Reversible Optical Control of Polarization in Epitaxial Ferroelectric Thin Films.

Light is an effective tool to probe the polarization and domain distribution in ferroelectric materials passively, that is, non-invasively, for example, via optical second harmonic generation (SHG). With the emergence of oxide electronics, there is now a strong demand to expand the role of light toward active control of the polarization. In this work, optical control of the ferroelectric polarization is demonstrated in prototypical epitaxial PbZrxTi1-xO3 (PZT)-based heterostructures. This is accomplished in three steps, using above-bandgap UV light, while tracking the response of the polarization with optical SHG. First, it is found that UV-light exposure induces a transient enhancement or suppression of the ferroelectric polarization in films with an upward- or downward-oriented polarization, respectively. This behavior is attributed to a modified charge screening driven by the separation of photoexcited charge carriers at the Schottky interface of the ferroelectric thin film. Second, by taking advantage of this optical handle on electrostatics, remanent optical poling from a pristine multi-domain into a single-domain configuration is accomplished. Third, via thermal annealing or engineered electrostatic boundary conditions, a complete reversibility of the optical poling is further achieved. Hence, this work paves the way for the all-optical control of the spontaneous polarization in ferroelectric thin films.

Critical slowing down near a magnetic quantum phase transition with fermionic breakdown.

When a system close to a continuous phase transition is subjected to perturbations, it takes an exceptionally long time to return to equilibrium. This critical slowing down is observed universally in the dynamics of bosonic excitations, such as order-parameter collective modes, but it is not generally expected to occur for fermionic excitations. Here using terahertz time-domain spectroscopy, we find evidence for fermionic critical slowing down in YbRh2Si2 close to a quantum phase transition between an antiferromagnetic phase and a heavy Fermi liquid. In the latter phase, the relevant quasiparticles are a quantum superposition of itinerant and localized electronic states with a strongly enhanced effective mass. As the temperature is lowered on the heavy-Fermi-liquid side of the transition, the heavy-fermion spectral weight builds up until the Kondo temperature TK ≈ 25 K, then decays towards the quantum phase transition and is, thereafter, followed by a logarithmic rise of the quasiparticle excitation rate below 10 K. A two-band heavy-Fermi-liquid theory shows that this is indicative of the fermionic critical slowing down associated with heavy-fermion breakdown near the quantum phase transition. The critical exponent of this breakdown could be used to classify this system among a wider family of fermionic quantum phase transitions that is yet to be fully explored.

Defeating depolarizing fields with artificial flux closure in ultrathin ferroelectrics.

Material surfaces encompass structural and chemical discontinuities that often lead to the loss of the property of interest in so-called dead layers. It is particularly problematic in nanoscale oxide electronics, where the integration of strongly correlated materials into devices is obstructed by the thickness threshold required for the emergence of their functionality. Here we report the stabilization of ultrathin out-of-plane ferroelectricity in oxide heterostructures through the design of an artificial flux-closure architecture. Inserting an in-plane-polarized ferroelectric epitaxial buffer provides the continuity of polarization at the interface; despite its insulating nature, we observe the emergence of polarization in our out-of-plane-polarized model of ferroelectric BaTiO3 from the very first unit cell. In BiFeO3, the flux-closure approach stabilizes a 251° domain wall. Its unusual chirality is probably associated with the ferroelectric analogue to the Dzyaloshinskii-Moriya interaction. We, thus, see that in an adaptively engineered geometry, the depolarizing-field-screening properties of an insulator can even surpass those of a metal and be a source of functionality. This could be a useful insight on the road towards the next generation of oxide electronics.

Pressure Control of Nonferroelastic Ferroelectric Domains in ErMnO3.

Mechanical pressure controls the structural, electric, and magnetic order in solid-state systems, allowing tailoring of their physical properties. A well-established example is ferroelastic ferroelectrics, where the coupling between pressure and the primary symmetry-breaking order parameter enables hysteretic switching of the strain state and ferroelectric domain engineering. Here, we study the pressure-driven response in a nonferroelastic ferroelectric, ErMnO3, where the classical stress-strain coupling is absent and the domain formation is governed by creation-annihilation processes of topological defects. By annealing ErMnO3 polycrystals under variable pressures in the MPa regime, we transform nonferroelastic vortex-like domains into stripe-like domains. The width of the stripe-like domains is determined by the applied pressure as we confirm by three-dimensional phase field simulations, showing that pressure leads to oriented layer-like periodic domains. Our work demonstrates the possibility to utilize mechanical pressure for domain engineering in nonferroelastic ferroelectrics, providing a lever to control their dielectric and piezoelectric responses.

