Non-volatile electric control of spin-charge conversion in a SrTiO3 Rashba system.

After 50 years of development, the technology of today's electronics is approaching its physical limits, with feature sizes smaller than 10 nanometres. It is also becoming clear that the ever-increasing power consumption of information and communication systems1 needs to be contained. These two factors require the introduction of non-traditional materials and state variables. As recently highlighted2, the remanence associated with collective switching in ferroic systems is an appealing way to reduce power consumption. A promising approach is spintronics, which relies on ferromagnets to provide non-volatility and to generate and detect spin currents3. However, magnetization reversal by spin transfer torques4 is a power-consuming process. This is driving research on multiferroics to achieve low-power electric-field control of magnetization5, but practical materials are scarce and magnetoelectric switching remains difficult to control. Here we demonstrate an alternative strategy to achieve low-power spin detection, in a non-magnetic system. We harness the electric-field-induced ferroelectric-like state of strontium titanate (SrTiO3)6-9 to manipulate the spin-orbit properties10 of a two-dimensional electron gas11, and efficiently convert spin currents into positive or negative charge currents, depending on the polarization direction. This non-volatile effect opens the way to the electric-field control of spin currents and to ultralow-power spintronics, in which non-volatility would be provided by ferroelectricity rather than by ferromagnetism.

Electric-field-induced multiferroic topological solitons.

Topologically protected spin whirls in ferromagnets are foreseen as the cart-horse of solitonic information technologies. Nevertheless, the future of skyrmionics may rely on antiferromagnets due to their immunity to dipolar fields, straight motion along the driving force and ultrafast dynamics. While complex topological objects were recently discovered in intrinsic antiferromagnets, mastering their nucleation, stabilization and manipulation with energy-efficient means remains an outstanding challenge. Designing topological polar states in magnetoelectric antiferromagnetic multiferroics would allow one to electrically write, detect and erase topological antiferromagnetic entities. Here we stabilize ferroelectric centre states using a radial electric field in multiferroic BiFeO3 thin films. We show that such polar textures contain flux closures of antiferromagnetic spin cycloids, with distinct antiferromagnetic entities at their cores depending on the electric field polarity. By tuning the epitaxial strain, quadrants of canted antiferromagnetic domains can also be electrically designed. These results open the path to reconfigurable topological states in multiferroic antiferromagnets.

Onset of Multiferroicity in Prototypical Single-Spin Cycloid BiFeO3 Thin Films.

In the room-temperature magnetoelectric multiferroic BiFeO3, the noncollinear antiferromagnetic state is coupled to the ferroelectric order, opening applications for low-power electric-field-controlled magnetic devices. While several strategies have been explored to simplify the ferroelectric landscape, here we directly stabilize a single-domain ferroelectric and spin cycloid state in epitaxial BiFeO3 (111) thin films grown on orthorhombic DyScO3 (011). Comparing them with films grown on SrTiO3 (111), we identify anisotropic in-plane strain as a powerful handle for tailoring the single antiferromagnetic state. In this single-domain multiferroic state, we establish the thickness limit of the coexisting electric and magnetic orders and directly visualize the suppression of the spin cycloid induced by the magnetoelectric interaction below the ultrathin limit of 1.4 nm. This as-grown single-domain multiferroic configuration in BiFeO3 thin films opens an avenue both for fundamental investigations and for electrically controlled noncollinear antiferromagnetic spintronics.

Visualizing Giant Ferroelectric Gating Effects in Large-Scale WSe2/BiFeO3 Heterostructures.

Multilayers based on quantum materials (complex oxides, topological insulators, transition-metal dichalcogenides, etc.) have enabled the design of devices that could revolutionize microelectronics and optoelectronics. However, heterostructures incorporating quantum materials from different families remain scarce, while they would immensely broaden the range of possible applications. Here we demonstrate the large-scale integration of compounds from two highly multifunctional families: perovskite oxides and transition-metal dichalcogenides (TMDs). We couple BiFeO3, a room-temperature multiferroic oxide, and WSe2, a semiconducting two-dimensional material with potential for photovoltaics and photonics. WSe2 is grown by molecular beam epitaxy and transferred on a centimeter-scale onto BiFeO3 films. Using angle-resolved photoemission spectroscopy, we visualize the electronic structure of 1 to 3 monolayers of WSe2 and evidence a giant energy shift as large as 0.75 eV induced by the ferroelectric polarization direction in the underlying BiFeO3. Such a strong shift opens new perspectives in the efficient manipulation of TMD properties by proximity effects.

