Ferroelectric incommensurate spin crystals.

Ferroics, especially ferromagnets, can form complex topological spin structures such as vortices1 and skyrmions2,3 when subjected to particular electrical and mechanical boundary conditions. Simple vortex-like, electric-dipole-based topological structures have been observed in dedicated ferroelectric systems, especially ferroelectric-insulator superlattices such as PbTiO3/SrTiO3, which was later shown to be a model system owing to its high depolarizing field4-8. To date, the electric dipole equivalent of ordered magnetic spin lattices driven by the Dzyaloshinskii-Moriya interaction (DMi)9,10 has not been experimentally observed. Here we examine a domain structure in a single PbTiO3 epitaxial layer sandwiched between SrRuO3 electrodes. We observe periodic clockwise and anticlockwise ferroelectric vortices that are modulated by a second ordering along their toroidal core. The resulting topology, supported by calculations, is a labyrinth-like pattern with two orthogonal periodic modulations that form an incommensurate polar crystal that provides a ferroelectric analogue to the recently discovered incommensurate spin crystals in ferromagnetic materials11-13. These findings further blur the border between emergent ferromagnetic and ferroelectric topologies, clearing the way for experimental realization of further electric counterparts of magnetic DMi-driven phases.

Piezoelectric and pyroelectric effects induced by interface polar symmetry.

Interfaces in heterostructures have been a key point of interest in condensed-matter physics for decades owing to a plethora of distinctive phenomena-such as rectification1, the photovoltaic effect2, the quantum Hall effect3 and high-temperature superconductivity4-and their critical roles in present-day technical devices. However, the symmetry modulation at interfaces and the resultant effects have been largely overlooked. Here we show that a built-in electric field that originates from band bending at heterostructure interfaces induces polar symmetry therein that results in emergent functionalities, including piezoelectricity and pyroelectricity, even though the component materials are centrosymmetric. We study classic interfaces-namely, Schottky junctions-formed by noble metal and centrosymmetric semiconductors, including niobium-doped strontium titanium oxide crystals, niobium-doped titanium dioxide crystals, niobium-doped barium strontium titanium oxide ceramics, and silicon. The built-in electric field in the depletion region induces polar structures in the semiconductors and generates substantial piezoelectric and pyroelectric effects. In particular, the pyroelectric coefficient and figure of merit of the interface are over one order of magnitude larger than those of conventional bulk polar materials. Our study enriches the functionalities of heterostructure interfaces, offering a distinctive approach to realizing energy transduction beyond the conventional limitation imposed by intrinsic symmetry.

Auxetic piezoelectric effect in heterostructures.

Inherent symmetry breaking at the interface has been fundamental to a myriad of physical effects and functionalities, such as efficient spin-charge interconversion, exotic magnetic structures and an emergent bulk photovoltaic effect. It has recently been demonstrated that interface asymmetry can induce sizable piezoelectric effects in heterostructures, even those consisting of centrosymmetric semiconductors, which provides flexibility to develop and optimize electromechanical coupling phenomena. Here, by targeted engineering of the interface symmetry, we achieve piezoelectric phenomena behaving as the electrical analogue of the negative Poisson's ratio. This effect, termed the auxetic piezoelectric effect, exhibits the same sign for the longitudinal (d33) and transverse (d31, d32) piezoelectric coefficients, enabling a simultaneous contraction or expansion in all directions under an external electrical stimulus. The signs of the transverse coefficients can be further tuned via in-plane symmetry anisotropy. The effects exist in a wide range of material systems and exhibit substantial coefficients, indicating potential implications for all-semiconductor actuator, sensor and filter applications.

Fast Photostriction in Ferroelectrics.

Light-induced nonthermal strain, known as the photostrictive effect, offers a potential way to excite mechanical strain and acoustic wave remotely. The anisotropic photostrictive effect induced by the combination of bulk photovoltaic effect (BPVE) and converse piezoelectric effect in ferroelectric materials is known as too small and slow for the applications requiring a high strain rate, such as ultrasound generation and high-speed signal transmission. Here, a strategy to achieve high rate dynamic photostrictive strain by utilizing local fast responses under modulating continuous light excitation in the resonance condition is reported. A strain rate of 8.06 × 10-3  s-1 is demonstrated under continuous light excitation, which is at least one order of magnitude higher than previous studies on bulk samples as seen in the literature. The significant photostrictive response exists even in depoled ferroelectric material without overall polarization. The theoretical analyses show that fast ferroelectric photostriction can be obtained through the combinational interaction mechanism of local BPVE and local converse piezoelectric effect existing only in the microscopic scale, thus circumventing the slow and low efficient BPVE charging up process across the macroscopic electrical terminals. The achieved fast photostriction and new understandings will open new opportunities to realize future wireless signal transmission and light-acoustic devices.

