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Tin hypothiodiphosphate (Sn2P2S6) is a ferroelectric semiconductor with electro-optic and photorefractive relevance. The lattice contains Sn2+ ions and (P2S6)4− anionic groups. In the present work, an Sn2P2S6 crystal is doped with Te during growth. Our results show that the Te ions occupy Sn sites and S sites, where they serve as electron and hole traps, respectively. Electron paramagnetic resonance (EPR) spectra from five trapped holes and one trapped electron are observed at low temperatures after exposure to 633 nm light. Spin-Hamiltonian parameters are extracted from the angular dependence of each spectrum. Holes are localized on (P2TeS5)4− units and form (P2TeS5)3− anions, with the five defects corresponding to Te on different S sites within the anion. These defects have large g shifts caused by the tellurium spin–orbit coupling parameter. Four of the five also have an isotropic hyperfine interaction with one Sn ion, which suggests that they have an adjacent Sn vacancy (leaving just one close Sn neighbor). Three trapped-hole spectra are photoinduced at 20 K and two appear after removing the light, warming to 120 K, and then returning to 20 K. Electrons are trapped in pairs at Te4+ ions occupying Sn2+ sites when the crystal is exposed to 633 nm light while at 20 K. The Te2+ ions that are formed have no observable EPR spectrum. Warming to 100 K releases one electron from Te2+ ions that have an adjacent Sn vacancy, and an EPR spectrum from Te3+ ions (5s25p) is seen when the crystal is returned to lower temperatures. [ABSTRACT FROM AUTHOR]

A new study explores the distinct roles of spontaneous polarization and piezoelectric polarization in piezo-phototronic coupling. This investigation focuses on differences in photocatalytic and piezo-photocatalytic performance using sodium bismuth titanate, a key ferroelectric material. The research aims to identify which type of polarization has a greater influence on piezo-phototronic effects. A theoretical assessment complements the experimental findings, providing additional insights. This study explores the enhanced piezo-phototronic performance of electrospun nanofibers compared to sol-gel particles under different illumination conditions (11 W UV, 250 W UV, and natural sunlight). Electrospun nanofibers exhibited a rate constant (k) improvement of 2.5 to 3.75 times, whereas sol-gel particles showed only 1.3 to 1.4 times higher performance when ultrasonication was added to photocatalysis. Analysis using first-principle methods revealed that nanofibers had an elastic modulus (C33) about 2.15 times lower than sol-gel particles, indicating greater flexibility. The elongation of the lattice along the z axis in the case of nanofibers reduced the covalency in the Bi–O and Ti–O bonds. These structural differences reduced spontaneous polarization and piezoelectric stress coefficients (e31 and e33). Despite having lower piezoelectric stress coefficients, higher flexibility in nanofibers led to a higher piezoelectric strain coefficient, 2.66 and 1.97 times greater than sol-gel particles, respectively. This improved the piezo-phototronic coupling for nanofibers. [ABSTRACT FROM AUTHOR]

To maximize the piezoelectric performance of Pb(Mg1/3Nb2/3)O3–PbTiO3 (PMN–PT) single crystals, a pulse poling (PP) method is proposed in this study. This study investigates the effects of pulse poling on the piezoelectric and dielectric properties of these PMN–PT single crystals and explores the polarization rotation mechanisms. Our findings indicate a significant improvement in the piezoelectric properties postpulse poling. The optimal PP conditions are identified as 30 pulse numbers at a pulsed electric field of 5 kV/cm. The dielectric constant ɛT33/ɛ0 and piezoelectric coefficient d33 of PMN–0.28PT post PP are 7000–7700 and 2200–2530 pC/N, respectively, representing increases of 49% and 66% compared with those of postdirect current poling (DCP). Additionally, the domain structures of the PMN–0.28PT single crystals after various DCP and PP treatments are examined and compared using piezoelectric force microscopy. The enhanced piezoelectric properties are attributed to the finer domain structures, as well as increased domain wall density achieved through PP. This research introduces a novel domain engineering approach to improve the electromechanical properties of relaxor ferroelectric single crystals. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The unique ability of ferroelectrics to generate high voltage under shock loading is limited by electrical breakdown within the shock-compressed ferroelectric material. Breakdown is a hybrid process of initiation and growth. The possible mechanisms of electrical breakdown in ferroelectric films and bulk ceramics subjected to high-pressure shock loading are discussed and experiments designed to elucidate which mechanisms govern breakdown. Gigapascal shock loading experiments were performed on poled Pb0.99(Zr0.95Ti0.05)0.98Nb0.02O3 ferroelectric film specimens in the range of 32–156 μm thickness to determine the dependence of the breakdown field on thickness and on film specimens in the range of 4–16 mm length to determine the dependence of the breakdown field on the duration of shock compression. The resulting breakdown-field vs thickness and breakdown-field vs shock transit time dependencies are consistent with a hybrid electron emission initiation and Joule heating microchannel growth mechanism. Further analysis of data previously obtained on shock-compressed 0.27Pb(In1/2Nb1/2)O3–0.47Pb(Mg1/3Nb2/3)O3–0.26PbTiO3 ferrvoelectric single crystals and Pb(Zr0.65Ti0.35)O3, Pb0.99(Zr0.52Ti0.48)0.99Nb0.01O3, Pb0.99(Zr0.95Ti0.05)0.98Nb0.02O3 bulk ceramics is consistent with this dual mechanism. It appears that neither chemical composition nor microstructure (single crystal vs polycrystalline) of the ferroelectric material has a significant effect on the breakdown mechanism in shocked ferroelectrics. [ABSTRACT FROM AUTHOR]

We find that the unit cell volume (V), which affects many properties, decreases too rapidly with strain when calculated with standard density functional theories (DFTs) such as local density approximation (LDA). We find that this demerit is moderated with the use of the Hubbard potential U for local electron correlation (DFT + U). However, the introduction of U to standard DFTs, e.g., LDA and Perdew–Burke–Ernzerhof functional (PBE) optimized for solids (PBEsol), leads to the excessive underestimation of the spontaneous polarization (PS) and frequently extinguishes PS. Therefore, we attempt to improve the overall accuracy of DFTs for ferroelectrics by using U in several DFT methods including PBE that overestimates PS and lattice constants. We demonstrate that PBE with U (PBE + U) is in excellent agreement with the experimental properties of BaTiO3 and SrTiO3, with improvements in the estimates of lattice constants, PS, the phonon frequency, the antiferrodistortive angle of 105 K-phase SrTiO3, the bandgap, the strain dependence of V, and hole polarons. When the lattice parameters and PS moderately agree with the experimental data, PBE + U with a single U set can produce both electron and hole polarons. Hence, PBE + U can be a practical substitute of hybrid functionals for perovskite oxide ferroelectrics, except for the estimation of the bandgap. Furthermore, we propose an approach to construct a functional accurately depicting the incipient ferroelectric state of SrTiO3. Additionally, these results suggest that conventional DFT underestimates PS under compressive in-plane strain and predicts the unrealistic deformation of ferroelectrics and that in-plane-strained lattices can mitigate the problems associated with U. [ABSTRACT FROM AUTHOR]

The Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) ferroelectric single crystals have been commercially available as important components in medical ultrasound transducers due to their excellent piezoelectric and electromechanical coupling performance. The variation in piezoelectric and dielectric properties of PMN-PT single crystals with ambient temperature is an important application indicator. In this work, the PMN-PT single crystals after direct current poling (DCP) and alternating current poling (ACP) were subjected to the cyclic thermal treatment process. The thermal cycling stability and microstructural changes in PMN-PT single crystals were investigated. The ACP single crystals exhibit a higher dielectric constant ε 33 T / ε 0 (6500–7600) and piezoelectric coefficient d33 (2100–2500 pC N−1) compared to the DCP single crystals (ε 33 T / ε 0 of 4100–5000, d33 of 1200–1300 pC N−1). Under thermal cycling at 60 °C, the DCP and ACP single crystals exhibit good thermal cycling stability after 150 cycles. Microstructural observations show that the domain structure of the DCP single crystals exhibits "staggered domain walls, inhomogeneous domain size, variety of domain structure," while the relatively homogeneous stripe-like domains were observed in the ACP single crystals. After thermal cycling, new fine striped domains appear in both the DCP and ACP single crystals due to the instability of rotated polarization, but the piezoelectric and dielectric properties are not greatly affected. This work provides an intensive understanding of the effects of thermal cycling on the domain structure, which is useful for applications. [ABSTRACT FROM AUTHOR]

The microscopic mechanism of ferroelectric switching is the motion of domain walls, which is actually accomplished by the movement of tiny steps on the domain walls. Using first-principles calculations, the detailed polarization structures and the motion barriers of neutral and charged steps on 180° domain walls of prototypical ferroelectrics PbTiO3 are elaborately revealed in this study. While the Bloch components get weakened near all neutral steps, they become weakened/strengthened near the head-to-head/tail-to-tail charged steps. The neutral step possesses a lower formation energy but a higher migration barrier, indicating that the charged step could move faster. Based on these results, the possible motion picture of steps on one 180° domain wall of tetragonal ferroelectrics is proposed, which provides a better understanding of the mechanism of domain wall motion and may shed light on the future development of domain wall–based functional devices. [ABSTRACT FROM AUTHOR]

Electric polarization typically originates from non-centrosymmetric charge distributions in compounds. In elemental crystalline materials, chemical bonds between atoms of the same element favor symmetrically distributed electron charges and centrosymmetric structures, making elemental ferroelectrics rare. Compared to atoms, elemental clusters are intrinsically less symmetric and can have various preferred orientations when they are assembled to form crystals. Consequently, the assembly of clusters with different orientations tends to break the inversion symmetry. By exploiting this concept, we show that sliding ferroelectricity naturally emerges in trilayer quasi-hexagonal phase (qHP) C60, a cluster-assembled carbon allotrope recently synthesized. Compared to many metallic or semi-metallic elemental ferroelectrics, trilayer qHP C60's have sizable band gaps and several ferroelectric structures, which are distinguishable by measuring their second-harmonic generation (SHG) responses. Some of these phases show both switchable out-of-plane and in-plane polarizations on the order of 0.2 pC/m. The out-of-plane and in-plane polarizations can be switched independently and enable an easy-to-implement construction of Van der Waals homostructures with ferroelectrically switchable chirality. [ABSTRACT FROM AUTHOR]

The manipulation of droplets and wetting properties is crucial in many applications that involve surface‐liquid interactions, especially on artificial superhydrophobic substrates. This study presents an active optoelectronic method to achieve transport and transition between two wetting states on patterned surfaces, namely Cassie–Baxter (CB) and Wenzel (W). The approach employs a photovoltaic iron‐doped lithium niobate crystal placed on the bottom of a micropatterned substrate without any adhesive or sticky bonding. Taking advantage of the bulk photovoltaic effect, charge separation can be induced by light inside the crystal, thus leading to virtual electrodes. The long‐range interaction between these virtual electrodes and the droplets on the top of the substrate allows for transitions between wetting states and droplet transport. Superhydrophobic wetting transitions between Cassie–Baxter and Wenzel are observed on different substrates using this technique. The forces acting on the droplet that cause the transition are determined numerically. The evolution of droplet deformation and contact angle during the generation of the virtual electrode depends on the shape and intensity of the light beam used for photoinduction, as well as on the compositional properties of the crystal. [ABSTRACT FROM AUTHOR]

Ferroelectrics are considered to be promising candidates for highly energy‐efficient electronic devices in future information technologies owing to their nonvolatile and low‐energy operation of spontaneous electric polarization. Driven by the pervasive and growing demands for miniaturization and energy efficiency in nanoelectronics, further reductions in the operating voltage of ferroelectric‐based devices are dispensable and thus have received immense attentions. Recent remarkable advances in atomic‐scale synthesis, cutting‐edge characterizations, and multiscale theoretical calculations of ferroelectrics have gained unprecedented insights into the manipulation of emergent functionalities in multiple length scales, which helps the discovery of nontrivial polar structures and designs of device architectures toward the promise of ultralow‐power consumption. Here, state‐of‐the‐art strategies for reducing operating voltage in ferroelectric materials and devices are reviewed. This article starts with a brief introduction and major achievements in ferroelectrics, and expounds on the techniques to probe the polarization‐switching process. Moreover, this article focuses predominantly on recent advancements in achieving low operating voltages through various prevalent strategies such as thickness scaling, defect engineering, chemical doping, surface and interfacial design, strain engineering. Finally, perspectives with scientific and technical challenges are discussed, aiming to facilitate the energy‐efficient applications of ferroelectric materials and devices in future information technologies. [ABSTRACT FROM AUTHOR]

