Ferroelectric Phase Transition Research Articles

The interplay between liquid–liquid and ferroelectric phase transitions in supercooled water

The distinctive characteristics of water, evident in its thermodynamic anomalies, have implications across disciplines from biology to geophysics. Considered a valid hypothesis to rationalize its unique properties, a liquid-liquid phase transition in water below the freezing point, in the so-called supercooled regime, has nowadays been observed in several molecular dynamics simulations and is being actively researched experimentally. The hypothesis of ferroelectric phase transition in supercooled water can be traced back to 1977, due to Stillinger. In this work, we highlight intriguing and far-reaching implications of water: The ferroelectric and liquid-liquid phase transitions can be designed as two facets of the same underlying phenomenon. Our results are based on the analysis of extensive molecular dynamics simulations and are explained in the context of a classical density functional theory in mean-field approximation valid for a polar liquid, where dipolar interaction is treated perturbatively. The theory underpins the potential role of ferroelectricity in promoting the liquid-liquid phase transition, being the density-polarization coupling inherent in the dipolar interaction potential. The existence of ferroelectric order in supercooled low-density liquid water is confirmed by the observation in molecular dynamics simulations of collective modes in space-time polarization correlation functions, traceable to spontaneous breaking of continuous rotational symmetry. Our work sheds light on water's supercooled behavior and opens the door to experimental investigations of the static and dynamic behavior of water's polarization.

Ferroelectric, Switchable Dielectric and Nonlinear Optical Properties in Inorganic-Organic Lead-Free 1D Hybrids Based on Bi(III) and Azetidine: (C3NH8)2[BiCl5], (C3NH8)2[BiBr5

This study investigates lead-free organic-inorganic hybrids (C3NH8)2[BiCl5] (ABC) and (C3NH8)2[BiBr5] (ABB), focusing on their structural, dielectric, ferroelectric, and optical properties. Both compounds exhibit paraelectric (I) to ferroelectric (II) phase transitions (PTs) at 230/233 K and 228/229 K, respectively, transitioning from orthorhombic (Pnma) to monoclinic (P21) phases, with distorted [BiX6]3- octahedra forming 1D chains. Quasielastic neutron scattering and solid-state 1H NMR studies reveal the localized motion of azetidinium cations. Dielectric measurements of ABC and ABB show step-like permittivity changes by 11-12 units post-transition I → II, demonstrating reversible switching behavior. Absorption studies reveal band gaps of 3.24 eV for ABC and 2.76 eV for ABB, classifying them as insulators. Luminescence spectra at 77K display 578 nm (ABC) and 708 nm (ABB) emissions, attributed to 3P1,0 → 1S0 transitions. Both compounds demonstrate stable second harmonic generation (SHG) switching of the on-off type. The switching performance is evaluated over multiple thermal cycles using the treq metric, which decreases with increasing temperature change rate and indicates that ABB's SHG switching is approximately 30% faster than that of ABC.

Directly measured electrocaloric heat in multilayer capacitors of lead scandium tantalate

Isothermal electrocaloric (EC) heat is a key—but rarely reported—parameter for cooling applications. Here, we employ calorimetry with large-area Peltiers (10 × 10 mm2) to study a multilayer capacitor (MLC) of well-ordered PbSc0.5Ta0.5O3 (PST) with a first-order ferroelectric phase transition. Our direct measurements of isothermal EC heat are consistent with complementary EC measurements of similar MLCs that display large EC effects, i.e., indirect EC measurements and direct measurements of adiabatic EC temperature change [Nair et al., Nature 575, 468 (2019)]. Using a field of 7.9 V μm−1, the EC heat associated with the electrically active PST peaks at 11 MJ m−3 near 300 K. At higher temperatures, as one approaches the critical point, the transition is seen to become less first order. Separately, we find that the inactive PST compromises quasi-direct EC measurements. In the future, isothermal EC heat should be directly measured as a matter of routine.

Softening of the optical phonon by reduced interatomic bonding strength without depolarization.

