Ferroelectric Research Articles

Polymerization‐induced Chiral Self‐assembly for the In situ Construction, Modulation, Amplification and Applications of Asymmetric Suprastructures

AbstractIn the polymerization‐induced chiral self‐assembly (PICSA) process, chiral functional monomers undergo spontaneous supramolecular self‐assembly and asymmetric stacking during living polymerization, leading to the in situ generation of chiroptical polymer assemblies characterized by diverse morphologies. The PICSA strategy facilitates precise control and manipulation of both non‐covalent supramolecular helices and covalent macromolecular helices within aggregated cores, thereby driving significant advancements in fields such as chiral recognition materials, asymmetric catalysts, nonlinear optical materials, and ferroelectric liquid crystals (LC). This minireview summarizes recent developments in the in situ chiroptical construction and modulation associated with the PICSA methodology. Furthermore, it seeks to elucidate emerging PICSA systems founded on various living polymerization mechanisms, exploring hierarchical chirality transfer processes and the pathway complexities in both equilibrium and non‐equilibrium conditions. This minireview also presents several illustrative examples that demonstrate the practical applications of chiral polymer materials synthesized through the PICSA approach, thereby illuminating future opportunities in this innovative field.

A nonvolatile magnon field effect transistor at room temperature

Information industry is one of the major drivers of the world economy. Its rapid growth, however, leads to severe heat problem which strongly hinders further development. This calls for a non-charge-based technology. Magnon, capable of transmitting spin information without electron movement, holds tremendous potential in post-Moore era. Given the cornerstone role of the field effect transistor in modern electronics, creating its magnonic equivalent is highly desired but remains a challenge. Here, we demonstrate a nonvolatile three-terminal lateral magnon field effect transistor operating at room temperature. The device consists of a ferrimagnetic insulator (Y3Fe5O12) deposited on a ferroelectric material [Pb(Mg1/3Nb2/3)0.7Ti0.3O3 or Pb(Zr0.52Ti0.48)O3], with three Pt stripes patterned on Y3Fe5O12 as the injector, gate, and detector, respectively. The magnon transport in Y3Fe5O12 can be regulated by the gate voltage pulses in a nonvolatile manner with a high on/off ratio. Our findings provide a solid foundation for designing energy-efficient magnon-based devices.

Mapping domain structures near a grain boundary in a lead zirconate titanate ferroelectric film using X-ray nanodiffraction

The effect of an electric field on local domain structure near a 24° tilt grain boundary in a 200 nm-thick Pb(Zr0.2Ti0.8)O3 bi-crystal ferroelectric film was probed using synchrotron nanodiffraction. The bi-crystal film was grown epitaxially on SrRuO3-coated (001) SrTiO3 24° tilt bi-crystal substrates. From the nanodiffraction data, real-space maps of the ferroelectric domain structure around the grain boundary prior to and during application of a 200 kV cm−1 electric field were reconstructed. In the vicinity of the tilt grain boundary, the distributions of densities of c-type tetragonal domains with the c axis aligned with the film normal were calculated on the basis of diffracted intensity ratios of c- and a-type domains and reference powder diffraction data. Diffracted intensity was averaged along the grain boundary, and it was shown that the density of c-type tetragonal domains dropped to ∼50% of that of the bulk of the film over a range ±150 nm from the grain boundary. This work complements previous results acquired by band excitation piezoresponse force microscopy, suggesting that reduced nonlinear piezoelectric response around grain boundaries may be related to the change in domain structure, as well as to the possibility of increased pinning of domain wall motion. The implications of the results and analysis in terms of understanding the role of grain boundaries in affecting the nonlinear piezoelectric and dielectric responses of ferroelectric materials are discussed.

Two-Dimensional Topological Ferroelectric Metal with Giant Shift Current.