Non-volatile electric-field control of inversion symmetry.

Competition between ground states at phase boundaries can lead to significant changes in properties under stimuli, particularly when these ground states have different crystal symmetries. A key challenge is to stabilize and control the coexistence of symmetry-distinct phases. Using BiFeO3 layers confined between layers of dielectric TbScO3 as a model system, we stabilize the mixed-phase coexistence of centrosymmetric and non-centrosymmetric BiFeO3 phases at room temperature with antipolar, insulating and polar semiconducting behaviour, respectively. Application of orthogonal in-plane electric (polar) fields results in reversible non-volatile interconversion between the two phases, hence removing and introducing centrosymmetry. Counterintuitively, we find that an electric field 'erases' polarization, resulting from the anisotropy in octahedral tilts introduced by the interweaving TbScO3 layers. Consequently, this interconversion between centrosymmetric and non-centrosymmetric phases generates changes in the non-linear optical response of over three orders of magnitude, resistivity of over five orders of magnitude and control of microscopic polar order. Our work establishes a platform for cross-functional devices that take advantage of changes in optical, electrical and ferroic responses, and demonstrates octahedral tilts as an important order parameter in materials interface design.

Magnetoelectric transfer of a domain pattern.

The utility of ferroic materials is determined by the formation of domains and their poling behavior under externally applied fields. For multiferroics, which exhibit several types of ferroic order at once, it is also relevant how the domains of the coexisting ferroic states couple and what kind of functionality this might involve. In this work, we demonstrate the reversible transfer of a domain pattern between magnetization and electric-polarization space in the multiferroic Dy0.7Tb0.3FeO3. A magnetic field transfers a ferromagnetic domain pattern into an identical ferroelectric domain pattern while erasing it at its magnetic origin. Reverse transfer completes the cycle. To assess the generality of our experiment, we elaborate on its conceptual origin and aspects of application.

Current-driven dynamics and ratchet effect of skyrmion bubbles in a ferrimagnetic insulator.

Magnetic skyrmions are compact chiral spin textures that exhibit a rich variety of topological phenomena and hold potential for the development of high-density memory devices and novel computing schemes driven by spin currents. Here, we demonstrate the room-temperature interfacial stabilization and current-driven control of skyrmion bubbles in the ferrimagnetic insulator Tm3Fe5O12 coupled to Pt, showing the current-induced motion of individual skyrmion bubbles. The ferrimagnetic order of the crystal together with the interplay of spin-orbit torques and pinning determine the skyrmion dynamics in Tm3Fe5O12 and result in a strong skyrmion Hall effect characterized by a negative deflection angle and hopping motion. Further, we show that the velocity and depinning threshold of the skyrmion bubbles can be modified by exchange coupling Tm3Fe5O12 to an in-plane magnetized Y3Fe5O12 layer, which distorts the spin texture of the skyrmions and leads to directional-dependent rectification of their dynamics. This effect, which is equivalent to a magnetic ratchet, is exploited to control the skyrmion flow in a racetrack-like device.

Multilevel polarization switching in ferroelectric thin films.

Ferroic order is characterized by hystereses with two remanent states and therefore inherently binary. The increasing interest in materials showing non-discrete responses, however, calls for a paradigm shift towards continuously tunable remanent ferroic states. Device integration for oxide nanoelectronics furthermore requires this tunability at the nanoscale. Here we demonstrate that we can arbitrarily set the remanent ferroelectric polarization at nanometric dimensions. We accomplish this in ultrathin epitaxial PbZr0.52Ti0.48O3 films featuring a dense pattern of decoupled nanometric 180° domains with a broad coercive-field distribution. This multilevel switching is achieved by driving the system towards the instability at the morphotropic phase boundary. The phase competition near this boundary in combination with epitaxial strain increases the responsiveness to external stimuli and unlocks new degrees of freedom to nano-control the polarization. We highlight the technological benefits of non-binary switching by demonstrating a quasi-continuous tunability of the non-linear optical response and of tunnel electroresistance.

