited by these lead-free BLSF films. We expect this work will pave the way for designing high performance bismuth layer-structured ferroelectric films targeted for dielectric energy storage applications.

Construction of spontaneously polarized ceramic via synergistic mechanical activation‒Biomimetic mineralization for activating air and water

Spontaneously polarized crystals with intrinsic electric dipole moment have attracted immense interest as excellent functional materials for extensive applications. It is of great significance to engineer sustainable spontaneously polarized materials with fascinating characteristics and performance for activating air and water. Herein, a novel strategy based on the synergy of mechanical activation (MA) and biomimetic mineralization (BM) was created to construct spontaneously polarized ceramic. MA induced the structural damage of clay and promoted the dissolution of ions and the release of free proteins, contributing to the formation of silicate precursor in BM process. After high temperature firing, the silicate precursor in clay was converted to form KCa3AlCa3Si4O16 (hexagonal crystal system, L6 symmetry type, and P63 space group) in the resulting spontaneously polarized ceramic. The non-centrosymmetric structure of KCa3AlCa3Si4O16 and the high intrinsic electric dipole moments contributed by K(1) polyhedrons resulted in high spontaneous polarization (0.2322 μC/cm2) and far-infrared emissivity (0.951) of spontaneously polarized ceramic. In air, spontaneously polarized ceramic can activate H2O and O2 molecules to form negative air ions owing to surface electric field. In water, spontaneously polarized ceramic can disaggregate large water clusters to form small water clusters ascribed to surface electric field and far-infrared emission; water pH can be regulated from weak acidity to approximate neutrality via the capture of electrons by H+ ions to produce releasable hydrogen gas. This work provides great promise for rational design and synthesis of spontaneously polarized materials for functional applications.

Chlorocholine perchlorate is an organic ferroelectric with two-step ladder-like dielectric, second harmonic generation effects, and ferroelectricity.

The simple organic salt chlorocholine perchlorate [ClCH2CH2N(CH3)3 ·ClO4] (CCP) is found to be a molecular ferroelectric with a high theoretical spontaneous polarization (Ps) value up to 17.09 μC cm-2. CCP could undergo two successive order-disorder phase transition at 332 and 365 K with space group changing from Cc to Cmc21 and then P63/mmc, accompanying with unusual two-step ladder-like dielectric, SHG signal with obvious "on/off" contrasts. This finding provides a new instance of further exploring successive thermal-stimuli multi-responsive switching materials applied as switches and sensors.

Electron Beam Induced Current Study of Photocurrent Gain in κ-Ga2O3 Schottky Diodes

The κ-Ga2O3 polytype is attracting attention because of its high spontaneous electric polarization, which exceeds that of III-Nitrides. However, little is known of its transport and photoconductive properties. The electron beam induced current gain effect in Schottky barriers prepared on thick films of κ-Ga2O3 has been studied. It is shown that the gain originates in the depletion region of the Schottky barrier. It is demonstrated that the induced current gain takes place only in some local regions, several which increases with applied bias. Such unusual behavior can be explained by an inhomogeneous distribution of hole traps or by a formation of conductive channels under applied bias.

Optimization of the electrical properties on lead-free barium titanate-based piezoelectric by combining grain growth with orthorhombic-tetragonal phase boundary

Barium titanate-based lead-free piezoceramics are considered as a key material for the fabrication of dielectric capacitors due to their large relative dielectric constant (εr) and are also identified as a remarkable electrocaloric material on account of their low Curie temperature (TC) and high spontaneous polarization (Ps). At this work, to optimize the electrical performances of BaTiO3-based Pb-free piezoceramics, chemical doping was used to tailor their composition. The aim is to boost Curie temperature while sustaining decent electrical properties. Besides, to enlighten the underlying physical mechanisms, first-principles calculations based on atomic coupling, orbital hybridization as well as electron localization were carried out. The experimental results show that the dielectric, ferroelectric, and piezoelectric properties are mainly determined by the orthorhombic-tetragonal (O-T) two-phase coexistence and grain size. Notably, a boosted dielectricity, ferroelectricity, and piezoelectricity accompanied by a raised TC is achieved at x = 0.10 mol%. Moreover, the highest TC∼125.40 ℃ is obtained at x = 0.40 mol% along with a degradation in dielectricity, ferroelectricity, and piezoelectricity.