The pursuit for "ferroelectric metal," which combines seemingly incompatible spontaneous electric polarization and metallicity, has been assiduously ongoing but remains elusive. Unlike traditional ferroelectrics with a wide band gap, ferroelectric (FE) metals can naturally incorporate nontrivial band topology near the Fermi level, endowing them with additional exotic properties. Here, we show first-principles evidence that the metallic PtBi_{2} monolayer is an intrinsic two-dimensional (2D) topological FE metal, characterized by out-of-plane polarization and a moderate switching barrier. Moreover, it exhibits a topologically nontrivial electronic structure with Z_{2} invariant equal to 1, leading to a significant FE bulk photovoltaic effect. A slight strain can further enhance this effect to a remarkable level, which far surpasses that of previously reported 2D and 3D FE materials. Our Letter provides an important step toward realizing intrinsic monolayer topological FE metals and paves a promising way for future nonlinear optical devices.

Crystallite size and phase purity in Pb1-xSrxTiO3 ferroelectric perovskites for biomedical applications via controlled sintering

ABSTRACT Lead strontium titanate (Pb1-xSrx)TiO3 (PST) is a ferroelectric perovskite material with tunable properties, including Curie temperature, spontaneous polarization, and high dielectric permittivity, making it promising for advanced biomedical applications, such as biosensors, bioimaging, and light-activated therapeutics. This study investigates the effect of varying sintering temperatures on the crystallite size and phase purity of PST, aiming to optimize its performance for biomedical devices. PbCO3, SrCO3, and TiO2 powders were processed via ball milling for 58 hours, followed by sintering at temperatures ranging from 500°C to 1100°C. Laser diffraction particle size analysis and X-ray diffraction (XRD) were used to assess the particle size and crystal phase transformations. The results demonstrate that higher sintering temperatures improve the PST phase composition, reducing impurities and enhancing crystallite growth. The most significant crystal growth was observed at 900°C, while the optimal phase purity and crystallite size (91.5 nm) were achieved at 1100°C, producing 100% single-phase PST. These findings emphasize the critical role of sintering temperature in tailoring PST’s properties, enhancing its suitability for electronic and microelectronic biomedical devices. Controlled sintering in perovskite materials opens new pathways for their application in medical diagnostics and therapeutic technologies.

Effect of Electric Field on Carbon Encapsulation and Catalytic Activity of Pd for Efficient Formic Acid Decomposition

Utilizing carbon coated ferroelectric materials to introduce polarization‐induced electric field (PIEF) stimulates research of electric field‐assisted catalysts for various reactions. However, effect of PIEF on carbon coating mechanism has not been studied. Herein, tourmaline nanoparticles (TNPs) with spontaneous dipole moments were applied as the PIEF supplier and sucrose was utilized as the carbon precursor to synthesize carbon coated TNPs (TNP@SC) to uncover the influence of PIEF on the carbon coating and catalytic activity of Pd toward formic acid decomposition (FAD). PIEF enhanced the adsorption capacity of TNPs for the caramelized intermediate species and increased H+ concentration by facilitating water ionization. Polymerization of adsorbed caramelized intermediate species on TNPs was accelerated. Uniformly coated carbon layer with more defects, larger specific surface area, and higher porosity was coated on TNP. Such surface properties of the carbon layer were beneficial for strongly anchoring ultrafine Pd nanoparticles. Owing to the specific properties of carbon layer and existence of PIEF, Pd/TNP@SC exhibited higher FAD activity than the catalysts absent of PIEF. Stronger PIEF leaded to higher initial turnover frequency. This study provides guidance to supply electric field for catalysis.

Enhanced performance of flexible BiFeO3 ferroelectric memory with Mica substrate via SrTiO3 buffer layer

BiFeO3 (BFO) application in flexible wearable devices is garnering interest because of its unique ferroelectric and magnetic properties. However, the integration of high-quality BFO films onto flexible substrates presents significant technical challenges. Here, we successfully fabricated high-quality BFO films on mica substrates by using pulsed laser deposition, and report the fatigue characteristics of BFO films on flexible substrates for the first time. The results demonstrated that, after 108 bipolar switching cycles, the polarization only degraded by 0.28%, indicating superior fatigue characteristics compared to previously reported BFO films. Additionally, the device ferroelectric properties remained largely unchanged, with a bending radius of 3.5 mm. The fabricated flexible Pt/BFO/La0.65Sr0.35MnO3(LSMO)/SrTiO3(STO)/mica non-volatile memory devices exhibited mechanical flexibility and fatigue resistance. These findings not only highlight the potential of flexible BFO films for wearable electronic devices and flexible memory devices, they also provide valuable insight for the future development of high-performance flexible ferroelectric materials.