Anisotropic Ion Migration and Electronic Conduction in van der Waals Ferroelectric CuInP2S6.

Van der Waals (vdW) thio- and seleno-phosphates have recently gained considerable attention for the use as "active" dielectrics in two-dimensional/quasi-two-dimensional electronic devices. Bulk ionic conductivity in these materials has been identified as a key factor for the control of their electronic properties. However, direct evidence of specific ion species' migration at the nanoscale, particularly under electric fields, and its impact on material properties has been elusive. Here, we report on direct evidence of a phase-selective anisotropic Cu-ion-hopping mechanism in copper indium thiophosphate (CuInP2S6) through detailed scanning probe microscopy measurements. A two-step Cu-hopping path including a first intralayer hopping (in-plane) and second interlayer hopping (out-of-plane) crossing the vdW gap is unveiled. Evidence of electrically controlled Cu ion migration is further verified by nanoscale energy-dispersive X-ray spectroscopy (EDS) mapping. These findings offer new insight into anisotropic ionic manipulation in layered vdW ferroelectric/dielectric materials for emergent vdW electronic device design.

Emergent Antipolar Phase in BiFeO3-La0.7Sr0.3MnO3 Superlattice.

Ferroelectric-paraelectric superlattices show emerging new states, such as polar vortices, through the interplay and different energy scales of various thermodynamic constraints. By introducing magnetic coupling at BiFeO3-La0.7Sr0.3MnO3 interfaces epitaxially grown on SrTiO3 substrate, we find, for the first time in thin films, a sub-nanometer thick lamella-like BiFeO3. The emergent phase is characterized by an arrangement of a two unit cell thick lamella-like structure featuring antiparallel polarization, resulting an antiferroelectric-like structure typically associated with a morphotropic phase transition. The antipolar phase is embedded within a nominal R3c structure and is independent of the BiFeO3 thickness (4-30 unit cells). Moreover, the superlattice structure with the morphotropic phase demonstrates azimuth-independent second harmonic generation responses, indicating a change of overall symmetry mediated by a delicate spatial distribution of the emergent phase. This work enriches the understanding of a metastable state manipulated by thermodynamic constraints by lattice strain and magnetic coupling.

Electric-Field Control of the Orbital Occupancy and Magnetic Moment of a Transition-Metal Oxide.

By using soft-x-ray linear and magnetic dichroism on La_{0.825}Sr_{0.175}MnO_{3}/PbZr_{0.2}Ti_{0.8}O_{3} ferromagnetic-ferroelectric heterostructures we demonstrate a nonvolatile modulation of the Mn 3d orbital anisotropy and magnetic moment. X-ray absorption spectroscopy at the Mn L_{2,3} edges shows that the ferroelectric polarization direction modifies the carrier density, the spin moment, and the orbital splitting of t_{2g} and e_{g} Mn 3d states. These results are consistent with polar distortions of the oxygen octahedra surrounding the Mn ions induced by the switching of the ferroelectric polarization.

Persistent photoconductivity in strained epitaxial BiFeO3 thin films.

A drastic change in the conductivity of strained BiFeO3 (BFO) films is observed after illuminating them with above-band gap light. This has been termed as persistent photoconductivity. The enhanced conductivity decays exponentially with time. A trapping character of the sub-band levels and their subsequent gradual emptying is proposed as a possible mechanism.

Nucleation-induced self-assembly of multiferroic BiFeO3-CoFe2O4 nanocomposites.

Large areas of perfectly ordered magnetic CoFe2O4 nanopillars embedded in a ferroelectric BiFeO3 matrix were successfully fabricated via a novel nucleation-induced self-assembly process. The nucleation centers of the magnetic pillars are induced before the growth of the composite structure using anodic aluminum oxide (AAO) and lithography-defined gold membranes as hard mask. High structural quality and good functional properties were obtained. Magneto-capacitance data revealed extremely low losses and magneto-electric coupling of about 0.9 µC/cmOe. The present fabrication process might be relevant for inducing ordering in systems based on phase separation, as the nucleation and growth is a rather general feature of these systems.