Achieving High Permittivity Paraelectric Behavior in Mesogen-Free Sulfonylated Chiral Polyethers with Smectic C Liquid Crystalline Self-Assembly

Ferroelectric liquid crystalline polymers (LCPs) with a high spontaneous polarization (Ps) are of great interest for the fabrication of advanced electronic devices. However, conventional ferroelectric LCPs typically exhibit low spontaneous polarization, only around 1 mC/m2. To increase the orientational polarization for ferroelectric LCPs, in this work, we designed mesogen-free comb-shaped LCPs based on isotactic polyepichlorohydrin, which contained highly dipolar sulfonyl groups (dipole moment of 4.5 Debye) in the side chains. The goal was to increase dipole density and induce ferroelectric switching. In this new series of mesogen-free LCPs, the sulfonyl groups were first moved away from the main chain to mitigate strong dipole–dipole interactions. Second, methyl-branched alkyl side chains were implemented to decrease the crystallizability and induce the Smectic C (SmC) self-assembly. Intriguingly, these SmC samples, for the first time, exhibited typical paraelectric behavior (i.e., slim S-shaped single hysteresis loops) with a high dielectric constant in the range of 20–30. Learning from the knowledge obtained from this study, we will be able to design new mesogen-free LCPs with tailor-made dipole–dipole interactions and realize ferroelectricity.

Ferroelectric field effect transistors for electronics and optoelectronics

Ferroelectric materials have shown great value in the modern semiconductor industry and are considered important function materials due to their high dielectric constant and tunable spontaneous polarization. A ferroelectric field effect transistor (FeFET) is a field effect transistor (FET) with ferroelectric polarization field introduced to regulate carriers in semiconductors. With the coupling of ferroelectric and semiconductor, FeFETs are attractive for advanced electronic and optoelectronic applications, including emerging memories, artificial neural networks, high-performance photodetectors, and smart sensors. In this review, representative research results of FeFETs are reviewed from the perspective of structures and applications. Here, the background and significance of ferroelectrics and FeFETs are given. Furthermore, methods of building FeFETs in different structures and physical models describing the characteristics of FeFET are introduced. Important applications of FeFETs in electronics and optoelectronics are presented, with a comparison of performance between FeFETs and FETs without ferroelectrics, including memories and memristive devices, photodetectors, negative capacitance FETs, sensors, and multifunctional devices. Finally, based on the above discussions, promising applications and challenges of FeFETs are summarized.

Realizing high energy density in BiFeO3-based ceramics capacitors via bandgap engineering and polarization optimization

BiFeO3-based lead-free ferroelectrics possess high spontaneous polarization. Nevertheless, achieving ultrahigh recoverable energy density in BiFeO3-based ceramics is limited by large remanent polarization and insufficient breakdown strength. Herein, (0.7-x)BiFeO3-0.3Ba(Hf0.05Ti0.95)O3-xNaTaO3 ceramics were designed and prepared. It exhibited a high recoverable energy density of 6.3 J/cm3 and high efficiency of 86.6 % due to the contribution of large breakdown strength and optimized polarization (high maximum polarization and small remanent polarization). These contributions stem from NaTaO3 being introduced into the 0.7BiFeO3-0.3Ba(Hf0.05Ti0.95)O3 matrix, which successfully brought in widened bandgap Eg, increased resistivity, and enhanced relaxor behavior. Large breakdown strength is also promoted by dense microstructure and decreased average grain size. This work proves that the strategies of bandgap engineering and polarization optimization for improving energy storage performance in BiFeO3 are practicable.

Spatially-Resolved Study of the Electronic Transport and Resistive Switching in Polycrystalline Bismuth Ferrite

Ferroelectric materials attract much attention for applications in resistive memory devices due to the large current difference between insulating and conductive states and the ability of carefully controlling electronic transport via the polarization set-up. Bismuth ferrite films are of special interest due to the combination of high spontaneous polarization and antiferromagnetism, implying the possibility to provide multiple physical mechanisms for data storage and operations. Macroscopic conductivity measurements are often hampered to unambiguously characterize the electric transport, because of the strong influence of the diverse material microstructure. Here, we studied the electronic transport and resistive switching phenomena in polycrystalline bismuth ferrite using advanced conductive atomic force microscopy (CAFM) at different temperatures and electric fields. The new approach to the CAFM spectroscopy and corresponding data analysis are proposed, which allow deep insight into the material band structure at high lateral resolution. Contrary to many studies via macroscopic methods, postulating electromigration of the oxygen vacancies, we demonstrate resistive switching in bismuth ferrite to be caused by the pure electronic processes of trapping/releasing electrons and injection of the electrons by the scanning probe microscopy tip. The electronic transport was shown to be comprehensively described by the combination of the space charge limited current model, while a Schottky barrier at the interface is less important due to the presence of the built-in subsurface charge.

