Magnetic skin effect in Pb(Fe _{1/2}$Nb _{1/2}$)O3.

Relaxor-ferroelectrics display exceptional dielectric properties resulting from the underlying random dipolar fields induced by strong chemical inhomogeneity. An unusual structural aspect of relaxors is a skin-effect where the near-surface region in single crystals exhibit structures and critical phenomena that differ from the bulk. Relaxors are unique in that this skin effect extends over a macroscopic lengthscale of ∼100 µmwhereas usual surface layers only extend over a few unit cells (or ∼nm). We present a muon spectroscopy study of Pb(Fe_{1/2}Nb_{1/2})O3(PFN) which displays ferroelectric order, including many relaxor-like dielectric properties such as a frequency broadened dielectric response, and antiferromagnetism with spatially short-range polar correlations and hence can be termed a multiferroic. In terms of the magnetic behavior determined by the Fe3+(S=5/2,L ≈ 0) ions, PFN has been characterized as a unique example of a 'cluster spin-glass'. We use variable momentum muon spectroscopy to study the depth dependence of the slow magnetic relaxations in a large 1 cm3crystal of PFN. Zero-fieldpositivemuon spin relaxation is parameterized using a stretched exponential, indicative of a distribution of relaxation rates of the Fe3+spins. This bandwidth of frequencies changes as a function of muon momentum, indicative of a change in the Fe3+relaxation rates as a function of muon implantation depth in our single crystal. Usingnegativemuon elemental analysis, we find small-to-no measurable change in the Fe3+/Nb5+concentration with depth implying that chemical concentration alone cannot account for the change in the relaxational dynamics. PFN displays an analogous magnetic skin effect reported to exist in the structural properties of relaxor-ferroelectrics.

Designed Spin-Texture-Lattice to Control Anisotropic Magnon Transport in Antiferromagnets.

Spin waves in magnetic materials are promising information carriers for future computing technologies due to their ultra-low energy dissipation and long coherence length. Antiferromagnets are strong candidate materials due, in part, to their stability to external fields and larger group velocities. Multiferroic antiferromagnets, such as BiFeO3 (BFO), have an additional degree of freedom stemming from magnetoelectric coupling, allowing for control of the magnetic structure, and thus spin waves, with the electric field. Unfortunately, spin-wave propagation in BFO is not well understood due to the complexity of the magnetic structure. In this work, long-range spin transport is explored within an epitaxially engineered, electrically tunable, 1D magnonic crystal. A striking anisotropy is discovered in the spin transport parallel and perpendicular to the 1D crystal axis. Multiscale theory and simulation suggest that this preferential magnon conduction emerges from a combination of a population imbalance in its dispersion, as well as anisotropic structural scattering. This work provides a pathway to electrically reconfigurable magnonic crystals in antiferromagnets.

Epsilon-near-zero regime for ultrafast opto-spintronics.

Over the last two decades, breakthrough works in the field of non-linear phononics have revealed that high-frequency lattice vibrations, when driven to high amplitude by mid- to far-infrared optical pulses, can bolster the light-matter interaction and thereby lend control over a variety of spontaneous orderings. This approach fundamentally relies on the resonant excitation of infrared-active transverse optical phonon modes, which are characterized by a maximum in the imaginary part of the medium's permittivity. Here, in this Perspective article, we discuss an alternative strategy where the light pulses are instead tailored to match the frequency at which the real part of the medium's permittivity goes to zero. This so-called epsilon-near-zero regime, popularly studied in the context of metamaterials, naturally emerges to some extent in all dielectric crystals in the infrared spectral range. We find that the light-matter interaction in the phononic epsilon-near-zero regime becomes strongly enhanced, yielding even the possibility of permanently switching both spin and polarization order parameters. We provide our perspective on how this hitherto-neglected yet fertile research area can be explored in future, with the aim to outline and highlight the exciting challenges and opportunities ahead.

Machine Learning-Powered Ultrahigh Controllable and Wearable Magnetoelectric Piezotronic Touching Device.

