Unconventional Polarization-Switching Mechanism in (Hf, Zr)O_{2} Ferroelectrics and Its Implications.

HfO_{2}-based ferroelectric thin films are promising for their application in ferroelectric devices. Predicting the ultimate magnitude of polarization and understanding its switching mechanism are critical to realize the optimal performance of these devices. Here, a generalized solid-state variable cell nudged elastic band method is employed to predict the switching pathway associated with domain-wall motion in (Hf,Zr)O_{2} ferroelectrics. It is found that the polarization reversal pathway, where threefold coordinated O atoms pass across the nominal unit-cell boundaries defined by the Hf/Zr atomic planes, is energetically more favorable than the conventional pathway where the O atoms do not pass through these planes. This finding implies that the polarization orientation in the orthorhombic Pca2_{1} phase of HfO_{2} and its derivatives is opposite to that normally assumed, predicts the spontaneous polarization magnitude of about 70 µC/cm^{2} that is nearly 50% larger than the commonly accepted value, signifies a positive intrinsic longitudinal piezoelectric coefficient, and suggests growth of ferroelectric domains, in response to an applied electric field, structurally reversed to those usually anticipated. These results provide important insights into the understanding of ferroelectricity in HfO_{2}-based ferroelectrics.

Symmetry Control of Unconventional Spin-Orbit Torques in IrO2.

Spin-orbit torques generated by a spin current are key to magnetic switching in spintronic applications. The polarization of the spin current dictates the direction of switching required for energy-efficient devices. Conventionally, the polarizations of these spin currents are restricted to be along a certain direction due to the symmetry of the material allowing only for efficient in-plane magnetic switching. Unconventional spin-orbit torques arising from novel spin current polarizations, however, have the potential to switch other magnetization orientations such as perpendicular magnetic anisotropy, which is desired for higher density spintronic-based memory devices. Here, it is demonstrated that low crystalline symmetry is not required for unconventional spin-orbit torques and can be generated in a nonmagnetic high symmetry material, iridium dioxide (IrO2 ), using epitaxial design. It is shown that by reducing the relative crystalline symmetry with respect to the growth direction large unconventional spin currents can be generated and hence spin-orbit torques. Furthermore, the spin polarizations detected in (001), (110), and (111) oriented IrO2 thin films are compared to show which crystal symmetries restrict unconventional spin transport. Understanding and tuning unconventional spin transport generation in high symmetry materials can provide a new route towards energy-efficient magnetic switching in spintronic devices.

Néel Spin Currents in Antiferromagnets.

Ferromagnets are known to support spin-polarized currents that control various spin-dependent transport phenomena useful for spintronics. On the contrary, fully compensated antiferromagnets are expected to support only globally spin-neutral currents. Here, we demonstrate that these globally spin-neutral currents can represent the Néel spin currents, i.e., staggered spin currents flowing through different magnetic sublattices. The Néel spin currents emerge in antiferromagnets with strong intrasublattice coupling (hopping) and drive the spin-dependent transport phenomena such as tunneling magnetoresistance (TMR) and spin-transfer torque (STT) in antiferromagnetic tunnel junctions (AFMTJs). Using RuO_{2} and Fe_{4}GeTe_{2} as representative antiferromagnets, we predict that the Néel spin currents with a strong staggered spin polarization produce a sizable fieldlike STT capable of the deterministic switching of the Néel vector in the associated AFMTJs. Our work uncovers the previously unexplored potential of fully compensated antiferromagnets and paves a new route to realize the efficient writing and reading of information for antiferromagnetic spintronics.

