Epitaxial SrTiO3 films with dielectric constants exceeding 25,000.

SignificanceSemiconductor interfaces are among the most important in use in modern technology. The properties they exhibit can either enable or disable the characteristics of the materials they connect for functional performance. While much is known about important junctions involving conventional semiconductors such as Si and GaAs, there are several unsolved mysteries surrounding interfaces between oxide semiconductors. Here we resolve a long-standing issue concerning the measurement of anomalously low dielectric constants in SrTiO3 films with record high electron mobilities. We show that the junction between doped and undoped SrTiO3 required to make dielectric constant measurements masks the dielectric properties of the undoped film. Through modeling, we extract the latter and show that it is much higher than previously measured.

Emergence of Improper Electronic Ferroelectricity and Flat Band in Twisted Bilayer Tl2S.

Two-dimensional (2D) ferroelectrics possessing out-of-plane (OP) polarization are highly desirable for applications and fundamental physics. Here, by first-principles calculations, we reveal that large-angle interlayer twisting can efficiently stabilize an unexpected ordering of sizable electric dipoles, producing OP polarization out of the centrosymmetric ground-state structure of Tl2S, in great contrast to the recently proposed interlayer-sliding ferroelectricity. The ferroelectricity originates from a nonlinear coupling between a polar order dominantly contributed by electrons and an unstable phonon mode associated with a commensurate k point (1/3, 1/3, 0) in the two constituent monolayers, therefore indicating an improper and electronic ferroelectric nature. More interestingly, a flat band and a van Hove singularity occur in its electronic structures just below the Fermi level in the large-angle twisted bilayer Tl2S. The unusual coexistence of improper electronic ferroelectricity, a flat band, and a van Hove singularity in one 2D material offers exceptional opportunities for exploring novel physics and applications.

Prediction of a Novel Electromechanical Response in Polar Polymers with Rigid Backbones: Contrasting Furan-Derived Nanothreads to Poly(Vinylidene Fluoride).

Syn furan nanothreads have all oxygen atoms arranged on one side of the thread backbone; these polar threads present intriguing opportunities in electromechanical response owing to their rigid ladder-like backbone. We retrained a C/H/O reactive force field to simulate their response to external electric field for both end-anchored individual threads and bulk nanothread crystals, contrasting the results to those for poly(vinylidene fluoride) (PVDF) polymer. Whereas the field induces a length-independent torque in PVDF through backbone rotation about σ bonds, furan-derived nanothreads generate a length-dependent torque by progressively twisting their rigid backbone. This mode of response couples the rotational history of the electric field to axial tension in the anchored thread. In simulations of densely packed syn furan nanothread crystals without anchors, the crystals pole in a field (∼3 GV/m at 300 K) similar to that seen in simulations of PVDF, suggesting that crystals of polar nanothreads can be ferroelectric.

Tunable Multistate Ferroelectricity of Unit-Cell-Thick BaTiO3 Revived by a Ferroelectric SnS Monolayer via Interfacial Sliding.

Stabilization of multiple polarization states at the atomic scale is pivotal for realizing high-density memory devices beyond prevailing bistable ferroelectric architectures. Here, we show that two-dimensional ferroelectric SnS or GeSe is able to revive and stabilize the ferroelectric order of three-dimensional ferroelectric BaTiO3, even when the latter is thinned to one unit cell in thickness. The underlying mechanism for overcoming the conventional detrimental critical thickness effect is attributed to facile interfacial inversion symmetry breaking by robust in-plane polarization of SnS or GeSe. Furthermore, when invoking interlayer sliding, we can stabilize multiple polarization states and achieve efficient interstate switching in the heterostructures, accompanied by dynamical ferroelectric skyrmionic excitations. When invoking sliding and twisting, the moiré domains exhibit nontrivial polar vortexes, which can be laterally displaced via different sliding schemes. These findings provide an intuitive avenue for simultaneously overcoming the standing critical thickness issue in bulk ferroelectrics and weak polarization issue in sliding ferroelectricity.

Flexoelectric Engineering of Bulk Photovoltaic Photodetector.