Recent advancements in nanomaterials have enabled the application of nanotechnology to the development of cutting-edge sensing and actuating devices. For instance, nanostructures' collective and predictable responses to various stimuli can be monitored to determine the physical environment of the nanomaterial, such as temperature or applied pressure. To achieve optimal sensing and actuation capabilities, the nanostructures should be controllable. However, current applications are limited by inherent challenges in controlling nanostructures that counteract many sensing mechanisms that are reliant on their area or spacing. This work presents a technique utilizing the piezo-magnetoelectric properties of nanoparticles to enable strain sensing and actuation in a flexible and wearable patch. The alignment of nanoparticles has been achieved using demagnetization fields with computational simulations confirming device characteristics under various types of deformation followed by experimental demonstrations. The device exhibits favorable piezoelectric performance, hydrophobicity, and body motion-sensing capabilities, as well as machine learning-powered touch-sensing/actuating features.

Relevance of Platinum Underlayer Crystal Quality for the Microstructure and Magnetic Properties of the Heterostructures YbFeO3/Pt/YSZ(111).

The hexagonal ferrite h-YbFeO3 grown on YSZ(111) by pulsed laser deposition is foreseen as a promising single multiferroic candidate where ferroelectricity and antiferromagnetism coexist for future applications at low temperatures. We studied in detail the microstructure as well as the temperature dependence of the magnetic properties of the devices by comparing the heterostructures grown directly on YSZ(111) (i.e., YbPt_Th0nm) with h-YbFeO3 films deposited on substrates buffered with platinum Pt/YSZ(111) and in dependence on the Pt underlayer film thickness (i.e., YbPt_Th10nm, YbPt_Th40nm, YbPt_Th55nm, and YbPt_Th70nm). The goal was to deeply understand the importance of the crystal quality and morphology of the Pt underlayer for the h-YbFeO3 layer crystal quality, surface morphology, and the resulting physical properties. We demonstrate the relevance of homogeneity, continuity, and hillock formation of the Pt layer for the h-YbFeO3 microstructure in terms of crystal structure, mosaicity, grain boundaries, and defect distribution. The findings of transmission electron microscopy and X-ray diffraction reciprocal space mapping characterization enable us to conclude that an optimum film thickness for the Pt bottom electrode is ThPt = 70 nm, which improves the crystal quality of h-YbFeO3 films grown on Pt-buffered YSZ(111) in comparison with h-YbFeO3 films grown on YSZ(111) (i.e., YbPt_Th0nm). The latter shows a disturbance in the crystal structure, in the up-and-down atomic arrangement of the ferroelectric domains, as well as in the Yb-Fe exchange interactions. Therefore, an enhancement in the remanent and in the total magnetization was obtained at low temperatures below 50 K for h-YbFeO3 films deposited on Pt-buffered substrates Pt/YSZ(111) when the Pt underlayer reached ThPt = 70 nm.

Ultrafast Optically Induced Perturbation of Oxygen Octahedral Rotations in Multiferroic BiFeO3 Thin Films.

The functional properties of complex oxides, including magnetism and ferroelectricity, are closely linked to subtle structural distortions. Ultrafast optical excitations provide the means to manipulate structural features and ultimately to affect the functional properties of complex oxides with picosecond-scale precision. We report that the lattice expansion of multiferroic BiFeO3 following above-bandgap optical excitation leads to distortion of the oxygen octahedral rotation (OOR) pattern. The continuous coupling between OOR and strain was probed using time-resolved X-ray free-electron laser diffraction with femtosecond time resolution. Density functional theory calculations predict a relationship between the OOR and the elastic strain consistent with the experiment, demonstrating a route to employing this approach in a wider range of systems. Ultrafast control of the functional properties of BiFeO3 thin films is enabled by this approach because the OOR phenomena are related to ferroelectricity, and via the Fe-O-Fe bond angles, the superexchange interaction between Fe atoms.

Photon-Dipole-Spin Interactions in M(TCNE)x/P(VDF-TrFE) Multiferroic Heterostructure Available for Bimodal Control of Multistate Data-Storage.