Switchable Anomalous Hall Effects in Polar-Stacked 2D Antiferromagnet MnBi2Te4.

van der Waals (vdW) assembly of two-dimensional (2D) materials allows polar layer stacking to realize novel properties switchable by the induced electric polarization. Here, based on symmetry analyses and density-functional calculations, we explore the emergence of the anomalous Hall effect (AHE) in antiferromagnetic MnBi2Te4 films assembled by polar layer stacking. We demonstrate that breaking P̂T̂ symmetry in an MnBi2Te4 bilayer produces a magnetoelectric effect and a spontaneous AHE switchable by electric polarization. We find that reversible polarization at one of the interfaces in a three-layer MnBi2Te4 film drives a metal-insulator transition, as well as switching between the AHE and quantum AHE (QAHE). Finally, we predict that engineering interlayer polarization in a three-layer MnBi2Te4 film allows converting MnBi2Te4 from a trivial insulator to a Chern insulator. Overall, our work emphasizes the topological properties in 2D vdW antiferromagnets induced by polar layer stacking, which do not exist in a bulk material.

Observation of anti-damping spin-orbit torques generated by in-plane and out-of-plane spin polarizations in MnPd3.

Large spin-orbit torques (SOTs) generated by topological materials and heavy metals interfaced with ferromagnets are promising for next-generation magnetic memory and logic devices. SOTs generated from y spin originating from spin Hall and Edelstein effects can realize field-free magnetization switching only when the magnetization and spin are collinear. Here we circumvent the above limitation by utilizing unconventional spins generated in a MnPd3 thin film grown on an oxidized silicon substrate. We observe conventional SOT due to y spin, and out-of-plane and in-plane anti-damping-like torques originated from z spin and x spin, respectively, in MnPd3/CoFeB heterostructures. Notably, we have demonstrated complete field-free switching of perpendicular cobalt via out-of-plane anti-damping-like SOT. Density functional theory calculations show that the observed unconventional torques are due to the low symmetry of the (114)-oriented MnPd3 films. Altogether our results provide a path toward realization of a practical spin channel in ultrafast magnetic memory and logic devices.

Prominent Size Effects without a Depolarization Field Observed in Ultrathin Ferroelectric Oxide Membranes.

The increasing miniaturization of electronics requires a better understanding of material properties at the nanoscale. Many studies have shown that there is a ferroelectric size limit in oxides, below which the ferroelectricity will be strongly suppressed due to the depolarization field, and whether such a limit still exists in the absence of the depolarization field remains unclear. Here, by applying uniaxial strain, we obtain pure in-plane polarized ferroelectricity in ultrathin SrTiO_{3} membranes, providing a clean system with high tunability to explore ferroelectric size effects especially the thickness-dependent ferroelectric instability with no depolarization field. Surprisingly, the domain size, ferroelectric transition temperature, and critical strain for room-temperature ferroelectricity all exhibit significant thickness dependence. These results indicate that the stability of ferroelectricity is suppressed (enhanced) by increasing the surface or bulk ratio (strain), which can be explained by considering the thickness-dependent dipole-dipole interactions within the transverse Ising model. Our study provides new insights into ferroelectric size effects and sheds light on the applications of ferroelectric thin films in nanoelectronics.

Interface-engineered ferroelectricity of epitaxial Hf0.5Zr0.5O2 thin films.

Ferroelectric hafnia-based thin films have attracted intense attention due to their compatibility with complementary metal-oxide-semiconductor technology. However, the ferroelectric orthorhombic phase is thermodynamically metastable. Various efforts have been made to stabilize the ferroelectric orthorhombic phase of hafnia-based films such as controlling the growth kinetics and mechanical confinement. Here, we demonstrate a key interface engineering strategy to stabilize and enhance the ferroelectric orthorhombic phase of the Hf0.5Zr0.5O2 thin film by deliberately controlling the termination of the bottom La0.67Sr0.33MnO3 layer. We find that the Hf0.5Zr0.5O2 films on the MnO2-terminated La0.67Sr0.33MnO3 have more ferroelectric orthorhombic phase than those on the LaSrO-terminated La0.67Sr0.33MnO3, while with no wake-up effect. Even though the Hf0.5Zr0.5O2 thickness is as thin as 1.5 nm, the clear ferroelectric orthorhombic (111) orientation is observed on the MnO2 termination. Our transmission electron microscopy characterization and theoretical modelling reveal that reconstruction at the Hf0.5Zr0.5O2/ La0.67Sr0.33MnO3 interface and hole doping of the Hf0.5Zr0.5O2 layer resulting from the MnO2 interface termination are responsible for the stabilization of the metastable ferroelectric phase of Hf0.5Zr0.5O2. We anticipate that these results will inspire further studies of interface-engineered hafnia-based systems.