Local mapping of generation and recombination lifetime in BiFeO3 single crystals by scanning probe photoinduced transient spectroscopy.

Carrier lifetime in photoelectric processes is the average time an excited carrier is free before recombining or trapping. Lifetime is directly related to defects and it is a key parameter in analyzing photovoltaic effects in semiconductors. We show here a scanning probe method combined with photoinduced current spectroscopy that allows mapping with nanoscale resolution of the generation and recombination lifetimes. Using this method we have analyzed the mechanism of the abnormal photovoltaic effect in multiferroic bismuth ferrite, BiFeO(3). We found that generation and recombination lifetimes in BiFeO(3) are large due to complex generation and recombination processes that involve shallow energy levels in the band gap. The domain walls do not play a major role in the photovoltaic mechanism.

Photoinduced Negative Differential Resistivity and Gunn Oscillations in SrTiO3.

SrTiO3 , a perovskite oxide, holds significant potential for application in the field of oxide electronics. Notably, its photoelectric activity in the low temperature regime, which overlaps with the quantum paraelectric state, exhibits remarkable characteristics. In this study, it is demonstrated that when photo-excited with above band gap energy photons, SrTiO3 exhibits non-linear transport of photocarriers and voltage-controlled negative resistance, resulting from an intervalley transfer of photo-induced electrons. As a consequence of the negative resistance, the photocurrent becomes unstable and spontaneously gives rise to low frequency Gunn-like oscillations.

Magnetoelectric coupling in ordered arrays of multilayered heteroepitaxial BaTiO3/CoFe2O4 nanodots.

Fully epitaxial BaTiO(3)/CoFe(2)O(4) ferroelectric/ferromagnetic multilayered nanodot arrays, a new type of magnetoelectric (ME) nanocomposite with both horizontal and vertical orderings, were fabricated via a stencil-derived direct epitaxy technique. By reducing the clamping effect, ferroelectric domain modification and distinct magnetization change proportional to different interfacial area around the BaTiO(3) phase transition temperatures were found, which may pave the way to quantitative introducing of ME coupling at nanoscale and build high density multistate memory devices.

Boosting Piezoelectricity under Illumination via the Bulk Photovoltaic Effect and the Schottky Barrier Effect in BiFeO3.

Piezoelectricity is a key functionality induced by conversion between mechanical and electrical energy. Enhancement of piezoelectricity in ferroelectrics often has been realized by complicated synthetical approaches to host unique structural boundaries, so-called morphotropic phase boundaries. While structural approaches are well-known, enhancing piezoelectricity by external stimuli has yet to be clearly explored, despite their advantages of offering not only simple and in situ control without any prior processing requirement, but compatibility with other functionalities. Here, it is shown that light is a powerful control parameter to enhance the piezoelectric property of BiFeO3 single crystals. A series of measurements based on piezoresponse force microscopy and conductive atomic force microscopy, under illumination, reveal a locally enhanced effective piezoelectric coefficient, dzz , eventually showing almost a sevenfold increase. This phenomenon is explained with theoretical models by introducing the two main underlying mechanisms attributed to the bulk photovoltaic effect and Schottky barrier effect, involving the role of open-circuit voltage and photocharge carrier density. These results provide key insights to light-induced piezoelectricity enhancement, offering its potential for multifunctional optoelectronic devices.

Enhanced Photoconductivity at Dislocations in SrTiO3.

Dislocations are 1D crystallographic line defects and are usually seen as detrimental to the functional properties of classic semiconductors. It is shown here that this not necessarily accounts for oxide semiconductors in which dislocations are capable of boosting the photoconductivity. Strontium titanate single crystals are controllably deformed to generate a high density of ordered dislocations of two slip systems possessing different mesoscopic arrangements. For both slip systems, nanoscale conductive atomic force microscope investigations reveal a strong enhancement of the photoconductivity around the dislocation cores. Macroscopic in-plane measurements indicate that the two dislocation systems result in different global photoconductivity behavior despite the similar local enhancement. Depending on the arrangement, the global photoresponse can be increased by orders of magnitude. Additionally, indications for a bulk photovoltaic effect enabled by dislocation-surrounding strain fields are observed for the first time. This proves that dislocations in oxide semiconductors can be of large interest for tailoring photoelectric functionalities. Direct evidence that electronic transport is confined to the dislocation core points to a new emerging research field.

Dual-Ferroelectric-Coupling-Engineered Two-Dimensional Transistors for Multifunctional In-Memory Computing.

