Revealing the Chemical and Structural Complexity of Electrochemical Ion Exchange in Layered Oxide Materials.

Soft chemistry techniques, such as ion exchange, hold great potential for the development of battery electrode materials that cannot be stabilized via conventional equilibrium synthesis methods. Nevertheless, the intricate mechanisms governing ion exchange remain elusive. Herein, we investigate the evolution of the long-range and local structure, as well as the ion (de)intercalation mechanism during electrochemical Li-to-Na ion exchange initiated from an O3-type lithium-layered oxide cathode. The in situ-formed mixed-cation electrolyte leads to competitive intercalation of Li and Na ions. While Li ion intercalation predominates at the beginning of initial discharge, Na ion cointercalation into a different layer results in ion redistribution and phase separation, with the emergence of a P3-Na phase alongside an O3-Li phase. Further, this study spatially resolves the heterogeneous nature of electrochemical ion exchange reactions within individual particles and provides insights into the correlations between local Ni redox processes and phase separation. Overall, electrochemical ion exchange leads to a mixed-phase cathode and alters its reaction kinetics. Those findings have important implications for the development of new metastable materials for renewable energy devices and ion separation applications.

Field-free spin-orbit switching of perpendicular magnetization enabled by dislocation-induced in-plane symmetry breaking.

Current induced spin-orbit torque (SOT) holds great promise for next generation magnetic-memory technology. Field-free SOT switching of perpendicular magnetization requires the breaking of in-plane symmetry, which can be artificially introduced by external magnetic field, exchange coupling or device asymmetry. Recently it has been shown that the exploitation of inherent crystal symmetry offers a simple and potentially efficient route towards field-free switching. However, applying this approach to the benchmark SOT materials such as ferromagnets and heavy metals is challenging. Here, we present a strategy to break the in-plane symmetry of Pt/Co heterostructures by designing the orientation of Burgers vectors of dislocations. We show that the lattice of Pt/Co is tilted by about 1.2° when the Burgers vector has an out-of-plane component. Consequently, a tilted magnetic easy axis is induced and can be tuned from nearly in-plane to out-of-plane, enabling the field-free SOT switching of perpendicular magnetization components at room temperature with a relatively low current density (~1011 A/m2) and excellent stability (> 104 cycles). This strategy is expected to be applicable to engineer a wide range of symmetry-related functionalities for future electronic and magnetic devices.

Machine Learning-Enabled Superior Energy Storage in Ferroelectric Films with a Slush-Like Polar State.

Heterogeneities in structure and polarization have been employed to enhance the energy storage properties of ferroelectric films. The presence of nonpolar phases, however, weakens the net polarization. Here, we achieve a slush-like polar state with fine domains of different ferroelectric polar phases by narrowing the large combinatorial space of likely candidates using machine learning methods. The formation of the slush-like polar state at the nanoscale in cation-doped BaTiO3 films is simulated by phase field simulation and confirmed by aberration-corrected scanning transmission electron microscopy. The large polarization and the delayed polarization saturation lead to greatly enhanced energy density of 80 J/cm3 and transfer efficiency of 85% over a wide temperature range. Such a data-driven design recipe for a slush-like polar state is generally applicable to quickly optimize functionalities of ferroelectric materials.

Significant Unconventional Anomalous Hall Effect in Heavy Metal/Antiferromagnetic Insulator Heterostructures.

The anomalous Hall effect (AHE) is a quantum coherent transport phenomenon that conventionally vanishes at elevated temperatures because of thermal dephasing. Therefore, it is puzzling that the AHE can survive in heavy metal (HM)/antiferromagnetic (AFM) insulator (AFMI) heterostructures at high temperatures yet disappears at low temperatures. In this paper, an unconventional high-temperature AHE in HM/AFMI is observed only around the Néel temperature of AFM, with large anomalous Hall resistivity up to 40 nΩ cm is reported. This mechanism is attributed to the emergence of a noncollinear AFM spin texture with a non-zero net topological charge. Atomistic spin dynamics simulation shows that such a unique spin texture can be stabilized by the subtle interplay among the collinear AFM exchange coupling, interfacial Dyzaloshinski-Moriya interaction, thermal fluctuation, and bias magnetic field.