Softening of the transverse optical (TO) phonon, which could trigger ferroelectric phase transition, can usually be achieved by enhancing the long-range Coulomb interaction over the short-range bonding force1, for example, by increasing the Born effective charges2. However, it suffers from depolarization effects3,4 as the induced ferroelectricity is suppressed on size reduction of the host materials towards high-density nanoscale electronics. Here, we present an alternative route to drive the TO phonon softening by showing that the abnormal soft TO phonon in rocksalt-structured ultrawide-bandgap BeO (ref. 5) is mainly induced by a substantial reduction in the short-range bonding interaction due to the Be-O bond stretching caused by an electron cloud-overlap-induced Coulomb repulsion between two adjacent oxygen ions that are arranged octahedrally around an extremely small Be ion. We further demonstrate the emergence of robust ferroelectricity in strain-induced perovskite BaZrO3 and ultrathin HfO2 and ZrO2 films6,7 grown epitaxially on lattice-mismatched SiO2/Si substrate arising from the softening of the TO phonon driven by a reduction in the short-range bonding strength of biaxial strain-induced stretching bonds. These findings shed light on developing a unified theory for ferroelectricity enhancement in ultrathin films free from depolarization fields by tailoring chemical bonds using ionic radius differences, strains, doping and lattice distortions.

Topological data analysis assisted machine learning for polar topological structures in oxide superlattices

Ferroelectric topological phases and phase transitions have been extensively investigated recently due to the rich physical insights and potential applications in next-generation electronic devices. However, precisely predicting the topological phase transitions under different internal and external conditions in polar oxide superlattice systems is challenging due to the complex energy competitions and highly nonlinear kinetics involved. Herein, we adopted a state-of-the-art mathematical concept called “persistent homology” from topological data analysis to extract the essential topological features for the polarization data in various topological structures. By implementing the persistent image as the descriptor, support vector regression (SVR) based convolutional neural network (CNN) models are developed for the automated and high precision classification and regression of topological states based on high-dimensional phase-field simulation data of the PTO/STO superlattice. Using this method, we can automatically construct the strain and electric field phase diagrams in seconds with high throughput phase-field data. We hope to spur further interest in the integration of state-of-the-art mathematical tools, machine learning algorithms, and condensed matter physics for predictions of topological phase transitions.

Strain-induced ferroelectric phase transition and second-harmonic generation enhancement in NbOCl2 monolayer

Strain-induced ferroelectric phase transition and second-harmonic generation enhancement in NbOCl2 monolayer

Improving piezoelectric performance in PMN-0.26 PT single crystal via low frequency AC poling

In this experiment, the alternating current poling (ACP) was applied to the 0.74 Pb(Mg1/3Nb2/3)O3-0.26PbTiO3 (PMN-0.26 PT) single crystal to explore the impact of low frequency (0.1 Hz) ACP on electrical performance. When the poling condition is loading 5 cycles at 14 kV/cm, high piezoelectric coefficient d33 of 1780 pC/N and giant dielectric constant of 5881 are obtained for the ACP treatment sample, enhanced 42.4 % and 14.3 % by contrast with the conventional direct current poling (DCP), respectively. The values of coercive field, maximum strain, and converse piezoelectric constant d33∗ vary considerably around the ferroelectric phase transition detected by polarization-electric field, as well as bipolar and unipolar electric field-induced strain hysteresis loops. In addition, the domain configuration of the ACP sample presents a more periodic stripe-like structure with narrower width and relatively more uniformity after three months aging as compared with the DCP sample, showing the importance of domain engineering in enhancing electrical performance of ferroelectric single crystals.

The origin of ferroelectricity in HfO2 from orbital hybridization and covalency

Fluorite-structured HfO2 ferroelectrics exhibit remarkable ferroelectricity owing to the robust thickness scalability, rendering them promising for next-generation ferroelectric memories. Unlike the well-understood perovskite structured ferroelectrics, such as Pb(Zr,Ti)O3, the origin of ferroelectricity in HfO2 remains elusive, which impedes the experimental fabrication of pure and stable ferroelectric orthorhombic phase in films. This study seeks to elucidate its origin by analyzing the covalent nature of local chemical bonding and changes in orbital hybridization and by catching the typical feather of the half-unit-cell spacer/polar layer in the orthorhombic phase. Notably, we find that the differences in the hybridization intensity of the 2s orbitals of two types of O atoms (OI and OII) and 5d orbitals of Hf atoms play a crucial role in inducing ferroelectric distortion. Furthermore, we demonstrate that the intrinsic mechanisms of stress in enhancing the ferroelectricity of HfO2 originate from the modulation of orbital hybridization intensity of the Hf–O bonds. These insights provide a vital theoretical foundation for further exploration of ferroelectric phase transitions and property modulation in HfO2 and similar fluorite-structured ferroelectrics.