Organic multiferroic heterostructure is one of the most promising structures for the future design of high-density flexible energy-efficient data storage. Here, organic ferromagnetic metal(tetracyanoethylene) (M(TCNE))x/ferroelectric poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) multiferroic heterostructures are fabricated, where the excited state in M(TCNE)x interacted with localized dipole in P(VDF-TrFE) provides a key link for the interfacial coupling. Thus, aligned dipoles in P(VDF-TrFE) by external electric field can affect the magnetization of Fe(TCNE)x effectively to result in a pronounced magnetization-voltage (M-V) hysteresis loop. Moreover, light-induced electron-hole pairs in Fe(TCNE)x with long lifetime effectively interact with the dipoles in P(VDF-TrFE) to lead to an effect in external light control of electric polarization of P(VDF-TrFE). Overall, the organic multiferroic heterostructure provides the possibility of realizing two storage modes, light control of dipole as well as electric field control of spin, which can broaden multifunctional applications of organic multiferroic materials in the area of multistate storage.

Concomitant Light-Reversible Magnetic Response in Multiferroic Oxide Heterostructures for Multiphysics Applications.

The concept of multiphysics, where materials respond to diverse external stimuli, such as magnetic fields, electric fields, light irradiation, stress, heat, and chemical reactions, plays a fundamental role in the development of innovative devices. Nanomanufacturing, especially in low-dimensional systems, enhances the synergistic interactions taking place on the nanoscale. Light-matter interaction, rather than electric fields, holds great promise for achieving low-power, wireless control over magnetism, solving two major technological problems: the feasibility of electrical contacts at smaller scales and the undesired heating of the devices. Here, we shed light on the remarkable reversible modulation of magnetism using visible light in epitaxial Fe3O4/BaTiO3 heterostructure. This achievement is underpinned by the convergence of two distinct mechanisms. First, the magnetoelastic effect, triggered by ferroelectric domain switching, induces a proportional change in coercivity and remanence upon laser illumination. Second, light-matter interaction induces charged ferroelectric domain walls' electrostatic decompensations, acting intimately on the magnetization of the epitaxial Fe3O4 film by magnetoelectric coupling. Crucially, our experimental results vividly illustrate the capability to manipulate magnetic properties using visible light. This concomitant mechanism provides a promising avenue for low-intensity visible-light manipulation of magnetism, offering potential applications in multiferroic devices.

Single or Vortex Ferroelectric and Ferromagnetic Domain Nanodot Array of Magnetoelectric BiFe0.9Co0.1O3.

Nanodots composed of multiferroic cobalt-substituted BiFeO3, a ferroelectric ferromagnet at room temperature, are fabricated by pulsed laser deposition using anodized porous alumina as masks. The obtained nanodots are approximately 60 nm in diameter, more than 10 nm in thickness, and approximately 70 Gbit/in.2 in density. Piezoresponse and magnetic force microscopies show both ferroelectricity and ferromagnetism with a single-domain nature. It is also found that the dot with 190 nm diameter had multidomain vortex ferroelectric and magnetic structures indicating the strong magnetoelectric coupling. The single-domain cobalt-substituted BiFeO3 nanodots are suitable for verifying magnetization reversal by the electric field, which is the first step in the development of low-power-consumption nonvolatile magnetic memory devices.

Investigation of electronic, ferroelectric and local electrical conduction behavior of RF sputtered BiFeO3thin films.

Most of the applied research on BiFeO3(BFO) focuses on magnetoelectric and spintronic applications. This calls for a detailed grasp of multiferroic and conduction properties. BFO thin films with (100) epitaxial growth has been deposited on a LaNiO3(LNO) buffered Pt/Ti/SiO2/Si(100) substrate using RF magnetron sputtering. The film formed at 15 mTorr, 570 °C, and with Ar/O24:1 had a reasonably high degree of (100)-preferential orientation, the least surface roughness, and a densely packed structure. We obtained ferroelectric loops with strong polarization (150µC cm-2). The leakage current density is as low as 10-2A cm-2at 100 kV cm-1, implying that space-charge-limited bulk conduction (SCLC) was the primary conduction channel for carriers within BFO films. Local electrical conduction behavior demonstrates that at lower voltages, the grain boundary dominates electrical conduction and is linked to the displacement of oxygen vacancies in the grain boundary under external electric fields. We hope that a deeper understanding of the conduction mechanism will help integrate BFO into viable technologies.