Emerging spin-phonon coupling through cross-talk of two magnetic sublattices.

Many material properties such as superconductivity, magnetoresistance or magnetoelectricity emerge from the non-linear interactions of spins and lattice/phonons. Hence, an in-depth understanding of spin-phonon coupling is at the heart of these properties. While most examples deal with one magnetic lattice only, the simultaneous presence of multiple magnetic orderings yield potentially unknown properties. We demonstrate a strong spin-phonon coupling in SmFeO3 that emerges from the interaction of both, iron and samarium spins. We probe this coupling as a remarkably large shift of phonon frequencies and the appearance of new phonons. The spin-phonon coupling is absent for the magnetic ordering of iron alone but emerges with the additional ordering of the samarium spins. Intriguingly, this ordering is not spontaneous but induced by the iron magnetism. Our findings show an emergent phenomenon from the non-linear interaction by multiple orders, which do not need to occur spontaneously. This allows for a conceptually different approach in the search for yet unknown properties.

Signatures of enhanced out-of-plane polarization in asymmetric BaTiO3 superlattices integrated on silicon.

In order to bring the diverse functionalities of transition metal oxides into modern electronics, it is imperative to integrate oxide films with controllable properties onto the silicon platform. Here, we present asymmetric LaMnO3/BaTiO3/SrTiO3 superlattices fabricated on silicon with layer thickness control at the unit-cell level. By harnessing the coherent strain between the constituent layers, we overcome the biaxial thermal tension from silicon and stabilize c-axis oriented BaTiO3 layers with substantially enhanced tetragonality, as revealed by atomically resolved scanning transmission electron microscopy. Optical second harmonic generation measurements signify a predominant out-of-plane polarized state with strongly enhanced net polarization in the tricolor superlattices, as compared to the BaTiO3 single film and conventional BaTiO3/SrTiO3 superlattice grown on silicon. Meanwhile, this coherent strain in turn suppresses the magnetism of LaMnO3 as the thickness of BaTiO3 increases. Our study raises the prospect of designing artificial oxide superlattices on silicon with tailored functionalities.

Writing of strain-controlled multiferroic ribbons into MnWO4.

Local and low-dimensional structures, such as interfaces, domain walls and structural defects, may exhibit physical properties different from the bulk. Therein, a wide variety of local phases were discovered including conductive interfaces, sheet superconductivity, and magnetoelectric domain walls. The confinement of combined magnetic and electric orders to spatially selected regions may be particularly relevant for future technological applications because it may serve as basis of electrically controllable magnetic memory devices. However, direct observation of magnetoelectric low-dimensional structures cannot readily be done partly because of the lack of experimental techniques locally probing their physical nature. Here, we report an observation of multiferroic ribbon-like domains in a non-multiferroic environment in MnWO4. Using optical second harmonic generation imaging, we reveal that a multiferroic phase is stabilized by locally generated strain while the bulk magnetic structure is non-multiferroic. We further find that the confined multiferroic state retains domains with different directions of electric polarization and we demonstrate deterministic writing of a multiferroic state embedded in a non-multiferroic environment.

Training the Polarization in Integrated La0.15 Bi0.85 FeO3 -Based Devices.

The functionalities of BiFeO3 -based magnetoelectric multiferroic heterostructures rely on the controlled manipulation of their ferroelectric domains and of the corresponding net in-plane polarization, as this aspect guides the voltage-controlled magnetic switching. Chemical substitution has emerged as a key to push the energy dissipation of the BiFeO3 into the attojoule range but appears to result in a disordered domain configuration. Using non-invasive optical second-harmonic generation on heavily La-substituted BiFeO3 films, it is shown that a weak net in-plane polarization remains imprinted in the pristine films despite the apparent domain disorder. It is found that this ingrained net in-plane polarization can be trained with out-of-plane electric fields compatible with applications. Operando studies on capacitor heterostructures treated in this way show the full restoration of the domain configuration of pristine BiFeO3 along with a giant net in-plane polarization enhancement. Thus, the experiments reveal a surprising robustness of the net in-plane polarization of BiFeO3 against chemical modification, an important criterion in ongoing attempts to integrate magnetoelectric materials into energy-efficient devices.

