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

Enhancement of polarization and related properties in heteroepitaxially constrained thin films of the ferroelectromagnet, BiFeO3, is reported. Structure analysis indicates that the crystal structure of film is monoclinic in contrast to bulk, which is rhombohedral. The films display a room-temperature spontaneous polarization (50 to 60 microcoulombs per square centimeter) almost an order of magnitude higher than that of the bulk (6.1 microcoulombs per square centimeter). The observed enhancement is corroborated by first-principles calculations and found to originate from a high sensitivity of the polarization to small changes in lattice parameters. The films also exhibit enhanced thickness-dependent magnetism compared with the bulk. These enhanced and combined functional responses in thin film form present an opportunity to create and implement thin film devices that actively couple the magnetic and ferroelectric order parameters.

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Epitaxial BiFeO3 multiferroic thin film heterostructures.

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

The piezoelectric properties of relaxor based ferroelectric single crystals, such as Pb(Zn1/3Nb2/3)O3–PbTiO3 and Pb(Mg1/3Nb2/3)O3–PbTiO3 were investigated for electromechanical actuators. In contrast to polycrystalline materials such as Pb(Zr,Ti)O3, morphotropic phase boundary compositions were not essential for high piezoelectric strain. Piezoelectric coefficients (d33’s)>2500 pC/N and subsequent strain levels up to >0.6% with minimal hysteresis were observed. Crystallographically, high strains are achieved for 〈001〉 oriented rhombohedral crystals, although 〈111〉 is the polar direction. Ultrahigh strain levels up to 1.7%, an order of magnitude larger than those available from conventional piezoelectric and electrostrictive ceramics, could be achieved being related to an E-field induced phase transformation. High electromechanical coupling (k33)>90% and low dielectric loss <1%, along with large strain make these crystals promising candidates for high performance solid state actuators.

Ultrahigh strain and piezoelectric behavior in relaxor based ferroelectric single crystals

BiFeO3 is perhaps the only material that is both magnetic and a strong ferroelectric at room temperature. As a result, it has had an impact on the field of multiferroics that is comparable to that of yttrium barium copper oxide (YBCO) on superconductors, with hundreds of publications devoted to it in the past few years. In this Review, we try to summarize both the basic physics and unresolved aspects of BiFeO3 (which are still being discovered with several new phase transitions reported in the past few months) and device applications, which center on spintronics and memory devices that can be addressed both electrically and magnetically.

Physics and Applications of Bismuth Ferrite

Elastic deformations induced by high electric fields in the solid solution system Pb(Mg1/3Nb2/3)O3-PbTiO3 have been measured using a strain gauge method at temperatures in the relaxation range. Unusual inverse hysteretic curves have been observed in the relation between the deformation and electric field typically in 90 mol% Pb-(Mg1/3Nb2/3)O3-10 mol% PbTiO3 at temperatures outside the range where they would be of practical use in electrostrictive displacement control.

Inverse hysteresis of field induced elastic deformation in the solid solution 90 mol% Pb(Mg1/3Nb2/3)O3-10 mol% PbTiO3

A simple model is developed to describe the inhomogeneous surface deformation profile of face plated 2-2 type piezocomposites. The contribution of face plate to the equilibrium condition is approximated by simple elastic bending of the plate. Analytical solutions were obtained for the inhomogeneous surface displacement profile. From these solutions one can predict the variation of the nonuniform surface displacement in a 2-2 composite with respect to material and geometry parameters. It is shown that the surface displacement uniformity depends on several factors: the ceramic aspect ratio, the spacing between ceramic plates, the thickness of face plate, the Young's modulus of the polymer and of the face plate. The calculated results indicate that stiffer face plates, softer polymer resin, and closer ceramic spacing could make the piezocomposite transducers have more uniform surface displacement. >

Effects of face plates on surface displacement profile in 2-2 piezoelectric composites

A type of high strain piezoelectric ceramic actuator, namely, pseudoshear multilayer actuator, is described. In this structure, a stack of prepoled rectangular piezoelectric transducer ceramic sheets are conductively bonded at alternate ends, while the bottom layer bonded on a fixed base. When driven, alternate layers elongate or shrink in the same direction through converse piezoelectric effect, which results in the actuator structure developing a strong shear motion about the face perpendicular to the bonding direction. Experimental results indicate that more than 50 μm displacement can be achieved from the top layer for an actuator consisting of 18 layers with dimensions of 25.57 mm×4.02 mm×0.51 mm (1×w×t). By reducing ceramic sheet thickness and using more layers, even large displacement can be obtained, and driving voltage can also be reduced while keeping the same field level. Nonlinear piezoelectric response under high driving field further enhances the displacement level.

A piezoelectric pseudoshear multilayer actuator

A novel approach to reduce electrode costs in ceramic capacitors is presented. Barium metaplumbate (BaPbO3) was fired onto sintered commercial (Ba, Sr)TiO3 disk capacitors as external electrodes. Samples were compared to disk capacitors of the same composition with electrodes made of sputtered gold and air-dried silver. The ceramic electrode led to substantial changes in the insulation resistance and dc breakdown strengths, but other properties remained the same. The feasibility of using BaPbO3 electrodes strongly depends on chemical reactions between the electrode and dielectric.

L. E. Cross

Papers

Inverse hysteresis of field induced elastic deformation in the solid solution 90 mol% Pb(Mg1/3Nb2/3)O3-10 mol% PbTiO3

Effects of face plates on surface displacement profile in 2-2 piezoelectric composites

A piezoelectric pseudoshear multilayer actuator

Barium Metaplumbate Ceramic Electrodes for Ceramic Capacitors

Pyroelectric properties of a new alanine- and phosphate-substituted triglycine sulphate (ATGSP) crystal