Exploring Aqueous Solution-Processed Pseudohalide Rare-Earth Double Perovskite Ferroelectrics toward X-Ray Detection with High Sensitivity.

Three-dimensional (3D) pseudohalide rare-earth double perovskites (PREDPs) have garnered significant attention for their versatile physical properties, including ferroelectricity, ferroelasticity, large piezoelectric responses, and circularly polarized luminescence. However, their potential for X-ray detection remains unexplored, and the low Curie temperature (TC) limits the performance window for PREDP ferroelectrics. Here, by applying the chemical regulation strategies involving halogen substitution on the organic cation and Rb/Cs substitution to the PREDP [(R)-M3HQ]2RbEu(NO3)6 [(R)-M3HQ=(R)-N-methyl-3-hydroxylquinuclidinium] with a low TC of 285 K, a novel 3D PREDP ferroelectric [(R)-CM3HQ]2CsEu(NO3)6 [(R)-CM3HQ=(R)-N-chloromethyl-3-hydroxylquinuclidinium] are successfully synthesized, for which the TC reaches 344 K. More importantly, such a strategy endowed [(R)-CM3HQ]2CsEu(NO3)6 with notable X-ray detection capabilities. Centimeter-sized [(R)-CM3HQ]2CsEu(NO3)6 single crystals fabricated from aqueous solutions demonstrated a sensitivity of 1307 μC Gyair -1 cm-2 and a low detectable dose rate of 152 nGyair s-1, the highest sensitivity reported for hybrid double perovskite ferroelectric detectors. This work positions PREDPs as promising candidates for the next generation of eco-friendly optoelectronic materials and also offers substantial insights into the interaction between structure, composition, and functionality in ferroelectric materials.

Extrinsic dielectric response due to domain wall motion in ferroelectric BaTiO[formula omitted]

BaTiO3 (BTO) is a prototypical perovskite ferroelectric, whose dielectric permittivity and loss spectra – which are strongly temperature and frequency dependent – include contributions from inhomogeneous polarization patterns, with domain walls (DWs) being the most common types. In order to elucidate how DWs influence dielectric response, we utilized a continuum approach based on the Landau–Ginzburg theory to model field-dependent properties of polydomain tetragonal phase of BTO near room temperature and above. A system with 180∘ DWs was evaluated as a case study, with both position-resolved and volume-averaged dielectric susceptibility and loss computed at different temperatures for a range of applied field frequencies and amplitudes. Our results demonstrate that cooperative dipole fluctuations in the vicinity of the DW provide a large (extrinsic) contribution to the system dielectric response relative to the intrinsic contribution stemming from within the domain. Dynamics of the DW profile fluctuations under applied field can be represented by a combination of breathing and sliding vibrational motions, with each exhibiting distinct dependence on the field frequency and amplitude. The implications of this behavior are important for understanding and improving control of coupled functional properties in ferroelectric materials, including their dielectric, electromechanical, and electrooptical responses. Furthermore, this investigation provides a computational benchmark for future studies and can be readily extended to other topological polarization patterns in ferroelectrics.

Observation of converse flexoelectric effect in topological semimetals

A strong coupling between electric polarization and elastic deformation in solids is an important factor in creating useful electromechanical nanodevices. Such coupling is typically allowed in insulating materials with inversion symmetry breaking as exemplified by the piezoelectric effect in ferroelectric materials. Therefore, materials with metallicity and centrosymmetry have tended to be out of scope in this perspective. Here, we report the observation of giant elastic deformation by the application of an alternating electric current in topological semimetals (V,Mo)Te2, regardless of the centrosymmetry. Considering the crystal and band structures and the asymmetric measurement configurations in addition to the absence of the electromechanical effect in a trivial semimetal TiTe2, the observed effect is discussed in terms of a Berry-phase-derived converse flexoelectric effect in metals. The observation of the flexoelectric effect in topological semimetals paves a way for a new type of nanoscale electromechanical sensors and energy harvesting.