Ferroelectric materials contain regions of uniform electrical polarization, known as domains. In Pb‐based relaxor‐ferroelectric perovskite oxides, these domains can be as small as a few nanometers, making standardized analysis of domain sizes challenging. Here, we present two methods for the quantitative analysis of domain sizes from transmission electron micrographs. One method uses statistical analysis of multiple line profiles, and the other analyses the intensity of streaks in the Fourier transform of the image. The techniques provide equivalent results for bright‐field images free of other microstructure or aberrations, while the Fourier method is much simpler to apply. [ABSTRACT FROM AUTHOR]

The morphotropic phase boundary (MPB) is particularly crucial for high piezoelectric performance of perovskite ferroelectrics. This study focus on the shift of MPB and its impacts on the piezoelectric properties of (1- x)Bi 0.997 La 0.003 FeO 3 - x BaTiO 3 ferroelectric ceramic. Although appropriate La doping reduces leakage current, the phase boundary is moved towards tetragonal (T) phase. By adjusting BaTiO 3 component, the concentration of rhombohedral (R) and T phase is restored back to almost equality at x = 0.295, achieving optimal piezoelectric properties (d 33 = 179 pC/N, k p = 33.06 %). Furthermore, through applying quenching on 0.30 ≤ x ≤ 0.32 samples occupied mainly by T phase, a higher d 33 value of 205 pC/N and a remarkable amplification of d 33 (about 40 %) are both realized at x = 0.32, which is ascribed to the shift of R/T phase ratio close to 1:1. These results confirm the importance of phase boundary movement and provide an effective approach for performance enhancement of BiFeO 3 -BaTiO 3 system. [ABSTRACT FROM AUTHOR]

The discovery of nanoscale ferroelectricity in hafnia (HfO2) has paved the way for next generation high‐density, non‐volatile devices. Although the surface conditions of nanoscale HfO2 present one of the fundamental mechanism origins, the impact of external environment on HfO2 ferroelectricity remains unknown. In this study, the deleterious effect of ambient moisture is examined on the stability of ferroelectricity using Hf0.5Zr0.5O2 (HZO) films as a model system. It is found that the development of an intrinsic electric field due to the adsorption of atmospheric water molecules onto the film's surface significantly impairs the properties of domain retention and polarization stability. Nonetheless, vacuum heating efficiently counteracts the adverse effects of water adsorption, which restores the symmetric electrical characteristics and polarization stability. This work furnishes a novel perspective on previous extensive studies, demonstrating significant impact of surface water on HfO2‐based ferroelectrics, and establishes the design paradigm for the future evolution of HfO2‐based multifunctional electronic devices. [ABSTRACT FROM AUTHOR]

Recent advances have uncovered an exotic sliding ferroelectric mechanism, which endows to design atomically thin ferroelectrics from non-ferroelectric parent monolayers. Although notable progress has been witnessed in understanding the fundamental properties, functional devices based on sliding ferroelectrics remain elusive. Here, we demonstrate the rewritable, non-volatile memories at room-temperature with a two-dimensional (2D) sliding ferroelectric semiconductor of rhombohedral-stacked bilayer MoS2. The 2D sliding ferroelectric memories (SFeMs) show superior performances with a large memory window of >8 V, a high conductance ratio of above 106, a long retention time of >10 years, and a programming endurance greater than 104 cycles. Remarkably, flexible SFeMs are achieved with state-of-the-art performances competitive to their rigid counterparts and maintain their performances post bending over 103 cycles. Furthermore, synapse-specific Hebbian forms of plasticity and image recognition with a high accuracy of 97.81% are demonstrated based on flexible SFeMs. Functional devices based on sliding ferroelectrics remain elusive. This work demonstrates the rewritable, non-volatile memory devices at room-temperature with two-dimensional sliding ferroelectric rhombohedral-stacked bilayer MoS2. The device shows overall good performance and can be made flexible. [ABSTRACT FROM AUTHOR]

Incipient ferroelectricity bridges traditional dielectrics and true ferroelectrics, enabling advanced electronic and memory devices. Firstly, we report incipient ferroelectricity in freestanding SrTiO3 nanomembranes integrated with monolayer MoS2 to create multifunctional devices, demonstrating stable ferroelectric order at low temperatures for cryogenic memory devices. Our observation includes ultra-fast polarization switching (~10 ns), low switching voltage (<6 V), over 10 years of nonvolatile retention, 100,000 endurance cycles, and 32 conductance states (5-bit memory) in SrTiO3-gated MoS2 transistors at 15 K and up to 100 K. Additionally, we exploit room-temperature weak polarization switching, a feature of incipient ferroelectricity, to construct a physical reservoir for pattern recognition. Our results showcase the potential of utilizing perovskite material properties enabled by advancements in freestanding film growth and heterogeneous integration, for diverse functional applications. Notably, the low 180 °C thermal budget for fabricating the 3D-SrTiO3/2D-MoS2 device stack enables the integration of diverse materials into silicon complementary metal-oxide-semiconductor technology, addressing challenges in compute-in-memory and neuromorphic applications. Sen et al. report the stacking of a perovskite incipient ferroelectric nanomembrane with atomically thin 2D material for a back-end-of-line compatible ferroelectric-like field effect transistors, functioning as a cryogenic memory at 15 K and as an inference engine at room temperature. [ABSTRACT FROM AUTHOR]

Ferroelectric films are highly sought-after in micro-electro-mechanical systems, particularly with the trend towards miniaturization. However, their tendency to depolarize and degradation in piezoelectric properties when exposed to packaging procedures at temperatures exceeding 260 °C remains a significant challenge. Here, we reveal the prerequisites for self-poling and leverage these insights to achieve unprecedented macroscopic performance through a two-step approach involving texture construction and hierarchical heterogeneity engineering. The significant [001] texture and fine Zr/Ti heterogeneity, facilitated by a PbO-TiO2 buffer, enable a piezoelectric charge coefficient of 550 pC/N in self-poled Pb(Zr0.52Ti0.48)O3 film. This material demonstrates impressive resilience to elevated temperatures up to 300 °C, experiencing less than a 16% degradation in performance. Our approach can be extended to other ferroelectric systems, offering an innovative solution for high-temperature packaging and harsh environments in practical electro-mechanical applications. The authors realize a high piezoelectric charge coefficient in a self-poled ferroelectric film, addressing the persistent challenge of piezoelectric property degradation during industrial packaging and shaping the landscape of commercial ferroelectrics for micro-electro-mechanical systems. [ABSTRACT FROM AUTHOR]