A nickel(ii)-based one-dimensional organic-inorganic halide perovskite ferroelectric with the highest Curie temperature.

Organic-inorganic halide perovskites (OIHPs) are very eye-catching due to their chemical tunability and rich physical properties such as ferroelectricity, magnetism, photovoltaic properties and photoluminescence. However, no nickel-based OIHP ferroelectrics have been reported so far. Here, we designed an ABX3 OIHP ferroelectric (3-pyrrolinium)NiCl3, where the 3-pyrrolinium cations are located on the voids surrounded by one-dimensional chains composed of NiCl6-face-sharing octahedra via hydrogen bonding interactions. Such a unique structure enables the (3-pyrrolinium)NiCl3 with a high spontaneous polarization (P s) of 5.8 μC cm-2 and a high Curie temperature (T c) of 428 K, realizing dramatic enhancement of 112 and 52 K compared to its isostructural (3-pyrrolinium)MCl3 (M = Cd, Mn). To our knowledge, remarkably, (3-pyrrolinium)NiCl3 should be the first case of nickel(ii)-based OIHP ferroelectric to date, and its T c of 428 K (35 K above that of BaTiO3) is the highest among all reported one-dimensional OIHP ferroelectrics. This work offers a new structural building block for enriching the family of OIHP structures and will inspire the further exploration of new nickel(ii)-based OIHP ferroelectrics.

A wide range room temperature antiferroelectric liquid crystal mixture with moderate spontaneous polarization and sub-millisecond switching time

A room-temperature antiferroelectric liquid crystal (AFLC) mixture has been prepared by doping two chiral fluorinated compounds into a four-component achiral phenyl pyrimidine-based host matrix. The suitability of the mixture for practical applications has been tested by optical polarizing microscopy, synchrotron X-ray diffraction, frequency-dependent dielectric, and electro-optic studies. The mixture possesses an antiferroelectric phase over a wide temperature range (nearly 82 °C) followed by a paraelectric phase for 13.7 °C. It is found to display very fast switching between 243 and 45 μs at the driving voltage of 3.2 V/μm in the SmC*A phase. At 20 °C, the mixture exhibits a moderately high spontaneous polarization (137 nC/cm2), low viscosity (1.01 Pa s) and fast switching (240μs). The formulated mixture is thus expected to be suitable for use in fast-response AFLC-based display devices.

Smectic C Self-Assembly in Mesogen-Free Liquid Crystalline Chiral Polyethers with Sulfonylated Methyl-Branched Side Chains.

To realize advanced electrical applications for ferroelectric liquid crystalline polymers, high spontaneous polarization (Ps ) is highly desired. However, current ferroelectric liquid crystalline polymers usually exhibit a low Ps . In this work, mesogen-free, chiral polyethers containing sulfonylated methyl-branched alkyl side chains with a (CH2 )3 O spacer between the sulfonyl and the branched alkyl groups are designed and synthesized. In contrast to the linear n-alkyl side chains, the methyl-branched alkyl side chains induce chain tilting in the smectic layers. When double chirality exists in both the main chain and the side chains, a crystalline structure is observed after mechanical stretching. Intriguingly, when single chirality exists in either the backbone or the side chains, a liquid crystalline smectic C phase is obtained. The electric displacement-electric field study, however, does not show typical ferroelectric switching, although the dielectric constants are relatively high for these liquid crystalline polymers. This is likely because the dipole-dipole interactions among neighboring sulfonyl groups along the main chain are so strong that the ferroelectric switching is hindered in the samples. For the future work, it is desired to weaken the dipole-dipole interaction to achieve ferroelectricity in these mesogen-free liquid crystalline polymers.