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 dielectric and piezoelectric properties (d-p properties) of four kinds of doped lead titanate zirconate piezoelectric ceramics (PZTs) have been measured from 4.2 to 300 K. The d-p properties of the materials converge with decreasing temperature down to liquid helium temperature, even though the properties have large differences at room temperatue. The values of mechanical and electrical quality factors,Q
m,Q
e, and of the frequency constant,N, of the materials increased at low temperature. It is evident from the freeze out inK′ and the associate temperature: frequency-dependent maxima in tan 5 that the relaxation processes including ferroelectric domain wall motion and thermal defect motion contribute to the d-p properties. The Navy type-III composition has a minimum temperature coefficient of d-p parameters and it is evident that PZT ceramics modified with Fe2O3 can provide good stability and also give the strongest piezoelectric response at liquid helium temperature.

Dielectric and piezoelectric properties of modified lead titanate zirconate ceramics from 4.2 to 300 K

Electric fatigue, namely the decay of the polarization and the consequent elastic strain with increased number of switching cycles under high a.c. field, severely limits the applications of ferroelectric and piezoelectric materials in high-strain electro-mechanical actuators and in thin films used in non-volatile memory devices. Electric fatigue tests have been conducted on lead zirconate titanate (PZT) and lanthanum-doped lead zirconate titanate (PLZT) ferroelectric ceramics. It was found that electric fatigue can be initiated by various factors, the porosity being one of them. Electric fatigue occurred in low-density(93%–97%) PLZT 7/65/35 ceramics after 104 switching cycles, while the high-density (>99%) PLZT specimens of the same composition did not fatigue after 109 switching cycles. It was also observed that for PZT ceramics, fatigue proceeded much more slowly in the samples with higher density (∼98%) than those with lower densities (92%–96%). A tentative explanation for the origin of the fatigue mechanism associated with porosity is proposed.

Effects of porosity on electric fatigue behaviour in PLZT and PZT ferroelectric ceramics

We report accurate temperature-dependent measurements of the optic index of refraction, the birefringence, and the strain in the ferroelectric, tungsten-bronze crystal ${\mathrm{Ba}}_{0.4}$${\mathrm{Sr}}_{0.6}$${\mathrm{Nb}}_{2}$${\mathrm{O}}_{6}$. This composition congruently melts, so large homogeneous high-quality crystals can be grown. From the experimental data, it appears that far above the ferroelectric phase transition temperature (${T}_{c}$\ensuremath{\approxeq}88 \ifmmode^\circ\else\textdegree\fi{}C), up to a temperature ${T}_{d}$ (\ensuremath{\approxeq}300 \ifmmode^\circ\else\textdegree\fi{}C), the crystals appear to possess a local, randomly oriented (up or down), polarization ${P}_{d}$. The values of ${T}_{d}$ obtained from the index and completely independent strain measurements are in very good agreement with each other, as are the values of ${P}_{d}$. Various aspects of our understanding of the polarization behavior and other effects in this ferroelectric system are discussed.

Measurements of strain and the optical indices in the ferroelectric Ba 0.4 Sr 0.6 Nb 2 O 6 : Polarization effects

The range of piezoelectric properties available in tungsten bronze crystals reviewed includes both longitudinal and shear mode responses. Specific crystal compositions investigated include Sr1-xBaxNb2O6 (SBN), Ba2-xSrxK1-yNayNb5O15 (BSKNN), K3Li2Nb5O15 (KLN), (Ba, Sr)6Ti2Nb8O30 (BSTN), Sr2-x-CaxNaNb5O15 (SCNN), Sr2KNb5O15 (SKN) and Pb1-xBaxNb2O6 (PBN). SBN, SCNN and SKN exhibit large piezoelectric d33 coefficients, while BSKNN, PBN:60 and KLN have large d15 shear coefficients. In La3+ -modified SBN:60, d33 can exceed 1000 pC/N, although its relaxor character increases with increasing La3+ content. The role of dopants in the 12-, 9- and 6-fold coordinated crystallographic sites is described with respect to the relaxor character of SBN crystals. The high piezoelectric and dielectric constants in these single crystals suggest their use in high frequency ultrasonic tomography. Both piezoelectric and electrostrictive options would appear to be available in the bronzes and the very high perfection of the availa...

Piezoelectricity in tungsten bronze crystals

Ferroelectric properties in gadolinium molybdate are shown to originate from a new mechanism completely different from that in conventional ferroelectric materials. In this crystal the spontaneous polarization results from an elastic instability which gives rise to a spontaneous strain in the original piezoelectric paraelectric phase. The dielectric permittivity of the clamped crystal ($\ensuremath{\epsilon}_{33}^{x}$) is low and independent of temperature, while the elastic constant ($c_{66}^{E}$) shows a strong temperature dependence with a marked anomaly at the Curie point.

L. E. Cross

Papers

Dielectric and piezoelectric properties of modified lead titanate zirconate ceramics from 4.2 to 300 K

Effects of porosity on electric fatigue behaviour in PLZT and PZT ferroelectric ceramics

Measurements of strain and the optical indices in the ferroelectric Ba 0.4 Sr 0.6 Nb 2 O 6 : Polarization effects

Piezoelectricity in tungsten bronze crystals

Gadolinium Molybdate, a New Type of Ferroelectric Crystal