Magnetoelectric coupling of domains, domain walls and vortices in a multiferroic with independent magnetic and electric order.

Magnetically induced ferroelectrics exhibit rigidly coupled magnetic and electric order. The ordering temperatures and spontaneous polarization of these multiferroics are notoriously low, however. Both properties can be much larger if magnetic and ferroelectric order occur independently, but the cost of this independence is that pronounced magnetoelectric interaction is no longer obvious. Using spatially resolved images of domains and density-functional theory, we show that in multiferroics with separately emerging magnetic and ferroelectric order, the microscopic magnetoelectric coupling can be intrinsically strong even though the macroscopic leading-order magnetoelectric effect is forbidden by symmetry. We show, taking hexagonal ErMnO3 as an example, that a strong bulk coupling between the ferroelectric and antiferromagnetic order is realized because the structural distortions that lead to the ferroelectric polarization also break the balance of the competing superexchange contributions. We observe the manifestation of this coupling in uncommon types of topological defects like magnetoelectric domain walls and vortex-like singularities.

Nonreciprocal second harmonic generation in a magnetoelectric material.

Mirror symmetries are of particular importance because they are connected to fundamental properties and conservation laws. Spatial inversion and time reversal are typically associated to charge and spin phenomena, respectively. When both are broken, magnetoelectric cross-coupling can arise. In the optical regime, a difference between forward and backward propagation of light may result. Usually, this nonreciprocal response is small. We show that a giant nonreciprocal optical response can occur when transferring from linear to nonlinear optics, specifically second harmonic generation (SHG). CuB2O4 exhibits SHG transmission changes by almost 100% upon reversal of a magnetic field of just ±10 mT. The observed nonreciprocity results from an interference between magnetic-dipole and electric-dipole SHG. Although the former is inherently weaker than the latter, a resonantly enhanced magnetic-dipole transition has a comparable amplitude as a nonresonant electric-dipole transition, thus maximizing the nonreciprocity. Multiferroics and magnetoelectrics are an obvious materials platform to exhibit nonreciprocal nonlinear optical functionalities.

Inversion-Symmetry Engineering in Layered Oxide Thin Films.

Inversion-symmetry breaking is a ubiquitous concept in condensed-matter science: It is a prerequisite for technologically relevant effects such as piezoelectricity, nonlinear optical properties, and spin-transport phenomena. It also determines abstract properties, like the electronic topology in quantum materials. Therefore, the creation of materials where inversion symmetry can be turned on or off by design may be a versatile approach for controlling parity-related functionalities. Here, we engineer inversion symmetry on a sub-unit-cell level in ultrathin hexagonal manganite films. Although an odd number of half-unit-cell layers breaks inversion symmetry, an even number of such layers remains centrosymmetric. Optical second harmonic generation as an inversion-symmetry-sensitive functionality is thus activated and deactivated on demand and at the same time used for in situ tracking of the symmetry state of our films. Symmetry engineering on the sub-unit-cell level thus suggests a new platform for controlled activation and deactivation of symmetry-governed functionalities in oxide-electronic epitaxial thin films.

Efficient spin excitation via ultrafast damping-like torques in antiferromagnets.

Damping effects form the core of many emerging concepts for high-speed spintronic applications. Important characteristics such as device switching times and magnetic domain-wall velocities depend critically on the damping rate. While the implications of spin damping for relaxation processes are intensively studied, damping effects during impulsive spin excitations are assumed to be negligible because of the shortness of the excitation process. Herein we show that, unlike in ferromagnets, ultrafast damping plays a crucial role in antiferromagnets because of their strongly elliptical spin precession. In time-resolved measurements, we find that ultrafast damping results in an immediate spin canting along the short precession axis. The interplay between antiferromagnetic exchange and magnetic anisotropy amplifies this canting by several orders of magnitude towards large-amplitude modulations of the antiferromagnetic order parameter. This leverage effect discloses a highly efficient route towards the ultrafast manipulation of magnetism in antiferromagnetic spintronics.

In-situ monitoring of interface proximity effects in ultrathin ferroelectrics.

