Deterministic Orientation Control of Ferroelectric HfO2 Thin Film Growth by a Topotactic Phase Transition of an Oxide Electrode.

The scale-free ferroelectricity with superior Si compatibility of HfO2 has reawakened the feasibility of scaled-down nonvolatile devices and beyond the complementary metal-oxide-semiconductor (CMOS) architecture based on ferroelectric materials. However, despite the rapid development, fundamental understanding, and control of the metastable ferroelectric phase in terms of oxygen ion movement of HfO2 remain ambiguous. In this study, we have deterministically controlled the orientation of a single-crystalline ferroelectric phase HfO2 thin film via oxygen ion movement. We induced a topotactic phase transition of the metal electrode accompanied by the stabilization of the differently oriented ferroelectric phase HfO2 through the migration of oxygen ions between the oxygen-reactive metal electrode and the HfO2 layer. By stabilizing different polarization directions of HfO2 through oxygen ion migration, we can gain a profound understanding of the oxygen ion-relevant unclear phenomena of ferroelectric HfO2.

Enhanced ferroelectric switching speed of Si-doped HfO2 thin film tailored by oxygen deficiency.

Investigations concerning oxygen deficiency will increase our understanding of those factors that govern the overall material properties. Various studies have examined the relationship between oxygen deficiency and the phase transformation from a nonpolar phase to a polar phase in HfO2 thin films. However, there are few reports on the effects of oxygen deficiencies on the switching dynamics of the ferroelectric phase itself. Herein, we report the oxygen- deficiency induced enhancement of ferroelectric switching properties of Si-doped HfO2 thin films. By controlling the annealing conditions, we controlled the oxygen deficiency concentration in the ferroelectric orthorhombic HfO2 phase. Rapid high-temperature (800 °C) annealing of the HfO2 film accelerated the characteristic switching speed compared to low-temperature (600 °C) annealing. Scanning transmission electron microscopy and electron energy-loss spectroscopy (EELS) revealed that thermal annealing increased oxygen deficiencies, and first-principles calculations demonstrated a reduction of the energy barrier of the polarization flip with increased oxygen deficiency. A Monte Carlo simulation for the variation in the energy barrier of the polarization flipping confirmed the increase of characteristic switching speed.

Self-rectifying resistance switching memory based on a dynamic p-n junction.

Although resistance random access memory (RRAM) is considered as one of the most promising next-generation memories, the sneak-path issue is still challenging for the realization of high-density crossbar memory array. The integration of the rectifying effect with resistance switching has been considered feasible to suppress the sneaking current. Herein, we report a self-rectifying resistance switching (SR-RS) by a newly discovered Li ions migration induced dynamic p-n junction at the Li-doped ZnO and ZnO layer interface. The Au/Li-ZnO/ZnO/Pt structure exhibits a forming-free and stable resistance switching with a high resistance ratio of R OFF/R ON âˆ¼ 104 and a large rectification ratio ∼106. In the Li-ZnO/ZnO bilayer, the electric field drives the dissociation and recombination of the self-compensated [Formula: see text] complex pairs ([Formula: see text] p-type substitutional defect; [Formula: see text] n-type interstitial defect) through the transport of [Formula: see text] between the two layers, thereby induces the formation of a dynamic p-n junction. Using this structure as a memory stacking device, the maximum crossbar array size has been calculated to be ∼16 Mbit in the worst-case scenario, which confirms the potential of the proposed device structure for the selection-device free and high-density resistance random access memory applications.

Complementary Resistive Switching and Synaptic-Like Memory Behavior in an Epitaxial SrFeO2.5 Thin Film through Oriented Oxygen-Vacancy Channels.

Oxygen-vacancy-ordered brownmillerite oxides offer a reversible topotactic phase transition by significantly varying the oxygen stoichiometry of the material without losing its lattice framework. This phase transition leads to substantial changes in the physical and chemical properties of brownmillerite oxides, including electrical and ion conductivity, magnetic state, and oxygen diffusivity. In this study, the variations in the resistive switching mode of the epitaxial brownmillerite SrFeO2.5 thin film in the device were studied by systematically controlling the oxygen concentration, which could be varied by changing the compliance current during the first electroforming step. Depending on the compliance current, the SrFeO2.5 devices exhibited either low-power bipolar resistive switching or complementary resistive switching behaviors. A physical model based on the internal redistribution of oxygen ions between the interfaces with the top and the bottom electrodes was developed to explain the complementary resistive switching behavior. This model was experimentally validated using impedance spectroscopy. Finally, the gradual conductance variation in the brownmillerite SrFeO2.5 thin films was exploited to realize synaptic learning.

Scale-free ferroelectricity induced by flat phonon bands in HfO2.