Exploring Aqueous Solution‐Processed Pseudohalide Rare‐Earth Double Perovskite Ferroelectrics toward X‐Ray Detection with High Sensitivity

AbstractThree‐dimensional (3D) pseudohalide rare‐earth double perovskites (PREDPs) have garnered significant attention for their versatile physical properties, including ferroelectricity, ferroelasticity, large piezoelectric responses, and circularly polarized luminescence. However, their potential for X‐ray detection remains unexplored, and the low Curie temperature (TC) limits the performance window for PREDP ferroelectrics. Here, by applying the chemical regulation strategies involving halogen substitution on the organic cation and Rb/Cs substitution to the PREDP [(R)‐M3HQ]2RbEu(NO3)6 [(R)‐M3HQ=(R)‐N‐methyl‐3‐hydroxylquinuclidinium] with a low TC of 285 K, a novel 3D PREDP ferroelectric [(R)‐CM3HQ]2CsEu(NO3)6 [(R)‐CM3HQ=(R)‐N‐chloromethyl‐3‐hydroxylquinuclidinium] are successfully synthesized, for which the TC reaches 344 K. More importantly, such a strategy endowed [(R)‐CM3HQ]2CsEu(NO3)6 with notable X‐ray detection capabilities. Centimeter‐sized [(R)‐CM3HQ]2CsEu(NO3)6 single crystals fabricated from aqueous solutions demonstrated a sensitivity of 1307 μC Gyair−1 cm−2 and a low detectable dose rate of 152 nGyair s−1, the highest sensitivity reported for hybrid double perovskite ferroelectric detectors. This work positions PREDPs as promising candidates for the next generation of eco‐friendly optoelectronic materials and also offers substantial insights into the interaction between structure, composition, and functionality in ferroelectric materials.

Anomalous electrocaloric behaviors in (anti)ferroelectrics: a mini-review.

Solid-state cooling, represented by the electrocaloric effect (ECE) in (anti)ferroelectric materials, has emerged as an alternative green refrigeration technology by virtue of its high efficiency and miniaturization and is expected to substitute conventional vapor-compression. Significant progress has been made in developing high-performance EC materials since its revival. However, anomalous EC behaviors are frequently observed, including asymmetric and negative EC profiles, and the physical mechanism behind this is still under debate. Its rationalization is of great importance since full utilization of anomalous EC behaviors could enhance EC strength and/or cooling capacity. This mini-review gives a brief overview of research advances in EC anomalies in (anti)ferroelectrics with the hope of provoking thought on the design of reconstructed refrigeration cycles and superior EC materials for application in solid-state cooling devices.

Investigation on barrier layers of Pt/BaTiO3/Pt based thin film capacitors

Barium titanate is a ferroelectric material used as a dielectric in thin film capacitors owing to its high dielectric constant. Barrier layers are utilized in these capacitors to improve the capacitors' performance. In this paper, zinc oxide and aluminium oxide are kept on both sides of BaTiO3 as barrier layers in Pt/BT/Pt capacitors and different dielectric properties are studied. The parameters such as capacitance density, leakage current, ESR, dielectric loss and dielectric strength of Pt/BT/Pt capacitors with barrier layers of different sizes are simulated using COMSOL Multiphysics modeling software. Aluminum oxide of 2 nm thickness as a barrier layer gives optimal performance. The leakage current, dielectric loss, capacitance density, equivalent series resistance and dielectric strength of Pt/BT/Pt capacitor are found to be 0.519 mA, 9.62x10‐12, 172.8 fF/µm2, 9.62 kΩ, 108 V/m respectively whereas that of Pt/ALO/BT/ALO/Pt capacitor are found to be 1.56x10‐18A, 7.81x10‐18, 11.6 fF/µm2, 9.01x1015 Ω, 5.05x109 V/m respectively. The low capacitance in Pt/ALO/BT/ALO/Pt capacitor is due to the low dielectric constant of Al2O3 layer. The reduced leakage current and increased equivalent series resistance is due to the low conductivity of the Al2O3 layer. The use of aluminium layer can reduce the electric field leading to improved dielectric strength.