With the increasing demand for high‐performance computing and storage solutions, industries are under pressure to deliver enhanced‐density, high‐speed, cost‐efficient, and reliable memory technologies. The development of advanced high dielectric constant (high‐k) dielectrics for dynamic random‐access memory (DRAM) remains essential yet challenging, with a need for further advancements on scaling and mass production compatibility. A significant advancement has been the discovery of morphotropic phase boundary (MPB) in HfO2‐based ferroelectrics, offering a potential solution to enduring issues in DRAM capacitor technology. The superior performance of MPB‐based HfxZr1‐xO2 film systems as high‐k dielectrics (k > 60) provides a promising avenue for advancing DRAM technology. This review article aims to propel DRAM development by detailing the principles of MPB‐based high‐k dielectrics, outlining crucial material and engineering parameters, and addressing the need for precise evaluation and analysis, which have previously been neglected. It also discusses the ongoing challenges and future directions in this field. [ABSTRACT FROM AUTHOR]

2D ferroelectric materials present promising applications in information storage, sensor technology, and optoelectronics through their coupling with magnetics/valleytronics, mechanics, and optics, respectively. The integration of 2D ferroelectrics with magnetism enhances data storage density in memory devices by enabling electric‐field‐controlled magnetic states. Ferroelectric‐valley coupling holds promise for high‐speed, low‐energy electronics by leveraging the electrical control of valley polarization. Ferroelectric‐strain coupling results in various polar topologies, with potential applications in high‐density data storage technologies and sensor devices. Moreover, the coupling between ferroelectrics and optics facilitates the development of nonlinear photonics based on ferroelectric materials. This review summarizes the latest theoretical progress in the coupling mechanisms, including the Dzyaloshinskii‐Moriya‐interaction‐induced magnetoelectric coupling, symmetry‐linked ferroelectric‐valley coupling, ferroelectric‐strain‐coupling‐generated polar topologies, and second‐harmonic generation through ferroelectric‐light interactions. The current challenges and future opportunities in harnessing the coupling in 2D ferroelectric materials for multifunctional applications are provided. [ABSTRACT FROM AUTHOR]

Alternating current poling (ACP) has been proven to significantly improve the performance of relaxor-based perovskite ferroelectrics. However, there is still a lack of methods to scientifically optimize ACP conditions which has remarkable influence on the polarization effects. In this paper, the orthogonal experimental design (OED) is proposed to accomplish the optimization of ACP conditions with minimum experiments. Using this method, the optimal ACP conditions of Sm-doped PMN-PT rhombohedral single crystal were obtained, and giant piezoelectric coefficient d 33 and relative dielectric permittivity ε r /ε 0 of 4520 pC/N and 13290 were achieved, which is 24.5% and 29.5% higher than that under DCP. Because of the orthogonality, high efficiency and being user-friendly for individuals unfamiliar with the material mechanism, the proposed OED is expected to provide experimental instruction for ACP for all kinds of piezoelectric single crystal and ceramics. [ABSTRACT FROM AUTHOR]

A synergistic realization of high electrocaloric effect (ECE) and excellent temperature stability in ferroelectrics are foundation for practical applications, which is, however, a major challenge in ferroelectric cooling community thus far. In confront with this long‐standing issue, an emergent monomorphic ferrodistortion strategy in NaNbO3‐based relaxor is proposed with flexible tetragonal polar nanoregions immersing in short‐range oxygen octahedral tilt. This not only contributes to large quantities of polar entities to increase entropy change but also produces highly robust oxygen octahedral tilt to persist ferroelectricity and obstruct thermal agitations. Therefore, a high ΔT of 0.96 K and an ultrawide temperature span ΔTspan of 110 K with a record‐high figure of merit of 4.74 is achieved in Ta‐doped NaNbO3‐BaTiO3 ceramics and these superior EC performances present a remarkable breakthrough in ferroelectric bulks cooling. This work thus provides an innovative way of utilizing ferrodistortive relaxor feature with polar nanoregions immersing in oxygen octahedral tilt to simultaneously boost EC value and temperature stability and thus monomorphic ferrodistortion is proposed as an effective strategy to develop high‐performance entropy‐change materials. [ABSTRACT FROM AUTHOR]

Pb-based perovskites play pivotal roles in ferroelectric research. In the search for new Pb-based ferroelectrics, we investigated the ferroelectric properties of Dion–Jacobson type CsPb2Nb3O10 and exfoliated 2D nanosheets. Ferroelectricity in CsPb2Nb3O10 was demonstrated for the first time. CsPb2Nb3O10 adopted a polar tetragonal structure with a modest TC = 260 °C and polarization PS = 7.93 μC cm−2; the polarization mainly arose from the out-of-plane displacements of Nb5+ ions and nearby oxygens. CsPb2Nb3O10 layered perovskite offers additional advantages for tailoring ferroelectric nanomaterials, as exfoliated 2D nanosheets provide novel platforms for investigating ferroelectric properties down to the 2D limit. Piezoresponse force microscopy confirmed stable ferroelectricity even in exfoliated 2D Pb2Nb3O10 nanosheets. [ABSTRACT FROM AUTHOR]

Piezoelectricity, a fundamental property of perovskite ferroelectrics, endows the materials at the heart of electromechanical systems spanning from macro to micro/nano scales. Defect engineering strategies, particularly involving heterovalent trace impurities and derived vacancies, hold great potential for adjusting piezoelectric performance. Despite the prevalent use of defect engineering for modification, a comprehensive understanding of the specific features that positively impact material properties is still lacking, this knowledge gap impedes the advancement of a universally applicable defect selection and design strategy. In this work, we select perovskite KTa1−xNbxO3 single crystals with orthorhombic phase as the matrix and introduce Fe and Mn elements, which are commonly used in "hard" ferroelectrics as dopants. We investigate how transition-metal doping modifies piezoelectric properties from the perspective of intrinsic polarization behaviors. Interestingly, despite both being doped into the B-site as an acceptor, Mn doping enhances the local structural heterogeneity, greatly bolstering the piezoelectric coefficient beyond 1000 pC/N, whereas Fe doping tends to stabilize the polarization, leading to a substantial improvement in the mechanical quality factor up to 700. This work deciphers the diverse impacts of transition metal impurities on regulating polarization structures and modifying piezoelectric properties, providing a good paradigm for strategically designing perovskite ferroelectrics. Defect engineering holds great potential for adjusting piezoelectric performance. Here, the authors decipher the diverse impacts of transition metal impurities on modifying piezoelectric properties from the perspective of intrinsic polarization behaviors in KTa1−xNbxO3 crystals. [ABSTRACT FROM AUTHOR]