Imaging Topological Defects in a Noncollinear Antiferromagnet.

We report on the formation of topological defects emerging from the cycloidal antiferromagnetic order at the surface of bulk BiFeO_{3} crystals. Combining reciprocal and real-space magnetic imaging techniques, we first observe, in a single ferroelectric domain, the coexistence of antiferromagnetic domains in which the antiferromagnetic cycloid propagates along different wave vectors. We then show that the direction of these wave vectors is not strictly locked to the preferred crystallographic axes as continuous rotations bridge different wave vectors. At the junctions between the magnetic domains, we observe topological line defects identical to those found in a broad variety of lamellar physical systems with rotational symmetries. Our work establishes the presence of these magnetic objects at room temperature in the multiferroic antiferromagnet BiFeO_{3}, offering new possibilities for their use in spintronics.

Imaging and Harnessing Percolation at the Metal-Insulator Transition of NdNiO3 Nanogaps.

Competition between coexisting electronic phases in first-order phase transitions can lead to a sharp change in the resistivity as the material is subjected to small variations in the driving parameter, for example, the temperature. One example of this phenomenon is the metal-insulator transition (MIT) in perovskite rare-earth nickelates. In such systems, reducing the transport measurement area to dimensions comparable to the domain size of insulating and metallic phases around the MIT should strongly influence the shape of the resistance-temperature curve. Here we measure the temperature dependence of the local resistance and the nanoscale domain distribution of NdNiO3 areas between Au contacts gapped by 40-260 nm. We find that a sharp resistance drop appears below the bulk MIT temperature at ∼105 K, with an amplitude inversely scaling with the nanogap width. By using X-ray photoemission electron microscopy, we directly correlate the resistance drop to the emergence and distribution of individual metallic domains at the nanogap. Our observation provides useful insight into percolation at the MIT of rare-earth nickelates.

Depth profiling charge accumulation from a ferroelectric into a doped Mott insulator.

The electric field control of functional properties is a crucial goal in oxide-based electronics. Nonvolatile switching between different resistivity or magnetic states in an oxide channel can be achieved through charge accumulation or depletion from an adjacent ferroelectric. However, the way in which charge distributes near the interface between the ferroelectric and the oxide remains poorly known, which limits our understanding of such switching effects. Here, we use a first-of-a-kind combination of scanning transmission electron microscopy with electron energy loss spectroscopy, near-total-reflection hard X-ray photoemission spectroscopy, and ab initio theory to address this issue. We achieve a direct, quantitative, atomic-scale characterization of the polarization-induced charge density changes at the interface between the ferroelectric BiFeO3 and the doped Mott insulator Ca(1-x)Ce(x)MnO3, thus providing insight on how interface-engineering can enhance these switching effects.

Unidirectional Spin-Dependent Molecule-Ferromagnet Hybridized States Anisotropy in Cobalt Phthalocyanine Based Magnetic Tunnel Junctions.

Organic or molecular spintronics is a rising field of research at the frontier between condensed matter physics and chemistry. It aims to mix spin physics and the richness of chemistry towards designing new properties for spin electronics devices through engineering at the molecular scale. Beyond the expectation of a long spin lifetime, molecules can be also used to tailor the spin polarization of the injected current through the spin-dependent hybridization between molecules and ferromagnetic electrodes. In this Letter, we provide direct evidence of a hybrid interface spin polarization reversal due to the differing hybridization between phthalocyanine molecules and each cobalt electrode in Co/CoPc/Co magnetic tunnel junctions. Tunnel magnetoresistance and anisotropic tunnel magnetoresistance experiments show that interfacial hybridized electronic states have a unidirectional anisotropy that can be controlled by an electric field and that spin hybridization at the bottom and top interfaces differ, leading to an inverse tunnel magnetoresistance.