In-plane charged domain walls with memristive behaviour in a ferroelectric film.

Domain-wall nanoelectronics is considered to be a new paradigm for non-volatile memory and logic technologies in which domain walls, rather than domains, serve as an active element. Especially interesting are charged domain walls in ferroelectric structures, which have subnanometre thicknesses and exhibit non-trivial electronic and transport properties that are useful for various nanoelectronics applications1-3. The ability to deterministically create and manipulate charged domain walls is essential to realize their functional properties in electronic devices. Here we report a strategy for the controllable creation and manipulation of in-plane charged domain walls in BiFeO3 ferroelectric films a few nanometres thick. By using an in situ biasing technique within a scanning transmission electron microscope, an unconventional layer-by-layer switching mechanism is detected in which ferroelectric domain growth occurs in the direction parallel to an applied electric field. Based on atomically resolved electron energy-loss spectroscopy, in situ charge mapping by in-line electron holography and theoretical calculations, we show that oxygen vacancies accumulating at the charged domain walls are responsible for the domain-wall stability and motion. Voltage control of the in-plane domain-wall position within a BiFeO3 film gives rise to multiple non-volatile resistance states, thus demonstrating the key functional property of being a memristor a few unit cells thick. These results promote a better understanding of ferroelectric switching behaviour and provide a new strategy for creating unit-cell-scale devices.

Tunneling Valley Hall Effect Driven by Tilted Dirac Fermions.

Valleytronics is a research field utilizing a valley degree of freedom of electrons for information processing and storage. A strong valley polarization is critical for realistic valleytronic applications. Here, we predict a tunneling valley Hall effect (TVHE) driven by tilted Dirac fermions in all-in-one tunnel junctions based on a two-dimensional (2D) valley material. Different doping of the electrode and spacer regions in these tunnel junctions results in momentum filtering of the tunneling Dirac fermions, generating a strong transverse valley Hall current dependent on the Dirac-cone tilting. Using the parameters of an existing 2D valley material, we demonstrate that such a strong TVHE can host a giant valley Hall angle even in the absence of the Berry curvature. Finally, we predict that resonant tunneling can occur in a tunnel junction with properly engineered device parameters such as the spacer width and transport direction, providing significant enhancement of the valley Hall angle. Our work opens a new approach to generate valley polarization in realistic valleytronic systems.

Efficient perpendicular magnetization switching by a magnetic spin Hall effect in a noncollinear antiferromagnet.

Current induced spin-orbit torques driven by the conventional spin Hall effect are widely used to manipulate the magnetization. This approach, however, is nondeterministic and inefficient for the switching of magnets with perpendicular magnetic anisotropy that are demanded by the high-density magnetic storage and memory devices. Here, we demonstrate that this limitation can be overcome by exploiting a magnetic spin Hall effect in noncollinear antiferromagnets, such as Mn3Sn. The magnetic group symmetry of Mn3Sn allows generation of the out-of-plane spin current carrying spin polarization collinear to its direction induced by an in-plane charge current. This spin current drives an out-of-plane anti-damping torque providing the deterministic switching of the perpendicular magnetization of an adjacent Ni/Co multilayer. Due to being odd with respect to time reversal symmetry, the observed magnetic spin Hall effect and the resulting spin-orbit torque can be reversed with reversal of the antiferromagnetic order. Contrary to the conventional spin-orbit torque devices, the demonstrated magnetization switching does not need an external magnetic field and requires much lower current density which is useful for low-power spintronics.