Low Sintering Temperature Effect on Crystal Structure and Dielectric Properties of Lead-Free Piezoelectric Bi0.5Na0.5TiO3-NaFeTiO4

Bi0.5Na0.5TiO3 (BNT) emerges as a promising ferroelectric and piezoelectric lead-free candidate to substitute the contaminant Pb[TixZr1−x]O3 (PZT). However, to obtain optimal ferroelectric and piezoelectric properties, BNT must be sintered at high temperatures. In this work, the reduction of sintering temperature by using iron added to BNT is demonstrated, without significant detriment to the dielectric properties. BNT-xFe with iron from x = 0 to 0.1 mol (∆x = 0.025) were synthesized using high-energy ball milling followed by sintering at 900 °C. XRD analysis confirmed the presence of rhombohedral BNT together with a new phase of NaFeTiO4 (NFT), which was also corroborated using optical and electronic microscopy. The relative permittivity, in the range of 400 to 500 across all the frequencies, demonstrated the stabilization effect of the iron in BNT. Additionally, the presence of iron elevates the transition from ferroelectric to paraelectric structure, increasing it from 330 °C in the iron-free sample to 370 °C in the sample with the maximum iron concentration (0.1 mol). The dielectric losses maintain constant values lower than 0.1. In this case, low dielectric loss values are ideal for ferroelectric and piezoelectric materials, as they ensure minimal energy dissipation. Likewise, the electrical conductivity maintains a semiconductor behavior across a range of 50 Hz to 1 × 106 Hz, indicating the potential of these materials for applications at different frequencies. Additionally, the piezoelectric constant (d33) values decrease slightly when low concentrations of iron are added, maintaining values between 30 and 48 pC/N for BNT-0.025Fe and BNT-0.05Fe, respectively.

Influence of Mg2+ doping on the oxide ion conductivity of layered ferroelectric SrBi2Ta2O9

Layered perovskites structures are an interesting candidate to explore as a potential electrolyte materials for Solid oxide fuel cell (SOFC) applications. However, achieving a high ionic conductivity (∼0.01 S cm⁻1 below 650 °C) remains a significant challenge to lowering the SOFC operating temperatures. SrBi2Ta2O9 (SBT), an Aurivillius-based layered perovskite, is a well-known ferroelectric material with TC of 320 °C. Site exchange and Bi volatility related defects lead to ionic conductivity in SBT above 700 °C. Here, we aim to control the defect chemistry by doping to promote the oxygen vacancies. We show that Mg doping at the Ta-site in the perovskite block results in 4-fold increase in the bulk conductivity of SBT 3.65 × 10−4 S cm−1 and improvement in the ionic transport number from 0.26 to 0.71. The study provides an opportunity to design new oxide ion conductors in layered ferroelectric oxides.

Controlling Long-Term Plasticity in Neuromorphic Computing Through Modulation of Ferroelectric Polarization.

Electrolyte-gated transistors (EGTs) have significant potential for neuromorphic computing because they can control the number of ions by mimicking neurotransmitters. However, fast depolarization of the electric double layer (EDL) makes it difficult to achieve long-term plasticity (LTP). Additionally, most research utilizing organic ferroelectric materials has been focused on basic biological functions, and the impact on nonvolatile memory properties is still lacking. Herein, we present a polyvinylidene fluoride (PVDF)-based ion-gel synaptic device using PVDF and poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)) to implement LTP through the introduction of ferroelectric materials. The PVDF-based polymer slows the escape rate of TFSI anions from the electrolyte/channel layer through residual polarization. The fabricated synaptic devices successfully demonstrate LTP by controlling ion adsorption under the influence of PVDF-based polymers. Furthermore, it implements synaptic functions including paired pulse facilitation (PPF), high-pass filtering, and neurotransmitter control. To validate the potential of neuromorphic computing, we successfully achieved high recognition rates for artificial/convolutional neural network (A/CNN) simulations via sequential adsorption and desorption under ferroelectric polarization with long-term potentiation/depression (LTP/D). This study provides a rational ion adsorption strategy utilizing the ferroelectric polarization caused by the introduction of a PVDF-based polymer in the dielectric layer.