The bulk photovoltaic effect (BPVE) offers an interesting approach to generate a steady photocurrent in a single-phase material under homogeneous illumination, and it has been extensively investigated in ferroelectrics exhibiting spontaneous polarization that breaks inversion symmetry. Flexoelectricity breaks inversion symmetry via a strain gradient in the otherwise nonpolar materials, enabling manipulation of ferroelectric order without an electric field. Combining these two effects, we demonstrate active mechanical control of BPVE in suspended 2-dimensional CuInP2S6 (CIPS) that is ferroelectric yet sensitive to electric field, which enables practical photodetection with an order of magnitude enhancement in performance. The suspended CIPS exhibits a 20-fold increase in photocurrent, which can be continuously modulated by either mechanical force or light polarization. The flexoelectrically engineered photodetection device, activated by air pressure and without any optimization, possesses a responsivity of 2.45 × 10-2 A/W and a detectivity of 1.73 × 1011 jones, which are superior to those of ferroelectric-based photodetection and comparable to those of the commercial Si photodiode.

Emergent Inhomogeneity and Nonlocality in a Graphene Field-Effect Transistor on a Near-Parallel Moiré Superlattice of Transition Metal Dichalcogenides.

At near-parallel orientation, twisted bilayers of transition metal dichalcogenides exhibit interlayer charge transfer-driven out-of-plane ferroelectricity. Here, we report detailed electrical transport in a dual-gated graphene field-effect transistor placed on a 2.1° twisted bilayer WSe2. We observe hysteretic transfer characteristics and an emergent charge inhomogeneity with multiple local Dirac points evolving with an increasing electric displacement field (D). Concomitantly, we also observe a strong nonlocal voltage signal at D ∼ 0 V/nm that decreases rapidly with increasing D. A linear scaling of the nonlocal signal with longitudinal resistance suggests edge mode transport, which we attribute to the breaking of valley symmetry of graphene due to the spatially fluctuating electric field from the underlying polarized moiré domains. A quantitative analysis suggests the emergence of finite-size domains in graphene that modulate the charge and the valley currents simultaneously. This work underlines the impact of interfacial ferroelectricity that can trigger a new generation of devices.

Coexisting Magnetism, Ferroelectric, and Ferrovalley Multiferroic in Stacking-Dependent Two-Dimensional Materials.

Two-dimensional (2D) multiferroic materials have widespread application prospects in facilitating the integration and miniaturization of nanodevices. However, the magnetic, ferroelectric, and ferrovalley properties in one 2D material are rarely coupled. Here, we propose a mechanism for manipulating magnetism, ferroelectric, and valley polarization by interlayer sliding in a 2D bilayer material. Monolayer GdI2 is a ferromagnetic semiconductor with a valley polarization of up to 155.5 meV. More interestingly, the magnetism and valley polarization of bilayer GdI2 can be strongly coupled by sliding ferroelectricity, making these tunable and reversible. In addition, we uncover the microscopic mechanism of the magnetic phase transition by a spin Hamiltonian and electron hopping between layers. Our findings offer a new direction for investigating 2D multiferroic devices with implications for next-generation electronic, valleytronic, and spintronic devices.

Emergent Three-Dimensional Electric Dipole Sinewave in Bulk Perovskite Oxides.

The magnetic and electric dipoles of ferroics play a central role in their fascinating properties. In particular, topological configurations have shown promising potential for use in novel electromechanical and electronic devices. Magnetic configurations from simple collinear to complex topological are well-documented. In contrast, many complex topological features in the electric counterpart remain unexplored. Here, we report the first example of three-dimensional electric dipole sinewave topological structure in a PbZrO3-based bulk perovskite, which presents an interesting triple-hysteresis loop macroscopically. This polar configuration consists of two orthogonal sinewave electric dipole modulations decoded from a polar incommensurate phase by advanced diffraction and atomic-resolution imaging techniques. The resulting topology is unraveled to be the competition between the antiferroelectric and ferroelectric states, stabilized by the modulation of the Pb 6s2 lone pair and the antiferrodistortive effect. These findings further reinforce the similarity of the magnetic and electric topologies.

Strong Sliding Ferroelectricity and Interlayer Sliding Controllable Spintronic Effect in Two-Dimensional HgI2 Layers.

Exploration of two-dimensional (2D) sliding ferroelectric (FE) materials with experimentally detectable ferroelectricity and value-added novel functionalities is highly sought for the development of 2D "slidetronics". Herein, based on first-principles calculations, we identify the synthesizable van der Waals (vdW) layered crystals HgX2 (X = Br and I) as a new class of 2D sliding ferroelectrics. Both HgBr2 and HgI2 in 2D multilayered forms adopt the preferential stacking sequence, leading to room temperature stable out-of-plane (vertical) ferroelectricity that can be reversed via the sliding of adjacent monolayers. Owing to strong interlayer coupling and interfacial charge rearrangement, 2D HgI2 layers possess strong sliding ferroelectricity up to 0.16 µC/cm2, readily detectable in experiment. Moreover, robust sliding ferroelectricity and interlayer sliding controllable Rashba spin texture of FE-HgI2 layers enable potential applications as 2D spintronic devices such that the electric control of electron spin detection can be realized at the 2D regime.