Bicontinuous oxide heteroepitaxy with enhanced photoconductivity.

Self-assembled systems have recently attracted extensive attention because they can display a wide range of phase morphologies in nanocomposites, providing a new arena to explore novel phenomena. Among these morphologies, a bicontinuous structure is highly desirable based on its high interface-to-volume ratio and 3D interconnectivity. A bicontinuous nickel oxide (NiO) and tin dioxide (SnO2) heteroepitaxial nanocomposite is revealed here. By controlling their concentration, we fabricated tuneable self-assembled nanostructures from pillars to bicontinuous structures, as evidenced by TEM-energy-dispersive X-ray spectroscopy with a tortuous compositional distribution. The experimentally observed growth modes are consistent with predictions by first-principles calculations. Phase-field simulations are performed to understand 3D microstructure formation and extract key thermodynamic parameters for predicting microstructure morphologies in SnO2:NiO nanocomposites of other concentrations. Furthermore, we demonstrate significantly enhanced photovoltaic properties in a bicontinuous SnO2:NiO nanocomposite macroscopically and microscopically. This research shows a pathway to developing innovative solar cell and photodetector devices based on self-assembled oxides.

Synthesis of a New Ferroelectric Relaxor Based on a Combination of Antiferroelectric and Paraelectric Systems.

Relaxor ferroelectric-based energy storage systems are promising candidates for advanced applications as a result of their fast speed and high energy storage density. In the research field of ferroelectrics and relaxor ferroelectrics, the concept of solid solution is widely adopted to modify the overall properties and acquire superior performance. However, the combination between antiferroelectric and paraelectric materials was less studied and discussed. In this study, paraelectric barium hafnate (BaHfO3) and antiferroelectric lead hafnate (PbHfO3) are selected to demonstrate such a combination. A paraelectric to relaxor ferroelectric, to ferroelectric, and to antiferroelectric transition is observed by varying the composition x in the (Ba1-xPbx)HfO3 solid solution from 0 to 100%. It is noteworthy that ferroelectric phases can be realized without primal ferroelectric material. This study creates an original solid solution system with a rich spectrum of competing phases and demonstrates an approach to design relaxor ferroelectrics for energy storage applications and beyond.

A Narrowband Spintronic Terahertz Emitter Based on Magnetoelastic Heterostructures.

Narrowband terahertz (THz) radiation is crucial for high-resolution spectral identification, but a narrowband THz source driven by a femtosecond (fs) laser has remained scarce. Here, it is computationally predicted that a metal/dielectric/magnetoelastic heterostructure enables converting a fs laser pulse into a multicycle THz pulse with a narrow linewidth down to ∼1.5 GHz, which is in contrast to the single-cycle, broadband THz pulse from the existing fs-laser-excited emitters. It is shown that such narrowband THz pulse originates from the excitation and long-distance transport of THz spin waves in the magnetoelastic film, which can be enabled by a short strain pulse obtained from fs laser irradiation of the metal film when the thicknesses of the metal and magnetoelastic films both fall into a specific range. These results therefore reveal an approach to achieving optical generation of narrowband THz pulse based on heterostructure design, which also has implications in the design of THz magnonic devices.

Electric-field control of skyrmions in multiferroic heterostructure via magnetoelectric coupling.

Room-temperature skyrmions in magnetic multilayers are considered to be promising candidates for the next-generation spintronic devices. Several approaches have been developed to control skyrmions, but they either cause significant heat dissipation or require ultrahigh electric fields near the breakdown threshold. Here, we demonstrate electric-field control of skyrmions through strain-mediated magnetoelectric coupling in ferromagnetic/ferroelectric multiferroic heterostructures. We show the process of non-volatile creation of multiple skyrmions, reversible deformation and annihilation of a single skyrmion by performing magnetic force microscopy with in situ electric fields. Strain-induced changes in perpendicular magnetic anisotropy and interfacial Dzyaloshinskii-Moriya interaction strength are characterized experimentally. These experimental results, together with micromagnetic simulations, demonstrate that strain-mediated magnetoelectric coupling (via strain-induced changes in both the perpendicular magnetic anisotropy and interfacial Dzyaloshinskii-Moriya interaction is responsible for the observed electric-field control of skyrmions. Our work provides a platform to investigate electric-field control of skyrmions in multiferroic heterostructures and paves the way towards more energy-efficient skyrmion-based spintronics.

