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

The time dependence of quasi-static capacitance of linear and non-linear materials can be measured using a constant voltage ramp method. The measured data are consistent with a theoretical equation derived from a superposition theorem. The capacitance of fast polarization, saturated polarization and the time constant of the relaxation process can be obtained using a non-linear least squares method. Ultra slow relaxation for linear dielectrics and ferroelectrics are reported.

Quasi-static capacitance and ultra slow relaxation of linear and non-linear dielectrics

The PANEL (Piezoelectric Acoustic Noise ELiminator) transducer was developed for air acoustic noise cancellation in the frequency range of 200–1000 Hz. It has a thin panel structure, occupies less volume, and is lighter than an equivalent electromagnetic transducer. This device consists of a U‐shaped configuration of piezoelectric bimorph and unimorph actuators bridged by a triangular amplifying diaphragm, which acts as an effective source of the sound radiation into air. The role of the diaphragm is twofold: it amplifies by a factor of 5–20 the tip displacement of the piezoelectric actuators and it also increases the sound emitting area. Amplitude of the vibrations and usable frequency range of the transducer depend on the dimensions and material of the actuators and diaphragm. The overall dimensions of the device fabricated were 52×50×24 mm. Soft PZT ceramics were used. The diaphragm was made of a carbon fiber reinforced composite. The diaphragm vibrations reach 500 μm rms well below the fundamental res...

PANEL: A novel piezoelectric air acoustic transducer

Measurements of the fourth and sixth-order electrostriction constants have been performed on several fluoride perovskite single crystals. The results are compared with those observed in other similar materials, and the relationships between electrostriction and some physical properties are examined.

Electrostriction and its relationship to other properties in perovskite-type crystals

An experimental cell for making dielectric measurements on small soda glass samples with sodium amalgam electrodes is described. The cell allows a properly guarded nonblocking measurement of the dielectric properties on samples of 1.3 cm diameter. The performance is illustrated by a very brief description of measurements on glasses of composition 1.5 Na2O, 0.5 Al2O3, 5 SiO2.

Nonpolarizing Electrode System for Dielectric Measurements on Soda‐Glass

Thin films of PbZrO 3 -Pb(Zn 0.33 Nb 0.67 )0 3 , with PZN contents of 8- 12%, were fabricated through the sol-gel spin-on technique. The structural, low frequency capacitive, and polarization reversal characteristics were investigated as a function of composition in this solid solution system. The switching of ferroelectric polarization was tested by a sequence of square wave pulses consisting of two positive pulses followed by two negative pulses. Compositions with higher PZN contents are promising for switching applications; the films were typically characterized by a switched charge of 4-14 μC/cm 2 , coercive field of around 30 kV/cm, and relative permittivity of 400-800.

L. E. Cross

Papers

Quasi-static capacitance and ultra slow relaxation of linear and non-linear dielectrics

PANEL: A novel piezoelectric air acoustic transducer

Electrostriction and its relationship to other properties in perovskite-type crystals

Nonpolarizing Electrode System for Dielectric Measurements on Soda‐Glass

Ferroelectric Switching in Lead Zirconatelead Zinc Niobate Thin Films