Nonvolatile Multistate Manipulation of Topological Magnetism in Monolayer CrI3 through Quadruple-Well Ferroelectric Materials.

Nonvolatile multistate manipulation of two-dimensional (2D) magnetic materials holds promise for low dissipation, highly integrated, and versatile spintronic devices. Here, utilizing density functional theory calculations and Monte Carlo simulations, we report the realization of nonvolatile and multistate control of topological magnetism in monolayer CrI3 by constructing multiferroic heterojunctions with quadruple-well ferroelectric (FE) materials. The Pt2Sn2Te6/CrI3 heterojunction exhibits multiple magnetic phases upon modulating FE polarization states of FE layers and interlayer sliding. These magnetic phases include Bloch-type skyrmions and ferromagnetism, as well as a newly discovered topological magnetic structure. We reveal that the Dzyaloshinskii-Moriya interaction (DMI) induced by interfacial coupling plays a crucial role in magnetic skyrmion manipulation, which aligns with the Fert-Levy mechanism. Moreover, a regular magnetic skyrmion lattice survives when removing a magnetic field, demonstrating its robustness. The work sheds light on an effective approach to nonvolatile and multistate control of 2D magnetic materials.

Coexistence of Ferroelectricity and Ferromagnetism in Atomically Thin Two-Dimensional Cr2S3/WS2 Vertical Heterostructures.

Two-dimensional (2D) heterostructures with ferromagnetism and ferroelectricity provide a promising avenue to miniaturize the device size, increase computational power, and reduce energy consumption. However, the direct synthesis of such eye-catching heterostructures has yet to be realized up to now. Here, we design a two-step chemical vapor deposition strategy to growth of Cr2S3/WS2 vertical heterostructures with atomically sharp and clean interfaces on sapphire. The interlayer charge transfer and periodic moiré superlattice result in the emergence of room-temperature ferroelectricity in atomically thin Cr2S3/WS2 vertical heterostructures. In parallel, long-range ferromagnetic order is discovered in 2D Cr2S3 via the magneto-optical Kerr effect technique with the Curie temperature approaching 170 K. The charge distribution variation induced by the moiré superlattice changes the ferromagnetic coupling strength and enhances the Curie temperature. The coexistence of ferroelectricity and ferromagnetism in 2D Cr2S3/WS2 vertical heterostructures provides a cornerstone for the further design of logic-in-memory devices to build new computing architectures.

Ferroelectricity and Thermochromism in a 2D Dion-Jacobson Organic-Inorganic Hybrid Perovskite.

2D organic-inorganic hybrid perovskites (OIHPs) have become one of the hottest research topics due to their excellent environmental stability and unique optoelectronic properties. Recently, the ferroelectricity and thermochromism of 2D OIHPs have attracted increasing interests. Integrating ferroelectricity and thermochromism into perovskites can significantly promote the development of multichannel intelligent devices. Here, a novel 2D Dion-Jacobson OIHP of the formula (3AMP)PbI4 (where 3AMP is 3-(aminomethyl)pyridinium) is reported, which has a remarkable spontaneous polarization value (Ps) of 15.6 µC cm-2 and interesting thermochromism. As far it is known, such a large Ps value is the highest for 2D OIHPs recorded so far. These findings will inspire further exploration and application of multifunctional perovskites.

Ferroelectricity and Related Properties of Nitratecadmate(II) Hybrid with Metal-Vacancy.

All crystals are not ideal, and many of their properties are often determined not by the regular arrangement of atoms, but by the irregular arrangement of crystal defects. Many properties of materials can be controlled effectively by proper use of solid defects. By substitution of NH4 + ion of a hexagonal perovskite structure (H2 dabco)(NH4 )(NO3 )3 (dabco=1,4-diazabicyclo[2.2.2]octane, 1) with Cd2+ ion, we obtained a new metal-vacancy compound (H2 dabco)2 Cd(H2 O)2 (NO3 )6 (2). It exhibits a ferroelectric-paraelectric phase transition at 261 K. A comparison of the various-temperature single-crystal structures indicates that the coordination twist of Cd2+ ion leads to instability of the lattices and excellent ferroelectricity. These findings reveal that the vacancy can be utilized as an element to produce ferroelectricity and may start the chemistry of metal-vacancy coordination compounds. These findings reveals that the vacancy can be utilized as an effective means to tune the symmetry and produce ferroelectricity.