Discovery of robust yet reversibly switchable electric dipoles at reduced dimensions is critical to the advancement of nanoelectronics devices. Energy bands flat in momentum space generate robust localized states that are activated independently of each other. We determined that flat bands exist and induce robust yet independently switchable dipoles that exhibit a distinct ferroelectricity in hafnium dioxide (HfO2). Flat polar phonon bands in HfO2 cause extreme localization of electric dipoles within its irreducible half-unit cell widths (~3 angstroms). Contrary to conventional ferroelectrics with spread dipoles, those intrinsically localized dipoles are stable against extrinsic effects such as domain walls, surface exposure, and even miniaturization down to the angstrom scale. Moreover, the subnanometer-scale dipoles are individually switchable without creating any domain-wall energy cost. This offers unexpected opportunities for ultimately dense unit cell-by-unit cell ferroelectric switching devices that are directly integrable into silicon technology.

Stable Subloop Behavior in Ferroelectric Si-Doped HfO2.

The recent demand for analogue devices for neuromorphic applications requires modulation of multiple nonvolatile states. Ferroelectricity with multiple polarization states enables neuromorphic applications with various architectures. However, deterministic control of ferroelectric polarization states with conventional ferroelectric materials has been met with accessibility issues. Here, we report unprecedented stable accessibility with robust stability of multiple polarization states in ferroelectric HfO2. Through the combination of conventional voltage measurements, hysteresis temperature dependence analysis, piezoelectric force microscopy, first-principles calculations, and Monte Carlo simulations, we suggest that the unprecedented stability of intermediate states in ferroelectric HfO2 is due to the small critical volume size for nucleation and the large activation energy for ferroelectric dipole flipping. This work demonstrates the potential of ferroelectric HfO2 for analogue device applications enabling neuromorphic computing.

A Room-Temperature Ferroelectric Ferromagnet in a 1D Tetrahedral Chain Network.

Ferroelectricity occurs in crystals with broken spatial inversion symmetry. In conventional perovskite oxides, concerted ionic displacements within a 3D network of transition-metal-oxygen polyhedra (MOx ) manifest spontaneous polarization. Meanwhile, some 2D networks of MOx foster geometric ferroelectricity with magnetism, owing to the distortion of the polyhedra. Because of the fundamentally different mechanism of ferroelectricity in a 2D network, one can further challenge an uncharted mechanism of ferroelectricity in a 1D channel of MOx and estimate its feasibility. Here, ferroelectricity and coupled ferromagnetism in a 1D FeO4 tetrahedral chain network of a brownmillerite SrFeO2.5 epitaxial thin film are presented. The result provides a new paradigm for designing low-dimensional MOx networks, which is expected to benefit the realization of macroscopic ferro-ordering materials including ferroelectric ferromagnets.

Ferroelectric Polarization-Switching Dynamics and Wake-Up Effect in Si-Doped HfO2.

The ferroelectricity in ultrathin HfO2 offers a viable alternative to ferroelectric memory. A reliable switching behavior is required for commercial applications; however, many intriguing features of this material have not been resolved. Herein, we report an increase in the remnant polarization after electric field cycling, known as the "wake-up" effect, in terms of the change in the polarization-switching dynamics of a Si-doped HfO2 thin film. Compared with a pristine specimen, the Si-doped HfO2 thin film exhibited a partial increase in polarization after a finite number of ferroelectric switching behaviors. The polarization-switching behavior was analyzed using the nucleation-limited switching model characterized by a Lorentzian distribution of logarithmic domain-switching times. The polarization switching was simulated using the Monte Carlo method with respect to the effect of defects. Comparing the experimental results with the simulations revealed that the wake-up effect in the HfO2 thin film is accompanied by the suppression of disorder.

Selective control of multiple ferroelectric switching pathways using a trailing flexoelectric field.

Flexoelectricity is an electromechanical coupling between electrical polarization and a strain gradient 1 that enables mechanical manipulation of polarization without applying an electrical bias2,3. Recently, flexoelectricity was directly demonstrated by mechanically switching the out-of-plane polarization of a uniaxial system with a scanning probe microscope tip3,4. However, the successful application of flexoelectricity in low-symmetry multiaxial ferroelectrics and therefore active manipulation of multiple domains via flexoelectricity have not yet been achieved. Here, we demonstrate that the symmetry-breaking flexoelectricity offers a powerful route for the selective control of multiple domain switching pathways in multiaxial ferroelectric materials. Specifically, we use a trailing flexoelectric field that is created by the motion of a mechanically loaded scanning probe microscope tip. By controlling the SPM scan direction, we can deterministically select either stable 71° ferroelastic switching or 180° ferroelectric switching in a multiferroic magnetoelectric BiFeO3 thin film. Phase-field simulations reveal that the amplified in-plane trailing flexoelectric field is essential for this domain engineering. Moreover, we show that mechanically switched domains have a good retention property. This work opens a new avenue for the deterministic selection of nanoscale ferroelectric domains in low-symmetry materials for non-volatile magnetoelectric devices and multilevel data storage.