Voltage-based magnetization switching and reading in magnetoelectric spin-orbit nanodevices.

As CMOS technologies face challenges in dimensional and voltage scaling, the demand for novel logic devices has never been greater, with spin-based devices offering scaling potential, at the cost of significantly high switching energies. Alternatively, magnetoelectric materials are predicted to enable low-power magnetization control, a solution with limited device-level results. Here, we demonstrate voltage-based magnetization switching and reading in nanodevices at room temperature, enabled by exchange coupling between multiferroic BiFeO3 and ferromagnetic CoFe, for writing, and spin-to-charge current conversion between CoFe and Pt, for reading. We show that, upon the electrical switching of the BiFeO3, the magnetization of the CoFe can be reversed, giving rise to different voltage outputs. Through additional microscopy techniques, magnetization reversal is linked with the polarization state and antiferromagnetic cycloid propagation direction in the BiFeO3. This study constitutes the building block for magnetoelectric spin-orbit logic, opening a new avenue for low-power beyond-CMOS technologies.

A ferroelectric memristor.

Memristors are continuously tunable resistors that emulate biological synapses. Conceptualized in the 1970s, they traditionally operate by voltage-induced displacements of matter, although the details of the mechanism remain under debate. Purely electronic memristors based on well-established physical phenomena with albeit modest resistance changes have also emerged. Here we demonstrate that voltage-controlled domain configurations in ferroelectric tunnel barriers yield memristive behaviour with resistance variations exceeding two orders of magnitude and a 10 ns operation speed. Using models of ferroelectric-domain nucleation and growth, we explain the quasi-continuous resistance variations and derive a simple analytical expression for the memristive effect. Our results suggest new opportunities for ferroelectrics as the hardware basis of future neuromorphic computational architectures.

Room temperature electrical manipulation of giant magnetoresistance in spin valves exchange-biased with BiFeO3.

Magnetoelectric multiferroics are attractive materials for the development of low-power electrically controlled spintronic devices. Here we report the optimization of the exchange bias as well as the giant magnetoresistance effect (GMR) of spin valves deposited on top of BiFeO(3)-based heterostructures. We show that the exchange bias can be electrically controlled through a change in the relative proportion of 109° domain walls and propose solutions toward a reversible process.

Atomic and electronic structure of the BaTiO3/Fe interface in multiferroic tunnel junctions.

Artificial multiferroic tunnel junctions combining a ferroelectric tunnel barrier of BaTiO(3) with magnetic electrodes display a tunnel magnetoresistance whose intensity can be controlled by the ferroelectric polarization of the barrier. This effect, called tunnel electromagnetoresistance (TEMR), and the corollary magnetoelectric coupling mechanisms at the BaTiO(3)/Fe interface were recently reported through macroscopic techniques. Here, we use advanced spectromicroscopy techniques by means of aberration-corrected scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS) to probe locally the nanoscale structural and electronic modifications at the ferroelectric/ferromagnetic interface. Atomically resolved real-space spectroscopic techniques reveal the presence of a single FeO layer between BaTiO(3) and Fe. Based on this accurate description of the studied interface, we propose an atomistic model of the ferroelectric/ferromagnetic interface further validated by comparing experimental and simulated STEM images with atomic resolution. Density functional theory calculations allow us to interpret the electronic and magnetic properties of these interfaces and to understand better their key role in the physics of multiferroics nanostructures.

BiFeO3 Nanoparticles: The "Holy-Grail" of Piezo-Photocatalysts?