Efek Pendoping Nd3+ Pada Senyawa BaBi2-xNdxNb2O9 Terhadap Struktur, Sifat Dielektrik Dan Optik

The Aurivillius compound with formula BaBi2-xNdxNb2O9 (x = 0.05, 0.1, 0.2, and 0.4) has been successfully synthesized using the molten salt method, showing potential as a ferroelectric material. The impact of Nd3+ substitution on the structure, morphology, dielectric, and optical properties has been systematically analyzed. XRD data refinement confirms that BaBi2-xNdxNb2O9 (BBNN) exhibits an orthorhombic structure with an A21am space group. Anisotropic plate-like grains were observed across all samples, decreasing their size as Nd3+ content increases. The ferroelectric transition temperature (Tc) decreases due to structural distortion caused by the reduction of the lone pair 6s2 electron effect of Bi3+ when substituted with Nd3+. Moreover, this structural distortion also contributes to an increase in bandgap energy (Eg). The diffuse ferroelectric phase transition is characterized by a broadened Tc peak induced by Nd3+ substitution due to increased cationic disruption in the bismuth layers. The ferroelectric phase with a lower and broader Tc suggests that the x = 0.4 sample has the potential for electrocaloric applications.

Giant electro-optic response in transparent rhombohedral ferroelectric Sm-PIN-PMN-PT crystal based on domain engineering

The relaxor ferroelectric crystal Pb(Mg1/3Nb2/3)O3-xPbTiO3 (PMN-PT), located near the morphotropic phase boundary (MPB), exhibits exceptionally high piezoelectric and electro-optic (EO) responses. Nevertheless, lower optical transparency and phase transition temperature of PMN-PT limit its optical applications. The ternary system Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 (PIN-PMN-PT) holds promise in addressing these challenges with a higher Curie temperature. Additionally, specific ferroelectric domain polarization techniques can eliminate domain scattering, substantially enhancing the transparency of the crystal. In this study, we explore the optical properties of Sm-doped PIN-PMN-PT. We achieve a 2R domain-engineered state by polarizing along the (110) direction of the crystal. The high transparency allows us to extract an effective EO coefficient of up to 431.5 pm/V from the Sm-PIN-PMN-PT crystal at the telecommunications wavelength. Second-harmonic generation (SHG) probing verified the domain-engineered state in Sm-PIN-PMN-PT. The temperature-dependent SHG reveals the ferroelectric phase transition process, laying the groundwork for studying the stability of the EO response. The Sm-PIN-PMN-PT crystal exhibits an exceptionally high EO coefficient, which is crucial for the development of enhanced EO devices with high integration and low driving voltages.

Phase transitions in typical fluorite-type ferroelectrics

While ferroelectric hafnia (HfO2) has become a technically important material for microelectronics, the physical origin of its ferroelectricity remains poorly understood. The tetragonal P42/nmc phase is commonly assigned as its paraelectric mother phase but has no soft mode at the Brillouin zone center. In this work, we propose that the paraelectric—ferroelectric transition in the fluorite-type Pca21 ferroelectric family can be described by a Pcca—Pca21 transition, where the Pcca mother phase will evolve into either the Pca21 ferroelectric phase or the centrosymmetric P21/c monoclinic phase, depending on the strain conditions. The Pcca phase is directly linked to both phases in the context of continuous phase transition. Hafnia is regarded as a special case of this family in that it has accidental atomic degeneracy because all anions are oxygen. The theory is also correlated with the seven-coordination theory that explains the ferroelectricity in hafnia from a chemical perspective. In addition, the strain conditions to promote the ferroelectric phase in hafnia are discussed.