Brownmillerite thin films as fast ion conductors for ultimate-performance resistance switching memory.

An oxide-based resistance memory is a leading candidate to replace Si-based flash memory as it meets the emerging specifications for future memory devices. The non-uniformity in the key switching parameters and low endurance in conventional resistance memory devices are preventing its practical application. Here, a novel strategy to overcome the aforementioned challenges has been unveiled by tuning the growth direction of epitaxial brownmillerite SrFeO2.5 thin films along the SrTiO3 [111] direction so that the oxygen vacancy channels can connect both the top and bottom electrodes rather directly. The controlled oxygen vacancy channels help reduce the randomness of the conducting filament (CF). The resulting device displayed high endurance over 106 cycles, and a short switching time of ∼10 ns. In addition, the device showed very high uniformity in the key switching parameters for device-to-device and within a device. This work demonstrates a feasible example for improving the nanoscale device performance by controlling the atomic structure of a functional oxide layer.

Fabrication of Self-Healable and Patternable Polypyrrole/Agarose Hybrid Hydrogels for Smart Bioelectrodes.

We present a new class of electrically conductive, mechanically moldable, and thermally self-healable hybrid hydrogels. The hybrid gels consist of polypyrrole and agarose as the conductive component and self-healable matrix, respectively. By using the appropriate oxidizing agent under conditions of mild temperature, the polymerization of pyrrole occurred along the three-dimensional network of the agarose hydrogel matrix. In contrast to most commercially available hydrogels, the physical crosslinking of agarose gel allows for reversible gelation in the case of our hybrid gel, which could be manipulated by temperature variation, which controls the electrical on/off behavior of the hybrid gel electrode. Exploiting this property, we fabricated a hybrid conductive hydrogel electrode which also self-heals thermally. The novel composite material we report here will be useful for many technological and biological applications, especially in reactive biomimetic functions and devices, artificial muscles, smart membranes, smart full organic batteries, and artificial chemical synapses.

Sb/Cu2Sb-TiC-C Composite Anode for High-Performance Sodium-Ion Batteries.

A novel nanostructure consisting of copper-antimony alloy (Cu2Sb) particles dispersed in a conductive hybrid matrix of titanium carbide (TiC) and carbon (C) has been developed by high energy mechanical milling (HEMM) and explored for use as an anode in sodium-ion batteries. By controlling the molar ratio of Cu and Sb, Cu2Sb and Sb are able to co-exist in a matrix. The (Sb)/Cu2Sb-TiC-C samples have been characterized by X-ray diffraction and by high-resolution transmission electron microscopy. Specifically, the Cu2Sb-TiC-C composite anode demonstrates better cyclic performance as well as better rate-capability compared to Sb/Cu2Sb-TiC-C. Addition- ally, the introduction of the fluoroethylene carbonate (FEC) additive into the electrolyte leads to improved electrochemical performance even at high-rate current densities, when compared to the electrodes without the FEC additive, owing to the formation of a stable and thin SEI layer.

In-Plane Crystallinity Effect on the Unipolar Resistance Switching Behavior of NiO Thin Film.

We report on the resistance switching behavior of high quality NiO thin films grown on Pt(111)/SiOx/Si and Pt(111)/Al2O3 crystals. Polarity independent resistance switching, i.e., unipolar resistance switching exhibited a substrate crystallinity dependence during the resistance switching. The unipolar resistance switching was observed commonly in NiO film grown on both substrates. High resistance state of NiO thin film without in-plane crystallinity showed higher resistance than that of NiO films with in-plane crystallinity. The NiO thin film without in-plane crystallinity also required high set voltages for the resistance switching from high resistance state to low resistance state and showed nonlinear I-V characteristics at high voltage region before the resistance switching.

Flexoelectric effect in the reversal of self-polarization and associated changes in the electronic functional properties of BiFeO(3) thin films.

Flexoelectricity can play an important role in the reversal of the self-polarization direction in epitaxial BiFeO3 thin films. The flexoelectric and interfacial effects compete with each other to determine the self-polarization state. In Region I, the self-polarization is downward because the interfacial effect is more dominant than the flexoelectric effect. In Region II, the self-polarization is upward, because the flexoelectric effect becomes more dominant than the interfacial effect.

Ferroelectric switching dynamics of topological vortex domains in a hexagonal manganite.

Field-induced switching of ferroelectric domains with a topological vortex configuration is studied by atomic imaging and electrical biasing in an electron microscope, revealing the role of topological defects on the topologically-guided change of domain-wall pairs in a hexagonal manganite.