Nonreciprocal and Nonvolatile Electric-Field Switching of Magnetism in van der Waals Heterostructure Multiferroics.

Multiferroic materials provide robust and efficient routes for the control of magnetism by electric fields, which have been diligently sought after for a long time. Construction of two-dimensional (2D) vdW multiferroics is a more exciting endeavor. To date, the nonvolatile manipulation of magnetism through ferroelectric polarization still remains challenging in a 2D vdW heterostructure multiferroic. Here, we report a van der Waals (vdW) heterostructure multiferroic comprising the atomically thin layered antiferromagnet (AFM) CrI3 and ferroelectric (FE) α-In2Se3. We demonstrate anomalously nonreciprocal and nonvolatile electric-field control of magnetization by ferroelectric polarization. The nonreciprocal electric control originates from an intriguing antisymmetric enhancement of interlayer ferromagnetic coupling in the opposite ferroelectric polarization configurations of α-In2Se3. Our work provides numerous possibilities for creating diverse heterostructure multiferroics at the limit of a few atomic layers for multistage magnetic memories and brain-inspired in-memory computing.

Large nonlinear optical magnetoelectric response in a noncentrosymmetric magnetic Weyl semimetal.

Weyl semimetals resulting from either inversion (P) or time-reversal (T) symmetry breaking have been revealed to show the record-breaking large optical response due to intense Berry curvature of Weyl-node pairs. Different classes of Weyl semimetals with both P and T symmetry breaking potentially exhibit optical magnetoelectric (ME) responses, which are essentially distinct from the previously observed optical responses in conventional Weyl semimetals, leading to the versatile functions such as directional dependence for light propagation and gyrotropic effects. However, such optical ME phenomena of (semi)metallic systems have remained elusive so far. Here, we show the large nonlinear optical ME response in noncentrosymmetric magnetic Weyl semimetal PrAlGe, in which the polar structural asymmetry and ferromagnetic ordering break P and T symmetry. We observe the giant second harmonic generation (SHG) arising from the P symmetry breaking in the paramagnetic phase, being comparable to the largest SHG response reported in Weyl semimetal TaAs. In the ferromagnetically ordered phase, it is found that interference between this nonmagnetic SHG and the magnetically induced SHG emerging due to both P and T symmetry breaking results in the magnetic field switching of SHG intensity. Furthermore, such an interference effect critically depends on the light-propagating direction. The corresponding magnetically induced nonlinear susceptibility is significantly larger than the prototypical ME material, manifesting the existence of the strong nonlinear dynamical ME coupling. The present findings establish the unique optical functionality of P- and T-symmetry broken ME topological semimetals.

Giant Modulation of the Second Harmonic Generation by Magnetoelectricity in Two-Dimensional Multiferroic CuCrP2S6.

Multiferroic materials have attracted considerable attention owing to their unique magnetoelectric or magnetooptical properties. The recent discovery of few-layer van der Waals multiferroic crystals provides a new research direction for controlling the multiferroic properties in the atomic layer limit. However, research on few-layer multiferroic crystals is limited and the effect of thickness-dependent symmetries on those properties is less explored. In this study, the symmetries and magnetoelectric responses of van der Waals multiferroic CuCrP2S6 are investigated by optical second harmonic generation (SHG). Structural and magnetic phase transitions are successfully probed by the temperature-dependent SHG signals, revealing significant changes by applying the magnetic field reflecting the magnetoelectric effect. Moreover, it is found that symmetries and resultant magnetoelectric responses can be modulated by the number of layers. These results offer a new principle of controlling the multiferroicity and indicate that 2D van der Waals multiferroic material is a promising building block for functional nanodevices.