Cage‐confinement effect that imposes great constriction on the dynamic behaviors of guest molecules is an established platform for tailoring physical properties. Herein, the strategy of enhancing cage‐confinement effect to control molecular motion has been probed for the first time to exploit new high‐Tc ferroelectrics of 2D hybrid perovskites. By fine‐tailoring of the confined cations inside the perovskite cavities, we have successfully obtained new homologous ferroelectrics of (BA)2(MA)2Pb3Cl10 (1; BA=n‐butylamine, MA=methylamine) and (BA)2(EA)2Pb3Cl10 (2; EA=ethylamine). Intriguingly, this dynamics modulation of cage‐confined cations leads to a remarkable promotion of Curie temperature (Tc), boosting from 340 K (for 1) to 402 K (for 2). In situ solid‐state NMR spectroscopy and theoretical simulations on energy barrier confirm that the larger EA cation in 2 is subject to stronger confinement effect, of which potential energy barrier of molecular motion is ~3.5 times that of MA cation. This dynamic behavior greatly suppresses the dynamic motions of EA cation, while MA cation can easily accelerate motion and reach a fast motion limit, thus accounting for an enhancement of Tc (ΔT~62 K) in 2. The finding sheds light on the understanding of cage‐confined electric orders and the precise design of high‐performance ferroelectrics. [ABSTRACT FROM AUTHOR]

Ferroelectric (FE)‐antiferromagnetic (AFM) multiferroic materials have sparked growing interest due to their huge possibilities in energy‐saving, photoelectric devices, nonvolatile storage, and switches. However, realizing FE‐AFM properties in a hybrid molecular material is difficult because ferroelectric and magnetic orders are commonly mutually exclusive. Here, we report an FE‐AFM multiferroic semiconductor [NH4(18‐crown‐6)]2[Mn(SCN)4] (NCMS) by supramolecular assembly approach via molecular rotor synthon [NH4(18‐crown‐6)] and inorganic magnetic module [Mn(SCN)4]. Interestingly, NCMS shows good ferroelectricity with a spontaneous polarization (Ps) of 5.94 μC cm−2 higher than most crown‐ether‐based ferroelectrics. Especially, the realization of antiferromagnetism is for the first time in the crown ether hybrid perovskite ferroic systems. Additionally, semiconductor NCMS displays an X‐ray radiation detection response with a large photo/dark current on‐off ratio (197). Our study not only gives a deep insight into understanding multiferroic properties but also provides a novel and efficient approach to realizing high‐performance hybrid multiferroic materials. [ABSTRACT FROM AUTHOR]

Strong similarities for relativistic electrons stimulated from electron beams and electron clouds are merging the boundary of wave‐particle duality of electrons, one of which being superposition is Cherenkov radiations. Recent theoretical investigations into quantum Cherenkov effects for cone‐shape particles have hypothesized electron‐spin flip transitions in bound‐ and free‐electron systems like bulk silica and graphene. However, experimental validation of these predictions remains outstanding. Here, analogous phenomena of polariton‐version quantum Cherenkov radiations observed by broadband femtosecond pump‐probe experiments is reported, and demonstrate double‐cone emission processes involving of Cherenkov‐type phonon polaritons (PhPs) and plasmon‐PhPs in ultrashort‐pulse‐stimulated ferroelectric crystals and graphene, respectively. Through component analysis of double‐cone polariton emissions using an empirical quantum dynamics model, the initial polariton dynamics are restored by time translation corrections. The resulting quantum wave packets of PhPs are found to be correlated with femtosecond‐laser‐induced modifications inside ferroelectric lithium niobates, achieving a PhP threshold criterion for ultrasmooth femtosecond laser nanofabrication. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Lead‐based relaxor ferroelectrics exhibit giant piezoelectric properties owing to their heterogeneous structures. The average and local structures measured by single‐crystal X‐ray diffraction under DC and AC electric fields are reviewed in this article. The position‐dependent local lattice strain and the distribution of polar nanodomains and nanoregions show strong electric field dependence, which contributes to the giant piezoelectric properties. [ABSTRACT FROM AUTHOR]

Lithium niobate (LiNbO 3 , LN) is a ferroelectric crystal of interest for integrated photonics owing to its large second-order optical nonlinearity and the ability to impart periodic poling via an external electric field. However, on-chip device performance based on thin-film lithium niobate (TFLN) is presently limited by propagation losses arising from surface roughness and corrugations. Atomic layer etching (ALE) could potentially smooth these features and thereby increase photonic performance, but no ALE process has been reported for LN. Here, we report an isotropic ALE process for x -cut MgO-doped LN using sequential exposures of H 2 and SF 6 /Ar plasmas. We observe an etch rate of 1.59 ± 0.02 nm/cycle with a synergy of 96.9 %. We also demonstrate that ALE can be achieved with SF 6 /O 2 or Cl 2 /BCl 3 plasma exposures in place of the SF 6 /Ar plasma step with synergies of 99.5 % and 91.5 %, respectively. The process is found to decrease the sidewall surface roughness of TFLN waveguides etched by physical Ar + milling by 30% without additional wet processing. Our ALE process could be used to smooth sidewall surfaces of TFLN waveguides as a postprocessing treatment, thereby increasing the performance of TFLN nanophotonic devices and enabling new integrated photonic device capabilities. [ABSTRACT FROM AUTHOR]

The interplay between crystal ordering and stretchability is frequently encountered in contemporary materials science, particularly in the case of ferroelectrics. The inherent dilemma arises when these materials need to withstand repetitive mechanical deformations or stretching without sacrificing their crystal integrity, all while retaining their remarkable ferroelectric properties and even exhibiting self‐healing capabilities. This complexity further presents a significant challenge in the design and engineering of mechanically rigid molecular ferroelectric crystals, particularly for applications where both precise crystalline structure and mechanical adaptability are crucial. In this study, the humidity‐controlled expansion and contraction, dissolution, and recrystallization of a self‐assembled molecular ferroelectric‐in‐hydrogel framework are reported. Self‐healing ferroelectric‐in‐hydrogel networks exhibit a recyclable humidity‐tailored ionic conductivity from 2.86 × 10−6 to 1.36 × 10−5 S cm−1, facilitating the stretchable piezoelectric sensing. Additionally, the dynamic bond reforming interactions are observed, leading to the tailoring of Young's modulus from 452 to 170 MPa, maintaining ferroelectricity under a strain of 20% with a piezoelectric coefficient of 15.7 pC N−1. Upon lattice contraction, the molecular contacts undergo reforming, leading to the restoration of stretchable ferroelectrics/piezoelectrics and paving the way for stretchable bioelectronics for full‐body motion monitoring. The capabilities highlighted here open avenues for stretchable and self‐healing ferroelectric‐in‐hydrogel bioelectronic technologies. [ABSTRACT FROM AUTHOR]