A Room-Temperature Ferroelectric Resonant Tunneling Diode.

Resonant tunneling is a quantum-mechanical effect in which electron transport is controlled by the discrete energy levels within a quantum-well (QW) structure. A ferroelectric resonant tunneling diode (RTD) exploits the switchable electric polarization state of the QW barrier to tune the device resistance. Here, the discovery of robust room-temperature ferroelectric-modulated resonant tunneling and negative differential resistance (NDR) behaviors in all-perovskite-oxide BaTiO3 /SrRuO3 /BaTiO3 QW structures is reported. The resonant current amplitude and voltage are tunable by the switchable polarization of the BaTiO3 ferroelectric with the NDR ratio modulated by ≈3 orders of magnitude and an OFF/ON resistance ratio exceeding a factor of 2 × 104 . The observed NDR effect is explained an energy bandgap between Ru-t2g and Ru-eg orbitals driven by electron-electron correlations, as follows from density functional theory calculations. This study paves the way for ferroelectric-based quantum-tunneling devices in future oxide electronics.

Intrinsic ferroelectricity in Y-doped HfO2 thin films.

Ferroelectric HfO2-based materials hold great potential for the widespread integration of ferroelectricity into modern electronics due to their compatibility with existing Si technology. Earlier work indicated that a nanometre grain size was crucial for the stabilization of the ferroelectric phase. This constraint, associated with a high density of structural defects, obscures an insight into the intrinsic ferroelectricity of HfO2-based materials. Here we demonstrate that stable and enhanced polarization can be achieved in epitaxial HfO2 films with a high degree of structural order (crystallinity). An out-of-plane polarization value of 50 µC cm-2 has been observed at room temperature in Y-doped HfO2(111) epitaxial thin films, with an estimated full value of intrinsic polarization of 64 µC cm-2, which is in close agreement with density functional theory calculations. The crystal structure of films reveals the Pca21 orthorhombic phase with small rhombohedral distortion, underlining the role of the structural constraint in stabilizing the ferroelectric phase. Our results suggest that it could be possible to exploit the intrinsic ferroelectricity of HfO2-based materials, optimizing their performance in device applications.

Tunneling Magnetoresistance in Noncollinear Antiferromagnetic Tunnel Junctions.

Antiferromagnetic (AFM) spintronics has emerged as a subfield of spintronics driven by the advantages of antiferromagnets producing no stray fields and exhibiting ultrafast magnetization dynamics. The efficient method to detect an AFM order parameter, known as the Néel vector, by electric means is critical to realize concepts of AFM spintronics. Here, we demonstrate that noncollinear AFM metals, such as Mn_{3}Sn, exhibit a momentum dependent spin polarization which can be exploited in AFM tunnel junctions to detect the Néel vector. Using first-principles calculations, we predict a tunneling magnetoresistance (TMR) effect as high as 300% in AFM tunnel junctions with Mn_{3}Sn electrodes, where the junction resistance depends on the relative orientation of their Néel vectors and exhibits four nonvolatile resistance states. We argue that the spin-split band structure and the related TMR effect can also be realized in other noncollinear AFM metals like Mn_{3}Ge, Mn_{3}Ga, Mn_{3}Pt, and Mn_{3}GaN. Our work provides a robust method for detecting the Néel vector in noncollinear antiferromagnets via the TMR effect, which may be useful for their application in AFM spintronic devices.

Ferroelectric Control of Magnetic Skyrmions in Two-Dimensional van der Waals Heterostructures.