Domain Dynamics under Ultrafast Electric-Field Pulses.

Exploring the dynamic responses of a material is of importance to both understanding its fundamental physics at high frequencies and potential device applications. Here we develop a phase-field model for predicting the dynamics of ferroelectric materials and study the dynamic responses of ferroelectric domains and domain walls subjected to an ultrafast electric-field pulse. We discover a transition of domain evolution mechanisms from pure domain growth at a relatively low field to combined nucleation and growth of domains at a high field. We derive analytical models for the two regimes which allow us to extract the effective mass and damping coefficient of ferroelectric domain walls. The exhibition of two regimes for the ferroelectric domain dynamics at low and high electric fields is expected to be a general phenomenon that would appear for ferroic domains under other ultrafast stimuli. The present Letter also offers a general framework for studying domain dynamics and obtaining fundamental properties of domain walls and thus for manipulating the dynamic functionalities of ferroelectric materials.

Phase-Field Based Multiscale Modeling of Heterogeneous Solid Electrolytes: Applications to Nanoporous Li3PS4.

Modeling the effective ion conductivities of heterogeneous solid electrolytes typically involves the use of a computer-generated microstructure consisting of randomly or uniformly oriented fillers in a matrix. However, the structural features of the filler/matrix interface, which critically determine the interface ion conductivity and the microstructure morphology, have not been considered during the microstructure generation. Using nanoporous ß-Li3PS4 electrolyte as an example, we develop a phase-field model that enables generating nanoporous microstructures of different porosities and connectivity patterns based on the depth and the energy of the surface (pore/electrolyte interface), both of which are predicted through density functional theory (DFT) calculations. Room-temperature effective ion conductivities of the generated microstructures are then calculated numerically, using DFT-estimated surface Li-ion conductivity (3.14 × 10-3 S/cm) and experimentally measured bulk Li-ion conductivity (8.93 × 10-7 S/cm) of ß-Li3PS4 as the inputs. We also use the generated microstructures to inform effective medium theories to rapidly predict the effective ion conductivity via analytical calculations. When porosity approaches the percolation threshold, both the numerical and analytical methods predict a significantly enhanced Li-ion conductivity (1.74 × 10-4 S/cm) that is in good agreement with experimental data (1.64 × 10-4 S/cm). The present phase-field based multiscale model is generally applicable to predict both the microstructure patterns and the effective properties of heterogeneous solid electrolytes.

Epitaxial Halide Perovskite Lateral Double Heterostructure.

Epitaxial III-V semiconductor heterostructures are key components in modern microelectronics, electro-optics, and optoelectronics. With superior semiconducting properties, halide perovskite materials are rising as promising candidates for coherent heterostructure devices. In this report, spinodal decomposition is proposed and experimentally implemented to produce epitaxial double heterostructures in halide perovskite system. Pristine epitaxial mixed halide perovskites rods and films were synthesized via van der Waals epitaxy by chemical vapor deposition method. At room temperature, photon was applied as a knob to regulate the kinetics of spinodal decomposition and classic coarsening. By this approach, halide perovskite double heterostructures were created carrying epitaxial interfaces and outstanding optical properties. Reduced Fröhlich electron-phonon coupling was discovered in coherent halide double heterostructure, which is hypothetically attributed to the classic phonon confinement effect widely existing in III-V double heterostructures. As a proof-of-concept, our results suggest that halide perovskite-based epitaxial heterostructures may be promising for high-performance and low-cost optoelectronics, electro-optics, and microelectronics. Thus, ultimately, for practical device applications, it may be worthy to pursue these heterostructures via conventional vapor phase epitaxy approaches widely practised in III-V field.