Supramolecular Organic Ferroelectric Materials from Donor-Acceptor Systems.

Organic ferroelectric (FE) materials, though known for more than a century, are yet to reach close to the benchmark of inorganic or hybrid materials in terms of the magnitude of polarization. Amongst the different classes of organic systems, donor (D)-acceptor (A) charge-transfer (CT) complexes are recognized as promising for ferroelectricity owing to their neutral-to-ionic phase transition at low temperature. This review presents an overview of different supramolecular D-A systems that have been explored for FE phase transitions. The discussion begins with a general introduction of ferroelectricity and its different associated parameters. Then it moves on to show early examples of CT cocrystals that have shown FE properties at sub-ambient temperature. Subsequently, recent developments in the field of room temperature (RT) ferroelectricity, exhibited by H-bond-stabilized lock-arm supramolecular-ordering (LASO) in D-A co-crystals or other FE CT-crystals devoid of neutral-ionic phase transition are discussed. Then the discussion moves on to emerging reports on other D-A soft materials such as gel and foldable polymers; finally it shows very recent developments in ferroelectricity in supramolecular assemblies of single-component dipolar or ambipolar π-systems, exhibiting intra-molecular charge transfer. The effects of structural nuances such as H-bonding, balanced charge transfer and chirality on the observed ferroelectricity is described with the available examples. Finally, piezoelectricity in recently reported ambipolar ADA-type systems are discussed to highlight the future potential of these soft materials in micropower energy harvesting.

Improving the ferroelectric properties of Lu doped Hf0.5Zr0.5O2thin films by capping a CeOxlayer.

Lu doped Hf0.5Zr0.5O2(HZO) ferroelectric films were prepared on Pt/TiN/SiO2/Si substrate by chemical solution deposition method, and an interfacial engineering strategy for improving the ferroelectric property was explored by capping the Lu doped HZO films with a cerium oxide layer. Compared with the Lu doped HZO film without the CeOxcoating layer, the Lu doped HZO film with the CeOxcoating layer has a larger remanent polarization (2Pr= 34.72µC cm-2) and presents weaker wake-up behavior, which result from the higher orthogonal phase ratio and the lower oxygen vacancy of the CeOxcoated Lu doped HZO film. In addition, the CeOxcoating can remarkably improve the fatigue resistance and retention performance of the Lu doped HZO films. It is hoped that the results can provide an effective approach for the realization of high-performance and highly reliable hafnium oxide based ferroelectric thin films.

Enhanced polarization and endurance properties of ZrO2-based ferroelectric capacitor using HfO2interfacial layer.

Recently discovered ferroelectricity in fluorite-structure ZrO2thin film has attracted increasing and intense interest due to its lower crystallization temperature and higher content in nature in comparison to hafnium oxide. Here, the effect of HfO2interfacial layer on the ferroelectric properties of ZrO2thin films is investigated systematically by designing four types of interfacial structures. It is revealed that the ferroelectric orthorhombic phase, remanent polarization, and endurance can be improved in ZrO2thin film by inserting both a top- and bottom-HfO2interfacial layer. A maximal ferroelectric remanent polarization (2Pr) of 53.4µC cm-2and an optimal endurance performance of 3 × 107field cycles under frequency of 100 kHz are achieved in Pt/HfO2/ZrO2/HfO2/Pt capacitors, with ferroelectric stacks being crystallized at 450 °C via post-deposition annealing method. X-ray photoelectron spectroscopy analysis confirms that the HfO2bottom-layer plays a very important role in the formation of a higher ratio o-phase, thus enhancing the ferroelectricity. These results suggest that designing appropriate interfaces would help achieve excellent ferroelectric properties in ZrO2films.

Transition from fractal-dendritic to compact islands for the 2D-ferroelectric SnSe on graphene/Ir(111).