Quantum transport simulations of α-In2Se3 antiferroelectric tunnel junctions

Due to semiconductor characteristics and non-volatile ferroelectricity, two-dimensional (2D) In2Se3 are considered as potential candidates for next-generation storage and computing devices. Based on first principles calculations, we designed antiferroelectric tunnel junctions (AFTJs) using α-In2Se3 as channels. The tunneling barrier height is controlled by the antiferroelectric to ferroelectric (AFE-FE) phase transition of the channel. A maximum current ratio up to 426 is predicted between the AFE and FE phases, enabling the two distinct memory states. By constructing two AFTJs into a calculation unit, the total current can either be fully turned on/off or function as XNOR logic with bias as inputs. Our research provides a new approach to implementing integrated storage and computing devices, making it possible for efficient data-centric applications in the era of big data.

Active control of thermal conductivity of low-dimensional α -PbS by strain-induced ferroelectric

Active control of heat transfer in nanostructured materials is crucial for the development of microelectronic devices. Thermal switch is a typical heat management device, which has attracted widespread attention. In this work, based on first-principles calculations, we propose a two-dimensional thermal switch based on the strain-induced ferroelectric phase transition in α-PbS. It is found that thermal conductivity can be significantly reduced by external strain and a room temperature two-dimensional thermal switch with a switch ratio of 3.7 can be constructed. The calculated phonon lifetime and scattering rate reveal that phonons around 2 THz frequency range predominantly contribute to the modulation in thermal conductivity when the strain is smaller than 2.0%. A detailed analysis on phonon dispersion indicates that these phonons are LO2 and TO3 branches. When the strain is larger than 2.0%, the decrease in phonon group velocity leads to the reduction in thermal conductivity. Our work elucidates the mechanisms for changes in the thermal conductivity of α-PbS under strain and provides a low-dimensional thermal switch, which is promising for future applications in microelectronic devices.

Ferroelectricity Induced by a Combination of Crystallographic Chirality and Axial Vector.

Ferroelectric materials compatible with magnetism and/or conductive properties provide a platform for exploring unconventional phenomena, such as the magnetoelectric effect, nonreciprocal responses, and nontrivial superconductivity. Though recent studies on multiferroics have offered several approaches, the search for magnetic and/or conducting ferroelectric materials is still a challenging issue under the traditional "d0-ness" rule, refusing active d electrons. Here, we propose the emergence of ferroelectricity through a combination of crystallographic chirality and axial vector, accepting even non-d0 magnetic ions. This proposal is demonstrated in quasi-one-dimensional magnetic systems SrM2V2O8 (M = Ni, Mg, and Co). The ferroelectric phase transition is observed by measurements of neutron powder diffraction and dielectric properties in all compositions. Structural analyses and first-principles calculations indicate that these magnetic compounds are identified as proper-type ferroelectrics whose ferroelectric phase transition is achieved by spiral motions of crystallographic screw chains formed by edge-shared MO6 octahedra, considered as the combination of locally defined chirality and axial vector. Computationally predicted magnitude of spontaneous polarization of SrM2V2O8 reaches ∼100 μC/cm2, comparable to that of conventional ferroelectrics, despite the incorporation of non-d0 magnetic elements. The mechanism proposed in this study offers a unique approach to the exploration of new ferroelectrics beyond the traditional paradigms.

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.

Quantum phase transitions and cat states in cavity-coupled quantum dots

We study double quantum dots coupled to a quasistatic cavity mode with high mode-volume compression allowing for strong light-matter coupling. Besides the cavity-mediated interaction, electrons in different double quantum dots interact with each other via dipole-dipole (Coulomb) interaction. There is a first-order cavity-induced ferroelectric quantum phase transition when the attractive dipolar interaction is smaller than the critical value defined by the energy splitting in DQDs and a smooth transition, otherwise. We show that, in the smooth transition region, both the ground and the first excited states of an array of double quantum dots are cat states. Such states are actively discussed as high-fidelity qubits for quantum computing, and thus our proposal provides a platform for semiconductor implementation of such qubits. We also calculate gauge-invariant observables such as the net dipole moment, the optical conductivity, and the absorption spectrum beyond the semiclassical approximation. The results are robust against cavity losses and variations of system parameters. Published by the American Physical Society 2024

A Multiferroic Spin-Crossover Molecular Crystal.