Chiral organic-inorganic hybrid perovskites offer a promising platform for developing non-linear chiro-optical applications and chiral-induced spin selectivity. Here, we show that achiral hybrid perovskites that have highly ordered ferroelectric domains with orthogonal polarization exhibit planar chirality, as manifested by second harmonic generation with strong circular dichroism. Interestingly, the handedness of the second harmonic generation circular dichroism response can be alternatingly switched between orthogonally polarized domains and domain walls. To correlate the origin of planar chirality in these domains, atom-resolved atomic force microscopy is used to reveal distinct arrangements of atomic rows in these ferroelectric crystals that indicate planar symmetry breaking. Remarkably, a large SHG anisotropy factor of 0.41 is measured at the domain wall. Additionally, spatially resolved two-photon photoluminescence excitation measurement provide evidence of larger Rashba spin-splitting in these chiral ferroelectric domains compared to domain-free areas. Our discoveries of domain-dependent planar chirality and spin texture hold great promise for advancement of domain-specific chiro-optical applications. The authors find that highly ordered ferroelectric hybrid perovskite domains exhibit planar chirality that switches sign between adjacent domains, which manifest in a large dichroic ratio for circularly polarized second harmonic generation from the domain walls. [ABSTRACT FROM AUTHOR]

Due to the excellent shear‐mode piezoelectric properties, single‐domain tetragonal Pb(In1/2Nb1/2)O3‐Pb(Mg1/3Nb2/3)O3‐PbTiO3 (PIN‐PMN‐PT) crystals are believed to possess giant electro‐optic (EO) coefficients as well. However, the EO properties of single‐domain PIN‐PMN‐PT crystals have not been systematically studied because of the difficulties in the single‐domain sample preparation. Here, by this newly developed orthogonal poling method, single‐domain tetragonal PIN‐PMN‐39PT crystals are successfully obtained by poling the sample along the non‐spontaneous polarization direction at room temperature. Optical grade crystal with good transparency and high EO coefficient component γ51 (≈2800 pm V−1) is achieved. The orientation dependence of the EO coefficient is analyzed based on the measured full matrix of the EO coefficients. This work confirms the giant EO performance of domain‐engineered PIN‐PMN‐PT single crystals mainly comes from the contribution of EO coefficient component γ51 of single domain crystal other than the domain wall or domain switching related mechanisms. [ABSTRACT FROM AUTHOR]

Er3+-modified (Bi 0.5 Na 0.5) 0.945 Ba 0.055 Ti 0.98 (Fe 0.5 Sb 0.5) 0.02 O 3 (BNBT-FS) lead-free ferroelectric ceramics with large electrostrain and electrostrictive response were fabricated in our work. Results showed that Er3+-doping induced the destruction of ferroelectric order and significantly enhanced the field-induced strain. For 0.2 mol% modified sample, the unipolar strain reached 0.463 % under the electric field of 80 kV/cm, yielding a large normalized strain d 33 * (S max / E max) of 579 pm/V. For 0.4 mol% modified sample, high electrostrictive effect with temperature-insensitive electrostrictive coefficient Q 33 (0.022–0.026 m4/C2 in the temperature range of 25–100°C) was obtained. The large electrostrain and electrostrictive response in the present materials show the great potential of the materials for nonlinear actuators applications. [ABSTRACT FROM AUTHOR]

Functional gradient materials (FGMs) possess gradient-varying properties, which make them important in applications for connecting different materials and inhomogeneous environments. Ferroelectric single crystals have multiple excellent physical properties, but it is difficult to design gradient properties during the crystal growth. Here, a method is reported to achieve gradient piezoelectric properties in the tetragonal Mn&Fe-doped KTa1−xNbxO3 (Mn&Fe: KTN) crystals by alternating current poling and internal strain design. Furthermore, opposite piezoelectric coefficients are obtained in the direction perpendicular to the applied electric field, with a gradient variation from −221 to 227 pC/N. This phenomenon has been revealed to result from the co-regulating effect of flexoelectric field and alternating current electric field on defect dipoles and domain structures. This study contributes to the fabrication of functional gradient piezoelectric single crystals and expands the application scenarios of FGMs. [ABSTRACT FROM AUTHOR]

We report on the theoretical/numerical investigation of simultaneous second- and third-harmonic generation from a single wavelength input in quasi-phase-matched crystals. The presented technique consists of a quadratic crystal with two first-order quasi-phase-matched sections: one designed for quasi-phase-matching to second-harmonic generation and the other for quasi-phase-matching to third-harmonic generation via sum-frequency generation. We identify an optimal length ratio (optimal number of domains) for these sections in order to enhance the conversion to the third harmonic, achieving nearly complete energy transfer. The advantages of the method are demonstrated both numerically and analytically, with a specific example using periodically poled lithium niobate. Quadratic cascading with quasi-phase-matching proves to be an effective approach for achieving cubic-like effects with high conversion efficiencies. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Nitride ferroelectrics have recently emerged as promising alternatives to oxide ferroelectrics due to their compatibility with mainstream semiconductor processing. ScAlN, in particular, has exhibited remarkable piezoelectric coupling strength (K2) comparable to that of lithium niobate, making it a valuable choice for RF filters in wireless communications. Recently, ScAlN has sparked interest in its use for nanophotonic devices, chiefly due to its large bandgap facilitating operation in blue wavelengths coupled with promises of enhanced nonlinear optical properties such as a large second-order susceptibility (χ(2)). It is still an open question whether ScAlN can outperform oxide ferroelectrics concerning the Pockels effect—an electro-optic coupling extensively utilized in optical communications devices. In this paper, we present a comprehensive theoretical analysis and experimental demonstration of ScAlN's Pockels effect. Our findings reveal that the electro-optic coupling of ScAlN, despite being weak at low Sc concentration, may be significantly enhanced and exceed LiNbO3 at high levels of Sc doping, which points the direction of continued research efforts to unlock the full potential of ScAlN. The authors predict the Pockels effect of ScAlN with varying Sc concentration, realizing a ScAlN-on-insulator-on-silicon material platform, which allows the formation of low-loss, electrically-tunable microring resonators for accurate measurement of ScAlN's Pockels coefficients. [ABSTRACT FROM AUTHOR]