Recently, piezoelectric-based catalysis has been demonstrated to be an efficient means and promising alternative to sunlight-driven photocatalysis, where mechanical vibrations trigger redox reactions. Here, 60 nm-size BiFeO3 nanoparticles are shown to be very effective for piezo-degrading Rhodamine B (RhB) model dye with record degradation rate reaching 13 810 L mol-1  min-1 , and even 41 750 L mol-1  min-1 (i.e., 100% RhB degradation within 5 min) when piezocatalysis is synergistically combined with sunlight photocatalysis. These BiFeO3 piezocatalytic nanoparticles are also demonstrated to be versatile toward several dyes and pharmaceutical pollutants, with over 80% piezo-decomposition within 120 min. The maintained high piezoelectric coefficient combined with low dielectric constant, high-elastic modulus, and the nanosized shape make these BiFeO3  nanoparticles extremely efficient piezocatalysts. To avoid subsequent secondary pollution and enable their reusability, the BiFeO3 nanoparticles are further embedded in a polymer P(VDF-TrFE) matrix. The as-designed flexible, chemically stable, and recyclable nanocomposites still keep remarkable piezocatalytic and piezo-photocatalytic performances (i.e., 92% and 100% RhB degradation, respectively, within 20 min). This work opens a new research avenue for BiFeO3 that is the model multiferroic and offers a new platform for water cleaning, as well as other applications such as water splitting, CO2 reduction, or surface purification.

Temporal and spatial tracking of ultrafast light-induced strain and polarization modulation in a ferroelectric thin film.

Ultrashort light pulses induce rapid deformations of crystalline lattices. In ferroelectrics, lattice deformations couple directly to the polarization, which opens the perspective to modulate the electric polarization on an ultrafast time scale. Here, we report on the temporal and spatial tracking of strain and polar modulation in a single-domain BiFeO3 thin film by ultrashort light pulses. To map the light-induced deformation of the BiFeO3 unit cell, we perform time-resolved optical reflectivity and time-resolved x-ray diffraction. We show that an optical femtosecond laser pulse generates not only longitudinal but also shear strains. The longitudinal strain peaks at a large amplitude of 0.6%. The access of both the longitudinal and shear strains enables to quantitatively reconstruct the ultrafast deformation of the unit cell and to infer the corresponding reorientation of the ferroelectric polarization direction in space and time. Our findings open new perspectives for ultrafast manipulation of strain-coupled ferroic orders.

Nanoscale electrostatic manipulation of magnetic flux quanta in ferroelectric/superconductor BiFeO3/YBa2Cu3O(7-δ) heterostructures.

Using heterostructures that combine a large-polarization ferroelectric (BiFeO3) and a high-temperature superconductor (YBa2Cu3O(7-δ)), we demonstrate the modulation of the superconducting condensate at the nanoscale via ferroelectric field effects. Through this mechanism, a nanoscale pattern of normal regions that mimics the ferroelectric domain structure can be created in the superconductor. This yields an energy landscape for magnetic flux quanta and, in turn, couples the local ferroelectric polarization to the local magnetic induction. We show that this form of magnetoelectric coupling, together with the possibility to reversibly design the ferroelectric domain structure, allows the electrostatic manipulation of magnetic flux quanta.

Voltage-Controlled Reconfigurable Magnonic Crystal at the Sub-micrometer Scale.

Multiferroics offer an elegant means to implement voltage control and on the fly reconfigurability in microscopic, nanoscaled systems based on ferromagnetic materials. These properties are particularly interesting for the field of magnonics, where spin waves are used to perform advanced logical or analogue functions. Recently, the emergence of nanomagnonics is expected to eventually lead to the large-scale integration of magnonic devices. However, a compact voltage-controlled, on demand reconfigurable magnonic system has yet to be shown. Here, we introduce the combination of multiferroics with ferromagnets in a fully epitaxial heterostructure to achieve such voltage-controlled and reconfigurable magnonic systems. Imprinting a remnant electrical polarization in thin multiferroic BiFeO3 with a periodicity of 500 nm yields a modulation of the effective magnetic field in the micrometer-scale, ferromagnetic La2/3Sr1/3MnO3 magnonic waveguide. We evidence the magnetoelectric coupling by characterizing the spin wave propagation spectrum in this artificial, voltage induced, magnonic crystal and demonstrate the occurrence of a robust magnonic band gap with >20 dB rejection.

