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

Connectivity and piezoelectric-pyroelectric composites

High resolution x-ray powder diffraction measurements on poled PbZr1-xTixO3 (PZT) ceramic samples close to the rhombohedral-tetragonal phase boundary (the so-called morphotropic phase boundary) have shown that for both rhombohedral and tetragonal compositions the piezoelectric elongation of the unit cell does not occur along the polar directions but along those directions associated with the monoclinic distortion. This work provides the first direct evidence for the origin of the very high piezoelectricity in PZT.

https://arxiv.org/pdf/cond-mat/9912118.pdf

Origin of the high piezoelectric response in PbZr1-xTixO3

The temperature dependence of dielectric properties and electrical conduction of $({\mathrm{Sr}}_{1\ensuremath{-}1.5x}{\mathrm{Bi}}_{x}){\mathrm{TiO}}_{3} (0.0133l~xl~0.133)$ was measured from 10 to 800 K. Three sets of oxygen vacancies related dielectric peaks (peaks A, B, and $C)$ were observed. These peaks could be greatly suppressed or eliminated by annealing the samples in an oxidizing atmosphere, and enhanced or recreated by annealing in a reducing atmosphere. The results show that the Maxwell-Wagner polarization is not the main mechanism, and the Skanavi's model also cannot be directly applied. A tentative explanation was suggested. Peak A, observed in the temperature range of 100--350 K with the activation energy for dielectric relaxation ${E}_{\mathrm{relaxA}}=0.32--0.49$ eV, is attributed to the coupling effect of the conduction electrons with the motion of the off-centered Bi and Ti ions; the conduction carriers in this temperature range are from the first ionization of oxygen vacancies ${(V}_{o}).$ Peaks B and C are also discussed.

Oxygen-vacancy-related low-frequency dielectric relaxation and electrical conduction in B i : S r T i O 3

In Pb(Sc0.5Ta0.5)O3 it has been shown that the degree of order in the B‐site Sc3+, Ta5+ cations can be controlled by suitable thermal annealing. For samples which have been well‐ordered by long annealing, dielectric measurements on single crystals show a normal first‐order ferroelectric phase change at 13 °C and a maximum low‐temperature spontaneous polarization of 23.0 μc/cm2. With increasing disorder, the crystals begin to exhibit the classical diffuse phase transition of a ferroelectric relaxor, with a broad Curie range and strong low‐frequency dielectric dispersion in the transition range. X‐ray diffraction measurements of the size of the ordered microregions suggest that ordering proceeds by different mechanisms in single‐crystal versus ceramic samples, though the resulting effects upon the dielectric behavior are very similar.

The Role of B-Site Cation Disorder in Diffuse Phase-Transition Behavior of Perovskite Ferroelectrics

The perovskitelike ferroelectric system ${\mathrm{PbZr}}_{1\ensuremath{-}x}{\mathrm{Ti}}_{x}{\mathrm{O}}_{3}$ (PZT) has a nearly vertical morphotropic phase boundary (MPB) around $x=0.45--0.50.$ Recent synchrotron x-ray powder diffraction measurements by Noheda et al. [Appl. Phys. Lett. 74, 2059 (1999)] have revealed a monoclinic phase between the previously established tetragonal and rhombohedral regions. In the present work we describe a Rietveld analysis of the detailed structure of the tetragonal and monoclinic PZT phases on a sample with $x=0.48$ for which the lattice parameters are, respectively, ${a}_{t}=4.044$ \AA{}, ${c}_{t}=4.138$ \AA{}, at 325 K, and ${a}_{m}=5.721$ \AA{}, ${b}_{m}=5.708$ \AA{}, ${c}_{m}=4.138$ \AA{}, $\ensuremath{\beta}=90.496\ifmmode^\circ\else\textdegree\fi{},$ at 20 K. In the tetragonal phase the shifts of the atoms along the polar [001] direction are similar to those in ${\mathrm{PbTiO}}_{3}$ but the refinement indicates that there are, in addition, local disordered shifts of the Pb atoms of $\ensuremath{\sim}0.2$ \AA{} perpendicular to the polar axis. The monoclinic structure can be viewed as a condensation along one of the $〈110〉$ directions of the local displacements present in the tetragonal phase. It equally well corresponds to a freezing-out of the local displacements along one of the $〈100〉$ directions recently reported by Corker et al. [J. Phys.: Condens. Matter 10, 6251 (1998)] for rhombohedral PZT. The monoclinic structure therefore provides a microscopic picture of the MPB region in which one of the ``locally'' monoclinic phases in the ``average'' rhombohedral or tetragonal structures freezes out, and thus represents a bridge between these two phases.

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L. E. Cross

Papers

Connectivity and piezoelectric-pyroelectric composites

Origin of the high piezoelectric response in PbZr1-xTixO3

Oxygen-vacancy-related low-frequency dielectric relaxation and electrical conduction in B i : S r T i O 3

The Role of B-Site Cation Disorder in Diffuse Phase-Transition Behavior of Perovskite Ferroelectrics

Tetragonal-to-monoclinic phase transition in a ferroelectric perovskite : The structure of PbZr0.52Ti0.48O3