Conventional photodetectors overly pursue high light‐to‐electric conversion efficiency under weak light stimulation, while disregarding the saturated absorption‐induced blinding effect upon strong light, and achieving efficient photodetection covering a large power range remains a great challenge. In this work, MoS2/BaTiO3 heterostructures are constructed through a low‐cost exfoliation and transfer method combined with spin‐coating. The photoresponse behaviors before and after assembling the BaTiO3 nanoparticles onto the MoS2 nanoflake are investigated, indicating that the high conductivity of MoS2 and ferroelectricity of BaTiO3 can complement each other to improve the photoresponse of the hetero‐integrated device, acquiring a high photoresponsivity of 17402 A W−1 under 0.2 nW irradiation, and a significant 570 µA photocurrent under 8 mW irradiation, realizing a large linear dynamic range index of 152 dB, which is at the top level among layered semiconductor‐based detectors. Moreover, strong power near‐infrared light can be up‐converted to the visible band through the nonlinear effect of BaTiO3, subsequently absorbed by the MoS2 and contributing to the photocurrent, providing a solution to combat and alleviate the saturated absorption issue in photodetection. This work marks a significant advancement in achieving robust high‐performance photodetection by hetero‐integrating 2D materials with ferroelectrics. [ABSTRACT FROM AUTHOR]

An interdigital transducer structure was fabricated from multilayer graphene on the surface of the Y Z -cut of a LiNbO3 ferroelectric crystal. The multilayer graphene was prepared by CVD method and transferred onto the surface of the LiNbO3 substrate. The properties of the multilayer graphene film were studied by Raman spectroscopy. A multilayer graphene (MLG) interdigital transducer (IDT) structure for surface acoustic wave (SAW) excitation with a wavelength of Λ = 60 μm was fabricated on the surface of the LiNbO3 crystal using electron beam lithography (EBL) and plasma chemical etching. The amplitude–frequency response of the SAW delay time line was measured. The process of SAW excitation by graphene IDT was visualized by scanning electron microscopy. It was demonstrated that the increase in the SAW velocity using graphene was related to the minimization of the IDT mass. [ABSTRACT FROM AUTHOR]

Background: The unique non-uniform polar nanoregions and complex phase structure near morphotropic phase boundaries (MPBs) in relaxor ferroelectric materials lead to rich microstructure changes (domain transition, phase transition) under external field stimulation. This not only results in the material with extremely high electromechanical properties, but also greatly affects their mechanical properties and stability. Objective: This study investigated the fundamental mechanical properties of the rhombohedral phase (R-phase) and tetragonal phase (T-phase) structures of the relaxor ferroelectric single crystal PMN-PT material using the nanoindentation with different shapes of indenters. Methods: The basic mechanical properties of the material were measured by nanoindentation, and the fracture caused by indentation was analyzed by scanning electron microscopy. Results: The elastic modulus of R-phase relaxed ferroelectric materials showed a significant dependence on the indentation depth, and the hardness of different phases (R, T-phase) materials all show obvious indentation size effects (ISE). Under the loading of the spherical indenter, both R and T phase materials exhibited a pop-in phenomenon caused by the transition from elastic to inelastic. Under the loading of the Berkovich indenter, the R and T phase materials showed different fracture characteristics of crack propagation response with the increase of the indentation depth. Conclusions: The result demonstrate that the mechanical properties of relaxor ferroelectric materials are significantly related to their phase structure, providing guidance for the design of load bearing and material selection in the practical application of related ferroelectric devices. [ABSTRACT FROM AUTHOR]

Diverse domain patterns significantly influence the nonlinear electromechanical behaviors of ferroelectric nanomaterials, with polarization switching under strong electric fields being inherently a frequency-dependent phenomenon. Nevertheless, research in this area remains limited. In this study, we present a phase-field investigation of frequency-dependent electromechanical dynamics of a polycrystalline BaTiO3 nanofilm with a core-shell structure, subjected to applied frequencies ranging from 1 to 80 kHz. Our findings elucidate the microstructural mechanisms underlying the electromechanical behaviors observed in these materials. The effect of the grain size and the strains effect are also taken into account. Hysteresis and butterfly loops exhibit a marked change in shape as the frequency changes. We discuss the underlying domain-switching dynamics as a basis for evaluating such frequency-dependent properties. In addition, we examine the scaling behaviors of the dynamic hysteresis and the influence of grain boundaries on the domain structure. We can also observe from hysteresis loops that the remnant polarization and coercive field significantly diminish when grain sizes decrease from 60 to 5 nm. A smaller grain size of the nanofilm yields a larger percentage of the dielectric grain boundary, which "dilutes" the overall ferroelectricity of the film. A vortex domain structure is more likely to form at low frequency and a small grain size. [ABSTRACT FROM AUTHOR]

Relaxor ferroelectric single crystals of Pb(Mg1/3Nb2/3)O3–PbTiO3 (PMN–PT) have outstanding electromechanical properties in the linear regime. When operated across a phase transition, these properties are significantly enhanced. Understanding the phase transition mechanism under electromechanical external fields is crucial for the new application of PMN–PT that takes advantage of this phase transition. In the present study, the phase transition of PMN–0.3PT single crystals subjected to a mechanical loading/unloading process and the effects of electric field on the phase transition and electromechanical responses of PMN–0.3PT single crystal under coupled mechanical-electrical loading were systematically investigated using a thermodynamics-based phase-field model. The roles the different energy terms play in the evolution of domain and phase structures were assessed. These findings have important implications for both understanding of the phase transition of relaxor ferroelectric single crystal PMN–0.3PT and applications that take advantage of phase transitions in these materials. The model results for the reversible/irreversible phase transition of PMN–0.3PT during the mechanical loading/unloading process are qualitatively consistent with experimental results. [ABSTRACT FROM AUTHOR]