A Route to Two-Dimensional Room-Temperature Organometallic Multiferroics: The Marriage of d-p Spin Coupling and Structural Inversion Symmetry Breaking.

Two-dimensional (2D) room-temperature multiferroic materials are highly desirable but still very limited. Herein, we propose a potential strategy to obtain such materials in 2D metal-organic frameworks (MOFs) by utilizing the d-p direct spin coupling in conjunction with center-symmetry-breaking six-membered heterocyclic rings. Based on this strategy, a screening of 128 2D MOFs results in the identification of three multiferroics, that is, Cr(1,2-oxazine)2, Cr(1,2,4-triazine)2, and Cr(1,2,3,4-trazine)2, simultaneously exhibiting room-temperature ferrimagnetism and ferroelectricity/antiferroelectricity. The room-temperature ferrimagnetic order (306-495 K) in these MOFs originates from the strong d-p direct magnetic exchange interaction between Cr cations and ligand anions. Specifically, Cr(1,2-oxazine)2 exhibits ferroelectric behavior with an out-of-plane polarization of 4.24 pC/m, whereas the other two manifest antiferroelectric characteristics. Notably, all three materials present suitable polarization switching barriers (0.18-0.31 eV). Furthermore, these MOFs are all bipolar magnetic semiconductors with moderate band gaps, in which the spin direction of carriers can be manipulated by electrical gating.

Understanding Complex Interplay among Different Instabilities in Multiferroic BiMn7O12 Using 57Fe Probe Mössbauer Spectroscopy.

Here, we report the results of a Mössbauer study on hyperfine electrical and magnetic interactions in quadruple perovskite BiMn7O12 doped with 57Fe probes. Measurements were performed in the temperature range of 10 K < T < 670 K, wherein BiMn6.9657Fe0.04O12 undergoes a cascade of structural (T1 ≈ 590 K, T2 ≈ 442 K, and T3 ≈ 240 K) and magnetic (TN1 ≈ 57 K, TN2 ≈ 50 K, and TN3 ≈ 24 K) phase transitions. The analysis of the electric field gradient (EFG) parameters, including the dipole contribution from Bi3+ ions, confirmed the presence of the local dipole moments pBi, which are randomly oriented in the paraelectric cubic phase (T > T1). The unusual behavior of the parameters of hyperfine interactions between T1 and T2 was attributed to the dynamic Jahn-Teller effect that leads to the softening of the orbital mode of Mn3+ ions. The parameters of the hyperfine interactions of 57Fe in the phases with non-zero spontaneous electrical polarization (Ps), including the P1 ↔ Im transition at T3, were analyzed. On the basis of the structural data and the quadrupole splitting Δ(T) derived from the 57Fe Mössbauer spectra, the algorithm, based on the Born effective charge model, is proposed to describe Ps(T) dependence. The Ps(T) dependence around the Im ↔ I2/m phase transition at T2 is analyzed using the effective field approach. Possible reasons for the complex relaxation behavior of the spectra in the magnetically ordered states (T < TN1) are also discussed.

Atomic-Scale Visualization of Multiferroicity in Monolayer NiI2.

Progress in layered van der Waals materials has resulted in the discovery of ferromagnetic and ferroelectric materials down to the monolayer limit. Recently, evidence of the first purely 2D multiferroic material was reported in monolayer NiI2. However, probing multiferroicity with scattering-based and optical bulk techniques is challenging on 2D materials, and experiments on the atomic scale are needed to fully characterize the multiferroic order at the monolayer limit. Here, scanning tunneling microscopy (STM) supported by density functional theory (DFT) calculations is used to probe and characterize the multiferroic order in monolayer NiI2. It is demonstrated that the type-II multiferroic order displayed by NiI2, arising from the combination of a magnetic spin spiral order and a strong spin-orbit coupling, allows probing the multiferroic order in the STM experiments. Moreover, the magnetoelectric coupling of NiI2 is directly probed by external electric field manipulation of the multiferroic domains. The findings establish a novel point of view to analyze magnetoelectric effects at the microscopic level, paving the way toward engineering new multiferroic orders in van der Waals materials and their heterostructures.