Smectic layer reorientation by surface mode in surface stabilized ferroelectric liquid crystal

Smectic layer reorientation by surface mode in surface stabilized ferroelectric liquid crystal

Superior energy storage performance in NaNbO3‐based lead‐free ceramics under low electric field

AbstractNaNbO3 (NN)‐based materials have attracted widespread attention due to their advanced energy storage performance and eco‐friendliness. However, achieving high recoverable energy storage densities (Wrec) and efficiency (η) typically requires ultrahigh electric fields (E > 300 kV/cm), which can limit practical use. In this work, we present a synergistic strategy that employs the ferroelectric material Bi0.5Na0.5TiO3 (BNT) to augment the Pmax and the linear material Bi0.2Sr0.7TiO3 (BST) to optimize the P–E loops. Furthermore, a two‐step sintering process is implemented to preserve high Pmax values under lower electric field. As a result, ternary (1−x)(0.90NN‐0.10BNT)‐xBST was successfully prepared, achieving a high Wrec of 5.1 J/cm3 and a η of 85% in x = 0.20 samples at a low electric field of 290 kV/cm. Moreover, the x = 0.20 samples showed good frequency stability (1–200 Hz) and temperature stability (27°C–100°C). These results provide guidance for the development of ceramics with high energy storage properties under low electric fields.

Probing ferroelectric phase transitions in barium titanate single crystals via in situ second harmonic generation microscopy

Ferroelectric materials play a crucial role in a broad range of technologies due to their unique properties that are deeply connected to the pattern and behavior of their ferroelectric (FE) domains. Chief among them, barium titanate (BaTiO3; BTO) sees widespread applications such as in electronics but equally is a ferroelectric model system for fundamental research, e.g., to study the interplay of such FE domains, the domain walls (DWs), and their macroscopic properties, owed to BTO’s multiple and experimentally accessible phase transitions. Here, we employ Second Harmonic Generation Microscopy (SHGM) to in situ investigate the cubic-to-tetragonal (at ∼126°C) and the tetragonal-to-orthorhombic (at ∼5°C) phase transition in single-crystalline BTO via three-dimensional (3D) DW mapping. We demonstrate that SHGM imaging provides the direct visualization of FE domain switching as well as the domain dynamics in 3D, shedding light on the interplay of the domain structure and phase transition. These results allow us to extract the different transition temperatures locally, to unveil the hysteresis behavior, and to determine the type of phase transition at play (first/second order) from the recorded SHGM data. The capabilities of SHGM in uncovering these crucial phenomena can easily be applied to other ferroelectrics to provide new possibilities for in situ engineering of advanced ferroic devices.

Modern developments in lasing with liquid crystals

A review of the recent developments in the field of lasing with liquid crystals (LCs) is presented. After an introduction into the principle of lasing the different relevant liquid crystal phases to the field are introduced, namely, the nematic and chiral nematic phase, Blue Phases, twist grain boundary and ferroelectric liquid crystals. The classic examples of liquid crystal lasing are shortly discussed, together with a variety of possibilities for tuning the lasing wavelength, before the modern trends in LC lasing are discussed in detail. These are particularly random lasers, where the effects of nanoparticles, quantum dots and solitons are highlighted, as well as localized surface plasmon resonance. Other modern laser systems that have attracted recent interest, white lasers, whispering gallery mode lasers and those with biological materials, for example, cellulose nanocrystals, are also introduced and the latest developments outlined.