In-memory computing featuring a radical departure from the von Neumann architecture is promising to substantially reduce the energy and time consumption for data-intensive computation. With the increasing challenges facing silicon complementary metal-oxide-semiconductor (CMOS) technology, developing in-memory computing hardware would require a different platform to deliver significantly enhanced functionalities at the material and device level. Here, we explore a dual-gate two-dimensional ferroelectric field-effect transistor (2D FeFET) as a basic device to form both nonvolatile logic gates and artificial synapses, addressing in-memory computing simultaneously in digital and analog spaces. Through diversifying the electrostatic behaviors in 2D transistors with the dual-ferroelectric-coupling effect, rich logic functionalities including linear (AND, OR) and nonlinear (XNOR) gates were obtained in unipolar (MoS2) and ambipolar (MoTe2) FeFETs. Combining both types of 2D FeFETs in a heterogeneous platform, an important computation circuit, i.e., a half-adder, was successfully constructed with an area-efficient two-transistor structure. Furthermore, with the same device structure, several key synaptic functions are shown at the device level, and an artificial neural network is simulated at the system level, manifesting its potential for neuromorphic computing. These findings highlight the prospects of dual-gate 2D FeFETs for the development of multifunctional in-memory computing hardware capable of both digital and analog computation.

Bond engineering of molecular ferroelectrics renders soft and high-performance piezoelectric energy harvesting materials.

Piezoelectric materials convert mechanical stress to electrical energy and thus are widely used in energy harvesting and wearable devices. However, in the piezoelectric family, there are two pairs of properties that improving one of them will generally compromises the other, which limits their applications. The first pair is piezoelectric strain and voltage constant, and the second is piezoelectric performance and mechanical softness. Here, we report a molecular bond weakening strategy to mitigate these issues in organic-inorganic hybrid piezoelectrics. By introduction of large-size halide elements, the metal-halide bonds can be effectively weakened, leading to a softening effect on bond strength and reduction in polarization switching barrier. The obtained solid solution C6H5N(CH3)3CdBr2Cl0.75I0.25 exhibits excellent piezoelectric constants (d33 = 367 pm/V, g33 = 3595 × 10-3 Vm/N), energy harvesting property (power density is 11 W/m2), and superior mechanical softness (0.8 GPa), promising this hybrid as high-performance soft piezoelectrics.

Skin layer of BiFeO(3) single crystals.

A surface layer ("skin") different from the bulk was found in single crystals of BiFeO(3). Impedance analysis and grazing incidence x-ray diffraction reveal a phase transition at T(*)∼275±5 °C that is confined within the surface of BiFeO(3). X-ray photoelectron spectroscopy and refraction-corrected x-ray diffraction as a function of incidence angle and photon wavelength indicate a reduced electron density and an elongated out-of-plane lattice parameter within a few nanometers of the surface. The skin will affect samples with large surface to volume ratios, as well as devices that rely on interfacial coupling such as exchange bias.

Ultrahigh density array of epitaxial ferroelectric nanoislands on conducting substrates.

An ultrahigh density array of epitaxial PbTiO(3) (PTO) nanoislands with uniform size was fabricated on a single-crystalline Nb-doped SrTiO(3) (100) substrate over a large area (cm(2) scale) by simple but robust method utilizing polystyrene-block-poly(4-vinylpridine) copolymer micelles. Each nanoisland has an average volume of 2.6 x 10(3) nm(3) (a height of 7 nm and a diameter of 22 nm). Because of uniform nanoislands over a large area, a synchrotron X-ray diffraction experiment was successfully employed to analyze the domain structures of PTO nanoislands. They showed well-defined epitaxy on the substrate, which was also confirmed by high-resolution transmission electron microscopy. All of the nanoislands existing in the entire area showed distinct piezoresponse that confirms the existence of ferroelectricity at this size. The results indicate that the critical size of ferroelectrics could be scaled-down further, thereby much increasing the density of ferroelectric devices.

Non-Kolmogorov-Avrami-Ishibashi switching dynamics in nanoscale ferroelectric capacitors.

Switching dynamics of nanoscale ferroelectric capacitors with a radius of 35 nm were investigated using piezoresponse force microscopy. Polarization switching starts with only one nucleation event occurring only at the predetermined places. The switching dynamics of nanoscale capacitors did not follow the classical Kolmogorov-Avrami-Ishibashi model. On the basis of the consideration of two separate (nucleation and growth) steps within a nonstatistical finite system, we have proposed a model which is in good agreement with the experimental results.