Learning through ferroelectric domain dynamics in solid-state synapses.

In the brain, learning is achieved through the ability of synapses to reconfigure the strength by which they connect neurons (synaptic plasticity). In promising solid-state synapses called memristors, conductance can be finely tuned by voltage pulses and set to evolve according to a biological learning rule called spike-timing-dependent plasticity (STDP). Future neuromorphic architectures will comprise billions of such nanosynapses, which require a clear understanding of the physical mechanisms responsible for plasticity. Here we report on synapses based on ferroelectric tunnel junctions and show that STDP can be harnessed from inhomogeneous polarization switching. Through combined scanning probe imaging, electrical transport and atomic-scale molecular dynamics, we demonstrate that conductance variations can be modelled by the nucleation-dominated reversal of domains. Based on this physical model, our simulations show that arrays of ferroelectric nanosynapses can autonomously learn to recognize patterns in a predictable way, opening the path towards unsupervised learning in spiking neural networks.

Space-charge Effect on Electroresistance in Metal-Ferroelectric-Metal capacitors.

Resistive switching through electroresistance (ER) effect in metal-ferroelectric-metal (MFM) capacitors has attracted increasing interest due to its potential applications as memories and logic devices. However, the detailed electronic mechanisms resulting in large ER when polarisation switching occurs in the ferroelectric barrier are still not well understood. Here, ER effect up to 1000% at room temperature is demonstrated in C-MOS compatible MFM nanocapacitors with a 8.8 nm-thick poly(vinylidene fluoride) (PVDF) homopolymer ferroelectric, which is very promising for silicon industry integration. Most remarkably, using theory developed for metal-semiconductor rectifying contacts, we derive an analytical expression for the variation of interfacial barrier heights due to space-charge effect that can interpret the observed ER response. We extend this space-charge model, related to the release of trapped charges by defects, to MFM structures made of ferroelectric oxides. This space-charge model provides a simple and straightforward tool to understand recent unusual reports. Finally, this work suggests that defect-engineering could be an original and efficient route for tuning the space-charge effect and thus the ER performances in future electronic devices.

Giant electroresistance of super-tetragonal BiFeO3-based ferroelectric tunnel junctions.

Ferroelectric tunnel junctions enable a nondestructive readout of the ferroelectric state via a change of resistance induced by switching the ferroelectric polarization. We fabricated submicrometer solid-state ferroelectric tunnel junctions based on a recently discovered polymorph of BiFeO3 with giant axial ratio ("T-phase"). Applying voltage pulses to the junctions leads to the highest resistance changes (OFF/ON ratio >10,000) ever reported with ferroelectric tunnel junctions. Along with the good retention properties, this giant effect reinforces the interest in nonvolatile memories based on ferroelectric tunnel junctions. We also show that the changes in resistance scale with the nucleation and growth of ferroelectric domains in the ultrathin BiFeO3 (imaged by piezoresponse force microscopy), thereby suggesting potential as multilevel memory cells and memristors.

Ferroelectric control of a Mott insulator.

The electric field control of functional properties is an important goal in oxide-based electronics. To endow devices with memory, ferroelectric gating is interesting, but usually weak compared to volatile electrolyte gating. Here, we report a very large ferroelectric field-effect in perovskite heterostructures combining the Mott insulator CaMnO3 and the ferroelectric BiFeO3 in its "supertetragonal" phase. Upon polarization reversal of the BiFeO3 gate, the CaMnO3 channel resistance shows a fourfold variation around room temperature, and a tenfold change at ~200 K. This is accompanied by a carrier density modulation exceeding one order of magnitude. We have analyzed the results for various CaMnO3 thicknesses and explain them by the electrostatic doping of the CaMnO3 layer and the presence of a fixed dipole at the CaMnO3/BiFeO3 interface. Our results suggest the relevance of ferroelectric gates to control orbital- or spin-ordered phases, ubiquitous in Mott systems, and pave the way toward efficient Mott-tronics devices.