Magnetic skyrmions are chiral nanoscale spin textures which are usually induced by the Dzyaloshinskii-Moriya interaction (DMI). Recently, magnetic skyrmions have been observed in two-dimensional (2D) van der Waals (vdW) ferromagnetic materials, such as Fe3GeTe2. The electric control of skyrmions is important for their potential application in low-power memory technologies. Here, we predict that DMI and magnetic skyrmions in a Fe3GeTe2 monolayer can be controlled by ferroelectric polarization of an adjacent 2D vdW ferroelectric In2Se3. Based on density functional theory and atomistic spin-dynamics modeling, we find that the interfacial symmetry breaking produces a sizable DMI in a Fe3GeTe2/In2Se3 vdW heterostructure. We show that the magnitude of DMI can be controlled by ferroelectric polarization reversal, leading to creation and annihilation of skyrmions. Furthermore, we find that the sign of DMI in a In2Se3/Fe3GeTe2/In2Se3 heterostructure changes with ferroelectric switching reversing the skyrmion chirality. The predicted electrically controlled skyrmion formation may be interesting for spintronic applications.

Oxide Two-Dimensional Electron Gas with High Mobility at Room-Temperature.

The prospect of 2-dimensional electron gases (2DEGs) possessing high mobility at room temperature in wide-bandgap perovskite stannates is enticing for oxide electronics, particularly to realize transparent and high-electron mobility transistors. Nonetheless only a small number of studies to date report 2DEGs in BaSnO3 -based heterostructures. Here, 2DEG formation at the LaScO3 /BaSnO3 (LSO/BSO) interface with a room-temperature mobility of 60 cm2  V-1  s-1 at a carrier concentration of 1.7 × 1013  cm-2 is reported. This is an order of magnitude higher mobility at room temperature than achieved in SrTiO3 -based 2DEGs. This is achieved by combining a thick BSO buffer layer with an ex situ high-temperature treatment, which not only reduces the dislocation density but also produces a SnO2 -terminated atomically flat surface, followed by the growth of an overlying BSO/LSO interface. Using weak beam dark-field transmission electron microscopy imaging and in-line electron holography technique, a reduction of the threading dislocation density is revealed, and direct evidence for the spatial confinement of a 2DEG at the BSO/LSO interface is provided. This work opens a new pathway to explore the exciting physics of stannate-based 2DEGs at application-relevant temperatures for oxide nanoelectronics.

Spin-neutral currents for spintronics.

Electric currents carrying a net spin polarization are widely used in spintronics, whereas globally spin-neutral currents are expected to play no role in spin-dependent phenomena. Here we show that, in contrast to this common expectation, spin-independent conductance in compensated antiferromagnets and normal metals can be efficiently exploited in spintronics, provided their magnetic space group symmetry supports a non-spin-degenerate Fermi surface. Due to their momentum-dependent spin polarization, such antiferromagnets can be used as active elements in antiferromagnetic tunnel junctions (AFMTJs) and produce a giant tunneling magnetoresistance (TMR) effect. Using RuO2 as a representative compensated antiferromagnet exhibiting spin-independent conductance along the [001] direction but a non-spin-degenerate Fermi surface, we design a RuO2/TiO2/RuO2 (001) AFMTJ, where a globally spin-neutral charge current is controlled by the relative orientation of the Néel vectors of the two RuO2 electrodes, resulting in the TMR effect as large as ~500%. These results are expanded to normal metals which can be used as a counter electrode in AFMTJs with a single antiferromagnetic layer or other elements in spintronic devices. Our work uncovers an unexplored potential of the materials with no global spin polarization for utilizing them in spintronics.

Giant Transport Anisotropy in ReS_{2} Revealed via Nanoscale Conducting-Path Control.

The low in-plane symmetry in layered 1T'-ReS_{2} results in strong band anisotropy, while its manifestation in the electronic properties is challenging to resolve due to the lack of effective approaches for controlling the local current path. In this work, we reveal the giant transport anisotropy in monolayer to four-layer ReS_{2} by creating directional conducting paths via nanoscale ferroelectric control. By reversing the polarization of a ferroelectric polymer top layer, we induce a conductivity switching ratio of >1.5×10^{8} in the ReS_{2} channel at 300 K. Characterizing the domain-defined conducting nanowires in an insulating background shows that the conductivity ratio between the directions along and perpendicular to the Re chain can exceed 5.5×10^{4} in monolayer ReS_{2}. Theoretical modeling points to the band origin of the transport anomaly and further reveals the emergence of a flat band in few-layer ReS_{2}. Our work paves the path for implementing highly anisotropic 2D materials for designing novel collective phenomena and electron lensing applications.