Spin-crossover (SCO) ferroelectrics with dual-function switches have attracted great attention for significant magnetoelectric application prospects. However, the multiferroic crystals with SCO features have rarely been reported. Herein, a molecular multiferroic Fe(II) crystalline complex [FeII(C8-F-pbh)2] (1-F, C8-F-pbh = (1Z,N'E)-3-F-4-(octyloxy)-N'-(pyridin-2-ylmethylene)-benzo-hydrazonate) showing the coexistence of ferroelectricity, ferroelasticity, and SCO behavior is presented for the first time. By H/F substitution, the low phase transition temperature (270K) of the non-fluorinated parent compound is significantly increased to 318K in 1-F, which exhibits a spatial symmetry breaking 222F2 type ferroelectric phase transition with clear room-temperature ferroelectricity. Besides, 1-F also displays a spin transition between high- and low-spin states, accompanied by the d-orbital breaking within the t2g 4eg 2 and t2g 6eg° configuration change of octahedrally coordinated FeII center. Moreover, the 222F2 type ferroelectric phase transition is also a ferroelastic one, verified by the ferroelectric domains reversal and the evolution of ferroelastic domains. To the knowledge, 1-F is the first multiferroic SCO molecular crystal. This unprecedented finding sheds light on the exploration of molecular multistability materials for future smart devices.

Intrinsic Out-Of-Plane and In-Plane Ferroelectricity in 2D AgCrS2 with High Curie Temperature.

2D ferroelectric materials have attracted extensive research interest due to potential applications in nonvolatile memory, nanoelectronics and optoelectronics. However, the available 2D ferroelectric materials are scarce and most of them are limited by the uncontrollable preparation. Herein, a novel 2D ferroelectric material AgCrS2 is reported that are controllably synthesized in large-scale via salt-assist chemical vapor deposition growth. By tuning the growth temperature from 800 to 900°C, the thickness of AgCrS2 nanosheets can be precisely modulated from 2.1 to 40nm. Structural and nonlinear optical characterizations demonstrate that AgCrS2 nanosheet crystallizes in a non-centrosymmetric structure with high crystallinity and remarkable air stability. As a result, AgCrS2 of various thicknesses display robust ferroelectric polarization in both in-plane (IP) and out-of-plane (OOP)directions with strong intercorrelation and high ferroelectric phase transition temperature (682 K). Theoretical calculations suggest that the ferroelectricity in AgCrS2 originates from the displacement of Ag atoms in AgS4 tetrahedrons, which changes the dipole moment alignment. Moreover, ferroelectric switching is demonstrated in both lateral and vertical AgCrS2 devices, which exhibit exotic nonvolatile memory behavior with distinct high and low resistance states. This study expands the scope of 2D ferroelectric materials and facilitates the ferroelectric-based nonvolatile memory applications.

Seeing ferroelectric phase transitions.

Seeing ferroelectric phase transitions.

The First Discovery of Spherical Carborane Molecular Ferroelectric Crystals

AbstractCarborane compounds, known for their exceptional thermal stability and non‐toxic attributes, have garnered widespread utility in medicine, supramolecular design, coordination/organometallic chemistry, and others. Although there is considerable interest among chemists, the integration of suitable carborane molecules into ferroelectric materials remains a formidable challenge. In this study, we employ the quasi‐spherical design strategy to introduce functional groups at the boron vertices of the o‐carborane cage, aiming to reduce molecular symmetry. This approach led to the successful synthesis of the pioneering ferroelectric crystals composed of cage‐like carboranes: 9‐OH‐o‐carborane (1) and 9‐SH‐o‐carborane (2), which undergo above‐room ferroelectric phase transitions (Tc) at approximately 367 K and 347 K. Interestingly, 1 and 2 represent uniaxial and multiaxial ferroelectrics respectively, with 2 exhibiting six polar axes and as many as twelve equivalent polarization directions. As the pioneering instance of carborane ferroelectric crystals, this study introduces a novel structural archetype for molecular ferroelectrics, thereby providing fresh insights into the exploration of molecular ferroelectric crystals with promising applications.