A ferroelectric crystal exhibits a stable and switchable electrical polarization that is manifested in the form of cooperative atomic displacements. A ferromagnetic crystal exhibits a stable and switchable magnetization that arises through the quantum mechanical phenomenon of exchange. There are very few 'multiferroic' materials that exhibit both of these properties, but the 'magnetoelectric' coupling of magnetic and electrical properties is a more general and widespread phenomenon. Although work in this area can be traced back to pioneering research in the 1950s and 1960s, there has been a recent resurgence of interest driven by long-term technological aspirations.

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Multiferroic and magnetoelectric materials

Recent research activities on the linear magnetoelectric (ME) effect?induction of magnetization by an electric field or of polarization by a magnetic field?are reviewed. Beginning with a brief summary of the history of the ME effect since its prediction in 1894, the paper focuses on the present revival of the effect. Two major sources for 'large' ME effects are identified. (i) In composite materials the ME effect is generated as a product property of a magnetostrictive and a piezoelectric compound. A linear ME polarization is induced by a weak ac magnetic field oscillating in the presence of a strong dc bias field. The ME effect is large if the ME coefficient coupling the magnetic and electric fields is large. Experiments on sintered granular composites and on laminated layers of the constituents as well as theories on the interaction between the constituents are described. In the vicinity of electromechanical resonances a ME voltage coefficient of up to 90?V?cm?1?Oe?1 is achieved, which exceeds the ME response of single-phase compounds by 3?5 orders of magnitude. Microwave devices, sensors, transducers and heterogeneous read/write devices are among the suggested technical implementations of the composite ME effect. (ii) In multiferroics the internal magnetic and/or electric fields are enhanced by the presence of multiple long-range ordering. The ME effect is strong enough to trigger magnetic or electrical phase transitions. ME effects in multiferroics are thus 'large' if the corresponding contribution to the free energy is large. Clamped ME switching of electrical and magnetic domains, ferroelectric reorientation induced by applied magnetic fields and induction of ferromagnetic ordering in applied electric fields were observed. Mechanisms favouring multiferroicity are summarized, and multiferroics in reduced dimensions are discussed. In addition to composites and multiferroics, novel and exotic manifestations of ME behaviour are investigated. This includes (i) optical second harmonic generation as a tool to study magnetic, electrical and ME properties in one setup and with access to domain structures; (ii) ME effects in colossal magnetoresistive manganites, superconductors and phosphates of the LiMPO4 type; (iii) the concept of the toroidal moment as manifestation of a ME dipole moment; (iv) pronounced ME effects in photonic crystals with a possibility of electromagnetic unidirectionality. The review concludes with a summary and an outlook to the future development of magnetoelectrics research.

https://iopscience.iop.org/article/10.1088/0022-3727/38/8/R01/pdf

Revival of the Magnetoelectric Effect

Magnetism and ferroelectricity are essential to many forms of current technology, and the quest for multiferroic materials, where these two phenomena are intimately coupled, is of great technological and fundamental importance. Ferroelectricity and magnetism tend to be mutually exclusive and interact weakly with each other when they coexist. The exciting new development is the discovery that even a weak magnetoelectric interaction can lead to spectacular cross-coupling effects when it induces electric polarization in a magnetically ordered state. Such magnetic ferroelectricity, showing an unprecedented sensitivity to ap plied magnetic fields, occurs in 'frustrated magnets' with competing interactions between spins and complex magnetic orders. We summarize key experimental findings and the current theoretical understanding of these phenomena, which have great potential for tuneable multifunctional devices.

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Multiferroics: a magnetic twist for ferroelectricity

Multiferroic materials, which show simultaneous ferroelectric and magnetic ordering, exhibit unusual physical properties — and in turn promise new device applications — as a result of the coupling between their dual order parameters. We review recent progress in the growth, characterization and understanding of thin-film multiferroics. The availability of high-quality thin-film multiferroics makes it easier to tailor their properties through epitaxial strain, atomic-level engineering of chemistry and interfacial coupling, and is a prerequisite for their incorporation into practical devices. We discuss novel device paradigms based on magnetoelectric coupling, and outline the key scientific challenges in the field.