Bismuth layer‐structured ferroelectrics (BLSF) show great potential as piezoelectric materials for high‐temperature applications. In this study, c‐axis/[001]‐textured CaBi4Ti4O15 (CBT) ceramic was synthesized through templated grain growth (TGG) method. A high Lotgering factor (f) of 96% was achieved in textured CBT ceramic using 20 wt% CBT homogeneous template. The piezoelectric coefficient d33 has significantly increased from 7.8 pC/N for random ceramic to 24.3 pC/N for textured ceramic (poled perpendicular to the c‐axis/[001] texture direction), representing an impressive 300% enhancement while maintaining an ultra‐high Curie temperature (TC) of 788°C. In addition, a low dielectric loss (tanδ = 0.4%) and relatively high resistivity (ρ = 1.1 × 1012 Ω·cm) were achieved simultaneously at room temperature. The significant enhancement of d33 in textured CBT ceramic origins from its strong piezoelectric anisotropy. The large d33,T⊥ is due to the nature of polarization switching in CBT (the spontaneous polarization PS of CBT is along a‐axis direction, and the switching of PS is restricted within the a–b plane). Furthermore, the variation of d33,T⊥ remained below 10% across the temperature range of 25–700°C, highlighting the excellent thermal stability of the textured CBT ceramics. These findings suggest that textured CBT ceramic is a promising piezoelectric material for high‐temperature sensor applications. [ABSTRACT FROM AUTHOR]

Recently, a number of two-dimensional van der Waals (vdW) ferroelectrics have been reported, showing the potential to develop various ultra-thin smart devices down to the atomic monolayer limit. In particular, they have been demonstrated to exhibit intriguing polar domain structures. However, phenomenological thermodynamic models of vdW ferroelectrics, which can capture their ferroic domain structure evolution, are still lacking, limiting our further exploration of domain-structure-related applications. In this work, combining first-principles calculations, we construct a phenomenological phase field model for monolayer ferroelectrics, FEβ-In2Se3. Based on the model, one can calculate the phase stability, ferroelectric hysteresis curves, and domain structures of FEβ-In2Se3 under different loading conditions, showing the feasibility of electromechanically driving the rotation of in-plane polarization and manipulation of the domain structures. By including the second-order partial derivative gradient energy term, the model further captures well the antiferroelectric–ferroelastic domain structures of β′-In2Se3 observed in previous experiments. The developed phase field model should help better understand the domain structure evolution behavior in low-dimensional materials and promote further exploration of domain-structure-related applications. [ABSTRACT FROM AUTHOR]

Recently, a number of two-dimensional van der Waals (vdW) ferroelectrics have been reported, showing the potential to develop various ultra-thin smart devices down to the atomic monolayer limit. In particular, they have been demonstrated to exhibit intriguing polar domain structures. However, phenomenological thermodynamic models of vdW ferroelectrics, which can capture their ferroic domain structure evolution, are still lacking, limiting our further exploration of domain-structure-related applications. In this work, combining first-principles calculations, we construct a phenomenological phase field model for monolayer ferroelectrics, FEβ-In2Se3. Based on the model, one can calculate the phase stability, ferroelectric hysteresis curves, and domain structures of FEβ-In2Se3 under different loading conditions, showing the feasibility of electromechanically driving the rotation of in-plane polarization and manipulation of the domain structures. By including the second-order partial derivative gradient energy term, the model further captures well the antiferroelectric–ferroelastic domain structures of β′-In2Se3 observed in previous experiments. The developed phase field model should help better understand the domain structure evolution behavior in low-dimensional materials and promote further exploration of domain-structure-related applications. [ABSTRACT FROM AUTHOR]

Reducing the switching energy and improving the switching speed of ferroelectrics remain an important goal in the pursuit of electronic devices with ultralow energy consumption and ultrafast response. Molecular ferroelectrics with concise dipole switching mechanism and facile structural tunability are a good platform for manipulating the ferroelectric domains. A methodology is demonstrated to manipulation of ferroelectric domain switching by tailor-made lattice parameters of molecular ferroelectrics, by following which, we succeeded in lowering the threshold electric field and improving the dynamics of ferroelectric switching. Our findings advance the fundamental understanding of microscopic mechanism and provide important insights in controllable tuning of ferroelectric domain switching. [ABSTRACT FROM AUTHOR]

Metal halide perovskite ferroelectrics combining spontaneous polarization and excellent semiconducting properties is an ideal platform for enabling self‐driven X‐ray detection. However, achievements to date have been only based on uniaxiality, which increases the complexity of device fabrication. Multi‐axial ferroelectric materials have multiple equivalent polarization directions, making them potentially amenable to multi‐axial self‐driven X‐ray detection, but the report on these types of materials is still a huge blank. Herein, a high‐quality (BA)2(EA)2Pb3I10 (1) biaxial ferroelectric single crystal was successfully grown, which exhibited significant spontaneous polarization along the c‐axis and b‐axis. Under X‐ray irradiation, bulk photovoltaic effect (BPVE) was exhibited along both the c‐axis and b‐axis, with open circuit voltages (Voc) of 0.23 V and 0.22 V, respectively. Then, the BPVE revealed along the inversion of polarized direction with the polarized electric fields. Intriguingly, due to the BPVE of 1, 1 achieved multi‐axial self‐driven X‐ray detection for the first time (c‐axis and b‐axis) with relatively high sensitivities and ultralow detection limits (17.2 nGyair s−1 and 19.4 nGyair s−1, respectively). This work provides a reference for the subsequent use of multi‐axial ferroelectricity for multi‐axial self‐driven optoelectronic detection. [ABSTRACT FROM AUTHOR]

The substitution of atoms with molecular building blocks to form hybrid organic–inorganic networks has been an important research theme for several decades. ABX3 molecular perovskites (MolPs) are a subclass of hybrid networks, adopting the perovskite structure with cationic and anionic molecules on the A-site and X-site. MolPs such as ((CH3)2NH2)Zn(HCOO)3 or ((n-C3H7)4N)Mn(C2N3)3 show a range of fascinating structure–chemical properties, including temperature-driven phase transitions that include a change of polarity as interesting for ferroelectrics, pressure-driven order–disorder phase transitions as interesting for barocaloric solid-state refrigeration, and most recently, melting-behaviour before decomposition with subsequent glass formation after cooling. In this feature article, we take a more personal perspective, overviewing the field's current state and outlining future directions. We start by comparing the MolPs' structural chemistry with their inorganic parents, a comparison that helps us identify opportunities for material design. After discussing the MolPs' potential as barocalorics, ferroelectrics, and in the area of glasses, we outline some challenges that lie ahead. Beyond their relevance as a hybrid analogue of inorganic perovskites, we find that MolPs' chemical parameter space provides exciting opportunities for systematically developing design guidelines for functional materials. [ABSTRACT FROM AUTHOR]