Role of scaffold network in controlling strain and functionalities of nanocomposite films.

Strain is a novel approach to manipulating functionalities in correlated complex oxides. However, significant epitaxial strain can only be achieved in ultrathin layers. We show that, under direct lattice matching framework, large and uniform vertical strain up to 2% can be achieved to significantly modify the magnetic anisotropy, magnetism, and magnetotransport properties in heteroepitaxial nanoscaffold films, over a few hundred nanometers in thickness. Comprehensive designing principles of large vertical strain have been proposed. Phase-field simulations not only reveal the strain distribution but also suggest that the ultimate strain is related to the vertical interfacial area and interfacial dislocation density. By changing the nanoscaffold density and dimension, the strain and the magnetic properties can be tuned. The established correlation among the vertical interface-strain-properties in nanoscaffold films can consequently be used to tune other functionalities in a broad range of complex oxide films far beyond critical thickness.

Fast 180° magnetization switching in a strain-mediated multiferroic heterostructure driven by a voltage.

Voltage-driven 180° magnetization switching provides a low-power alternative to current-driven magnetization switching widely used in spintronic devices. Here we computationally demonstrate a promising route to achieve voltage-driven in-plane 180° magnetization switching in a strain-mediated multiferroic heterostructure (e.g., a heterostructure consisting of an amorphous, slightly elliptical Co40Fe40B20 nanomagnet on top of a Pb(Zr,Ti)O3 film as an example). This 180° switching follows a unique precessional path all in the film plane, and is enabled by manipulating magnetization dynamics with fast, local piezostrains (rise/release time <0.1 ns) on the Pb(Zr,Ti)O3 film surface. Our analyses predict ultralow area energy consumption per switching (~0.03 J/m(2)), approximately three orders of magnitude smaller than that dissipated by current-driven magnetization switching. A fast overall switching time of about 2.3 ns is also demonstrated. Further reduction of energy consumption and switching time can be achieved by optimizing the structure and material selection. The present design provides an additional viable route to realizing low-power and high-speed spintronics.

Dynamic in situ observation of voltage-driven repeatable magnetization reversal at room temperature.

Purely voltage-driven, repeatable magnetization reversal provides a tantalizing potential for the development of spintronic devices with a minimum amount of power consumption. Substantial progress has been made in this subject especially on magnetic/ferroelectric heterostructures. Here, we report the in situ observation of such phenomenon in a NiFe thin film grown directly on a rhombohedral Pb(Mg1/3Nb2/3)0.7Ti0.3O3(PMN-PT) ferroelectric crystal. Under a cyclic voltage applied perpendicular to the PMN-PT without a magnetic field, the local magnetization of NiFe can be repetitively reversed through an out-of-plane excursion and then back into the plane. Using phase field simulations we interpret magnetization reversal as a synergistic effect of the metastable ferroelastic switching in the PMN-PT and an electrically rotatable local exchange bias field arising from the heterogeneously distributed NiO clusters at the interface.

Fast Magnetic Domain-Wall Motion in a Ring-Shaped Nanowire Driven by a Voltage.

Magnetic domain-wall motion driven by a voltage dissipates much less heat than by a current, but none of the existing reports have achieved speeds exceeding 100 m/s. Here phase-field and finite-element simulations were combined to study the dynamics of strain-mediated voltage-driven magnetic domain-wall motion in curved nanowires. Using a ring-shaped, rough-edged magnetic nanowire on top of a piezoelectric disk, we demonstrate a fast voltage-driven magnetic domain-wall motion with average velocity up to 550 m/s, which is comparable to current-driven wall velocity. An analytical theory is derived to describe the strain dependence of average magnetic domain-wall velocity. Moreover, one 180° domain-wall cycle around the ring dissipates an ultrasmall amount of heat, as small as 0.2 fJ, approximately 3 orders of magnitude smaller than those in current-driven cases. These findings suggest a new route toward developing high-speed, low-power-dissipation domain-wall spintronics.