Magnetoelectric Coupling at the Ni/Hf0.5Zr0.5O2 Interface.

Composite multiferroics containing ferroelectric and ferromagnetic components often have much larger magnetoelectric coupling compared to their single-phase counterparts. Doped or alloyed HfO2-based ferroelectrics may serve as a promising component in composite multiferroic structures potentially feasible for technological applications. Recently, a strong charge-mediated magnetoelectric coupling at the Ni/HfO2 interface has been predicted using density functional theory calculations. Here, we report on the experimental evidence of such magnetoelectric coupling at the Ni/Hf0.5Zr0.5O2(HZO) interface. Using a combination of operando XAS/XMCD and HAXPES/MCDAD techniques, we probe element-selectively the local magnetic properties at the Ni/HZO interface in functional Au/Co/Ni/HZO/W capacitors and demonstrate clear evidence of the ferroelectric polarization effect on the magnetic response of a nanometer-thick Ni marker layer. The observed magnetoelectric effect and the electronic band lineup of the Ni/HZO interface are interpreted based on the results of our theoretical modeling. It elucidates the critical role of an ultrathin NiO interlayer, which controls the sign of the magnetoelectric effect as well as provides a realistic band offset at the Ni/HZO interface, in agreement with the experiment. Our results hold promise for the use of ferroelectric HfO2-based composite multiferroics for the design of multifunctional devices compatible with modern semiconductor technology.

Defects in ferroelectric HfO2.

The discovery of ferroelectricity in polycrystalline thin films of doped HfO2 has reignited the expectations of developing competitive ferroelectric non-volatile memory devices. To date, it is widely accepted that the performance of HfO2-based ferroelectric devices during their life cycle is critically dependent on the presence of point defects as well as structural phase polymorphism, which mainly originates from defects either. The purpose of this review article is to overview the impact of defects in ferroelectric HfO2 on its functional properties and the resulting performance of memory devices. Starting from the brief summary of defects in classical perovskite ferroelectrics, we then introduce the known types of point defects in dielectric HfO2 thin films. Further, we discuss main analytical techniques used to characterize the concentration and distribution of defects in doped ferroelectric HfO2 thin films as well as at their interfaces with electrodes. The main part of the review is devoted to the recent experimental studies reporting the impact of defects in ferroelectric HfO2 structures on the performance of different memory devices. We end up with the summary and perspectives of HfO2-based ferroelectric competitive non-volatile memory devices.

Modulation of Spin-Orbit Torque from SrRuO3 by Epitaxial-Strain-Induced Octahedral Rotation.

Spin-orbit torque (SOT), which arises from the spin-orbit coupling of conduction electrons, is believed to be the key route for developing low-power, high-speed, and nonvolatile memory devices. Despite the theoretical prediction of pronounced Berry phase curvatures in certain transition-metal perovskite oxides, which lead to considerable intrinsic spin Hall conductivity, SOT from this class of materials has rarely been reported until recently. Here, the SOT generated by epitaxial SrRuO3 of three different crystal structures is systematically studied. The results of both spin-torque ferromagnetic resonance and in-plane harmonic Hall voltage measurements concurrently reveal that the intrinsic SOT efficiency of SrRuO3 decreases when the epitaxial strain changes from tensile to compressive. The X-ray diffraction data demonstrate a strong correlation between the magnitude of SOT and octahedral rotation around the in-plane axes of SrRuO3 , consistent with the theoretical prediction. This work offers new possibilities of tuning SOT with crystal structures and novel opportunities of integrating the unique properties of perovskite oxides with spintronic functionalities.