Multiferroics: progress and prospects in thin films.

Multiferroic magnetoelectric materials, which simultaneously exhibit ferroelectricity and ferromagnetism, have recently stimulated a sharply increasing number of research activities for their scientific interest and significant technological promise in the novel multifunctional devices. Natural multiferroic single-phase compounds are rare, and their magnetoelectric responses are either relatively weak or occurs at temperatures too low for practical applications. In contrast, multiferroic composites, which incorporate both ferroelectric and ferri-/ferromagnetic phases, typically yield giant magnetoelectric coupling response above room temperature, which makes them ready for technological applications. This review of mostly recent activities begins with a brief summary of the historical perspective of the multiferroic magnetoelectric composites since its appearance in 1972. In such composites the magnetoelectric effect is generated as a product property of a magnetostrictive and a piezoelectric substance. A...

Multiferroic magnetoelectric composites: Historical perspective, status, and future directions

We report on the coupling between ferroelectric and magnetic order parameters in a nanostructured BaTiO3-CoFe2O4 ferroelectromagnet. This facilitates the interconversion of energies stored in electric and magnetic fields and plays an important role in many devices, including transducers, field sensors, etc. Such nanostructures were deposited on single-crystal SrTiO3 (001) substrates by pulsed laser deposition from a single Ba-Ti-Co-Fe-oxide target. The films are epitaxial in-plane as well as out-of-plane with self-assembled hexagonal arrays of CoFe2O4 nanopillars embedded in a BaTiO3 matrix. The CoFe2O4 nanopillars have uniform size and average spacing of 20 to 30 nanometers. Temperature-dependent magnetic measurements illustrate the coupling between the two order parameters, which is manifested as a change in magnetization at the ferroelectric Curie temperature. Thermodynamic analyses show that the magnetoelectric coupling in such a nanostructure can be understood on the basis of the strong elastic interactions between the two phases.

http://science.sciencemag.org/content/sci/303/5658/661.full.pdf

Multiferroic BaTiO3-CoFe2O4 Nanostructures.

Dynamics of domain interfaces in a broad range of functional thin-film materials is an area of great current interest. In ferroelectric thin films, a significantly enhanced piezoelectric response should be observed if non-180° domain walls were to switch under electric field excitation. However, in continuous thin films they are clamped by the substrate, and therefore their contribution to the piezoelectric response is limited. In this paper we show that when the ferroelectric layer is patterned into discrete islands using a focused ion beam, the clamping effect is significantly reduced, thereby facilitating the movement of ferroelastic walls. Piezo-response scanning force microscopy images of such islands in PbZr0.2Ti0.8O3 thin films clearly point out that the 90° domain walls can move. Capacitors 1 μm2 show a doubling of the remanent polarization at voltages higher than ∼15 V, associated with 90° domain switching, coupled with a d33 piezoelectric coefficient of ∼250 pm V−1 at remanence, which is approximately three times the predicted value of 87 pm V−1 for a single domain single crystal.

Dynamics of ferroelastic domains in ferroelectric thin films.

Arrays of perpendicular ferromagnetic nanowires have recently attracted considerable interest for their potential use in many areas of advanced nanotechnology. We report a simple approach to create self-assembled nanowires of α-Fe through the decomposition of a suitably chosen perovskite. We illustrate the principle behind this approach using the reaction 2La0.5Sr0.5FeO3 → LaSrFeO4 + Fe + O2 that occurs during the deposition of La0.5Sr0.5FeO3 under reducing conditions. This leads to the spontaneous formation of an array of single-crystalline α-Fe nanowires embedded in LaSrFeO4 matrix, which grow perpendicular to the substrate and span the entire film thickness. The diameter and spacing of the nanowires are controlled directly by deposition temperature. The nanowires show uniaxial anisotropy normal to the film plane and magnetization close to that of bulk α-Fe. The high magnetization and sizable coercivity of the nanowires make them desirable for high-density data storage and other magnetic-device applications.

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T. Zhao

Papers

Multiferroic BaTiO3-CoFe2O4 Nanostructures.

Dynamics of ferroelastic domains in ferroelectric thin films.

Self-assembled single-crystal ferromagnetic iron nanowires formed by decomposition