Ferroics in Hybrid Organic-Inorganic Perovskites: Fundamentals, Design Strategies, and Implementation.

Hybrid organic-inorganic perovskites (HOIPs) afford highly versatile structure design and lattice dimensionalities; thus, they are actively researched as material platforms for the tailoring of ferroic behaviors. Unlike single-phase organic or inorganic materials, the interlayer coupling between organic and inorganic components in HOIPs allows the modification of strain and symmetry by chirality transfer or lattice distortion, thereby enabling the coexistence of ferroic orders. This review focuses on the principles for engineering one or multiple ferroic orders in HOIPs, and the conditions for achieving multiferroicity and magnetoelectric properties. The prospects of multilevel ferroic modulation, chiral spin textures, and spin orbitronics in HOIPs are also presented.

Directed Self-Assembly of Oxide Nanocomposites by Ion-Beam Lithography.

Vertically aligned self-assembled nanocomposite films have provided a unique platform to study magnetoelectric effects and other forms of coupling between complex oxides. However, the distribution in the locations and sizes of the phase-separated nanostructures limits their utility. In this work, we demonstrate a process to template the locations of the self-assembled structure using ion lithography, which is effective for general insulating substrates. This process was used to produce a nanocomposite consisting of fin-shaped vertical nanostructures of ferroelectric BiFeO3 and ferrimagnetic CoFe2O4 with a feature size of 100 nm on (111)-oriented SrTiO3 substrates. Cross-sectional imaging of the three-phase perovskite-spinel-substrate epitaxial interface reveals the selective nucleation of CoFe2O4 in the trenches of the patterned substrate, and the magnetic domains of CoFe2O4 were manipulated by applying an external magnetic field.

Theoretical Justification of Structural, Magnetoelectronic and Optical Properties in QFeO3 (Q = Bi, P, Sb): A First-Principles Study.

One of the primary objectives of scientific research is to create state-of-the-art multiferroic (MF) materials that exhibit interconnected properties, such as piezoelectricity, magnetoelectricity, and magnetostriction, and remain functional under normal ambient temperature conditions. In this study, we employed first-principles calculations to investigate how changing pnictogen elements affect the structural, electronic, magnetic, and optical characteristics of QFeO3 (Q = Bi, P, SB). Electronic band structures reveal that BiFeO3 is a semiconductor compound; however, PFeO3 and SbFeO3 are metallic. The studied compounds are promising for spintronics, as they exhibit excellent magnetic properties. The calculated magnetic moments decreased as we replaced Bi with SB and P in BiFeO3. A red shift in the values of ε2(ω) was evident from the presented spectra as we substituted Bi with Sb and P in BiFeO3. QFeO3 (Q = Bi, P, SB) showed the maximum absorption of incident photons in the visible region. The results obtained from calculating the optical parameters suggest that these materials have a strong potential to be used in photovoltaic applications.

Exploring RF Magnetron Sputtering Growth Composite Thin Film BiFeO3-Bi2Fe4O9 on C-Plane Al2O3 Substrate.

Nanocomposite films of BiFeO3-Bi2Fe4O9 were fabricated on a sapphire substrate Al2O3 using the method of gas discharge high-frequency cathodic sputtering of a ceramic target with a stoichiometric composition in an oxygen atmosphere. The results of the film analysis using X-ray structural analysis, Raman scattering, XPS, and atomic force microscopy are presented. The lattice parameters, surface topography, chemical composition of the films, concentration, and average sizes of the crystallites for each phase were determined. It was shown that the ratio of the BiFeO3 to Bi2Fe4O9 phases in the obtained film is approximately 1:2. The sizes of the crystallites range from 15 to 17 nm. The optical and magnetic properties of the nanocomposite layers were studied, and the band gap width and magnetization hysteresis characteristic of ferromagnetic behavior were observed. The band gap width was found to be 1.9 eV for the indirect and 2.6 eV for the direct interband transitions. The magnetic properties are characterized by a hysteresis loop resembling a "wasp-waist" shape, indicating the presence of magnetic anisotropy.