The development of energy-efficient nanoelectronics based on ferroelectrics is hampered by a notorious polarization loss in the ultrathin regime caused by the unscreened polar discontinuity at the interfaces. So far, engineering charge screening at either the bottom or the top interface has been used to optimize the polarization state. Yet, it is expected that the combined effect of both interfaces determines the final polarization state; in fact the more so the thinner a film is. The competition and cooperation between interfaces have, however, remained unexplored so far. Taking PbTiO3 as a model system, we observe drastic differences between the influence of a single interface and the competition and cooperation of two interfaces. We investigate the impact of these configurations on the PbTiO3 polarization when the interfaces are in close proximity, during thin-film synthesis in the ultrathin limit. By tailoring the interface chemistry towards a cooperative configuration, we stabilize a robust polarization state with giant polarization enhancement. Interface cooperation hence constitutes a powerful route for engineering the polarization in thin-film ferroelectrics towards improved integrability for oxide electronics in reduced dimension.

Interface and surface stabilization of the polarization in ferroelectric thin films.

Ferroelectric perovskites present a switchable spontaneous polarization and are promising energy-efficient device components for digital information storage. Full control of the ferroelectric polarization in ultrathin films of ferroelectric perovskites needs to be achieved in order to apply this class of materials in modern devices. However, ferroelectricity itself is not well understood in this nanoscale form, where interface and surface effects become particularly relevant and where loss of net polarization is often observed. In this work, we show that the precise control of the structure of the top surface and bottom interface of the thin film is crucial toward this aim. We explore the properties of thin films of the prototypical ferroelectric lead titanate (PbTiO3) on a metallic strontium ruthenate (SrRuO3) buffer using a combination of computational (density functional theory) and experimental (optical second harmonic generation) methods. We find that the polarization direction and strength are influenced by chemical and electronic processes occurring at the epitaxial interface and at the surface. The polarization is particularly sensitive to adsorbates and to surface and interface defects. These results point to the possibility of controlling the polarization direction and magnitude by engineering specific interface and surface chemistries.

Reverse and forward engineering of Drosophila corneal nanocoatings.

Insect eyes have an anti-reflective coating, owing to nanostructures on the corneal surface creating a gradient of refractive index between that of air and that of the lens material1,2. These nanocoatings have also been shown to provide anti-adhesive functionality3. The morphology of corneal nanocoatings are very diverse in arthropods, with nipple-like structures that can be organized into arrays or fused into ridge-like structures4. This diversity can be attributed to a reaction-diffusion mechanism4 and patterning principles developed by Alan Turing5, which have applications in numerous biological settings6. The nanocoatings on insect corneas are one example of such Turing patterns, and the first known example of nanoscale Turing patterns4. Here we demonstrate a clear link between the morphology and function of the nanocoatings on Drosophila corneas. We find that nanocoatings that consist of individual protrusions have better anti-reflective properties, whereas partially merged structures have better anti-adhesion properties. We use biochemical analysis and genetic modification techniques to reverse engineer the protein Retinin and corneal waxes as the building blocks of the nanostructures. In the context of Turing patterns, these building blocks fulfil the roles of activator and inhibitor, respectively. We then establish low-cost production of Retinin, and mix this synthetic protein with waxes to forward engineer various artificial nanocoatings with insect-like morphology and anti-adhesive or anti-reflective function. Our combined reverse- and forward-engineering approach thus provides a way to economically produce functional nanostructured coatings from biodegradable materials.

Relation between microscopic interactions and macroscopic properties in ferroics.

The driving force in materials to spontaneously form states with magnetic or electric order is of fundamental importance for basic research and device technology. The macroscopic properties and functionalities of these ferroics depend on the size, distribution and morphology of domains; that is, of regions across which such uniform order is maintained1. Typically, extrinsic factors such as strain profiles, grain size or annealing procedures control the size and shape of the domains2-5, whereas intrinsic parameters are often difficult to extract due to the complexity of a processed material. Here, we achieve this separation by building artificial crystals of planar nanomagnets that are coupled by well-defined, tuneable and competing magnetic interactions6-9. Aside from analysing the domain configurations, we uncover fundamental intrinsic correlations between the microscopic interactions establishing magnetically compensated order and the macroscopic manifestations of these interactions in basic physical properties. Experiment and simulations reveal how competing interactions can be exploited to control ferroic hallmark properties such as the size and morphology of domains, topological properties of domain walls or their thermal mobility.