Epitaxial growth is a versatile method to prepare two-dimensional van der Waals ferroelectrics like group IV monochalcogenides which have potential for novel electronic devices and sensors. We systematically study SnSe monolayer islands grown by molecular beam epitaxy, especially the effect of annealing temperature on shape and morphology of the edges. Characterization of the samples by scanning tunneling microscopy reveals that the shape of the islands changes from fractal-dendritic after deposition at room temperature to a compact rhombic shape through annealing, but ripening processes are absent up to the desorption temperature. A two-step growth process leads to large, epitaxially aligned rhombic islands bounded by well-defined110-edges (armchair-like), which we claim to be the equilibrium shape of the stoichiometric SnSe monolayer islands. The relaxation of the energetically favorable edges is detected in atomically resolved STM images. The experimental findings are supported by the results of our first-principles calculations, which provide insights into the energetics of the edges, their reconstructions, and yields the equilibrium shapes of the islands which are in good agreement with the experiment.

Ferroelectricity and multiferroicity in anti-Ruddlesden-Popper structures.

Combining ferroelectricity with other properties such as visible light absorption or long-range magnetic order requires the discovery of new families of ferroelectric materials. Here, through the analysis of a high-throughput database of phonon band structures, we identify a structural family of anti-Ruddlesden-Popper phases [Formula: see text]O (A=Ca, Sr, Ba, Eu, X=Sb, P, As, Bi) showing ferroelectric and antiferroelectric behaviors. The discovered ferroelectrics belong to the new class of hyperferroelectrics that polarize even under open-circuit boundary conditions. The polar distortion involves the movement of O anions against apical A cations and is driven by geometric effects resulting from internal chemical strains. Within this structural family, we show that [Formula: see text]O combines coupled ferromagnetic and ferroelectric order at the same atomic site, a very rare occurrence in materials physics.

Sliding ferroelectricity in 2D van der Waals materials: Related physics and future opportunities.

Near the 100th anniversary of the discovery of ferroelectricity, so-called sliding ferroelectricity has been proposed and confirmed recently in a series of experiments that have stimulated remarkable interest. Such ferroelectricity exists widely and exists only in two-dimensional (2D) van der Waals stacked layers, where the vertical electric polarization is switched by in-plane interlayer sliding. Reciprocally, interlayer sliding and the "ripplocation" domain wall can be driven by an external vertical electric field. The unique combination of intralayer stiffness and interlayer slipperiness of 2D van der Waals layers greatly facilitates such switching while still maintaining environmental and mechanical robustness at ambient conditions. In this perspective, we discuss the progress and future opportunities in this behavior. The origin of such ferroelectricity as well as a general rule for judging its existence are summarized, where the vertical stacking sequence is crucial for its formation. This discovery broadens 2D ferroelectrics from very few material candidates to most of the known 2D materials. Their low switching barriers enable high-speed data writing with low energy cost. Related physics like Moiré ferroelectricity, the ferroelectric nonlinear anomalous Hall effect, and multiferroic coupling are discussed. For 2D valleytronics, nontrivial band topology and superconductivity, their possible couplings with sliding ferroelectricity via certain stacking or Moiré ferroelectricity also deserve interest. We provide critical reviews on the current challenges in this emerging area.

Proton strings and rings in atypical nucleation of ferroelectricity in ice.

Ordinary ice has a proton-disordered phase which is kinetically metastable, unable to reach, spontaneously, the ferroelectric (FE) ground state at low temperature where a residual Pauling entropy persists. Upon light doping with KOH at low temperature, the transition to FE ice takes place, but its microscopic mechanism still needs clarification. We introduce a lattice model based on dipolar interactions plus a competing, frustrating term that enforces the ice rule (IR). In the absence of IR-breaking defects, standard Monte Carlo (MC) simulation leaves this ice model stuck in a state of disordered proton ring configurations with the correct Pauling entropy. A replica exchange accelerated MC sampling strategy succeeds, without open path moves, interfaces, or off-lattice configurations, in equilibrating this defect-free ice, reaching its low-temperature FE order through a well-defined first-order phase transition. When proton vacancies mimicking the KOH impurities are planted into the IR-conserving lattice, they enable standard MC simulation to work, revealing the kinetics of evolution of ice from proton disorder to partial FE order below the transition temperature. Replacing ordinary nucleation, each impurity opens up a proton ring generating a linear string, an actual FE hydrogen bond wire that expands with time. Reminiscent of those described for spin ice, these impurity-induced strings are proposed to exist in doped water ice too, where IRs are even stronger. The emerging mechanism yields a dependence of the long-time FE order fraction upon dopant concentration, and upon quenching temperature, that compares favorably with that known in real-life KOH doped ice.