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

1. Introduction 20642. Synthesis of Magnetic Nanoparticles 20662.1. Classical Synthesis by Coprecipitation 20662.2. Reactions in Constrained Environments 20682.3. Hydrothermal and High-TemperatureReactions20692.4. Sol-Gel Reactions 20702.5. Polyol Methods 20712.6. Flow Injection Syntheses 20712.7. Electrochemical Methods 20712.8. Aerosol/Vapor Methods 20712.9. Sonolysis 20723. Stabilization of Magnetic Particles 20723.1. Monomeric Stabilizers 20723.1.1. Carboxylates 20733.1.2. Phosphates 20733.2. Inorganic Materials 20733.2.1. Silica 20733.2.2. Gold 20743.3. Polymer Stabilizers 20743.3.1. Dextran 20743.3.2. Polyethylene Glycol (PEG) 20753.3.3. Polyvinyl Alcohol (PVA) 20753.3.4. Alginate 20753.3.5. Chitosan 20753.3.6. Other Polymers 20753.4. Other Strategies for Stabilization 20764. Methods of Vectorization of the Particles 20765. Structural and Physicochemical Characterization 20785.1. Size, Polydispersity, Shape, and SurfaceCharacterization20795.2. Structure of Ferro- or FerrimagneticNanoparticles20805.2.1. Ferro- and Ferrimagnetic Nanoparticles 20805.3. Use of Nanoparticles as Contrast Agents forMRI20825.3.1. High Anisotropy Model 20845.3.2. Small Crystal and Low Anisotropy EnergyLimit20855.3.3. Practical Interests of Magnetic NuclearRelaxation for the Characterization ofSuperparamagnetic Colloid20855.3.4. Relaxation of Agglomerated Systems 20856. Applications 20866.1. MRI: Cellular Labeling, Molecular Imaging(Inﬂammation, Apoptose, etc.)20866.2.

Magnetic Iron Oxide Nanoparticles: Synthesis, Stabilization, Vectorization, Physicochemical Characterizations, and Biological Applications

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

Doping is a widely applied technological process in materials science that involves incorporating atoms or ions of appropriate elements into host lattices to yield hybrid materials with desirable properties and functions. For nanocrystalline materials, doping is of fundamental importance in stabilizing a specific crystallographic phase, modifying electronic properties, modulating magnetism as well as tuning emission properties. Here we describe a material system in which doping influences the growth process to give simultaneous control over the crystallographic phase, size and optical emission properties of the resulting nanocrystals. We show that NaYF(4) nanocrystals can be rationally tuned in size (down to ten nanometres), phase (cubic or hexagonal) and upconversion emission colour (green to blue) through use of trivalent lanthanide dopant ions introduced at precisely defined concentrations. We use first-principles calculations to confirm that the influence of lanthanide doping on crystal phase and size arises from a strong dependence on the size and dipole polarizability of the substitutional dopant ion. Our results suggest that the doping-induced structural and size transition, demonstrated here in NaYF(4) upconversion nanocrystals, could be extended to other lanthanide-doped nanocrystal systems for applications ranging from luminescent biological labels to volumetric three-dimensional displays.

Simultaneous phase and size control of upconversion nanocrystals through lanthanide doping

The regulation of engineered nanoparticles requires a widely agreed definition of such particles. Nanoparticles are routinely defined as particles with sizes between about 1 and 100 nm that show properties that are not found in bulk samples of the same material. Here we argue that evidence for novel size-dependent properties alone, rather than particle size, should be the primary criterion in any definition of nanoparticles when making decisions about their regulation for environmental, health and safety reasons. We review the size-dependent properties of a variety of inorganic nanoparticles and find that particles larger than about 30 nm do not in general show properties that would require regulatory scrutiny beyond that required for their bulk counterparts.

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Towards a definition of inorganic nanoparticles from an environmental, health and safety perspective

We report here synthesis of phase-pure magnetoelectric BiFeO3 thin films with controlled oxygen stoichiometry on Pt/TiO2/SiO2/Si substrate using pulsed-laser deposition technique. Saturated ferroelectric hysteresis loop has been observed in phase-pure and highly resistive BiFeO3 thin films. The dielectric response study of the films with temperature indicates an anomaly in dielectric constant e(T), in the vicinity of Neel temperature (∼380 °C). This anomaly in e(T) is explained as an influence of vanishing magnetic ordering on electric ordering of magnetoelectric BiFeO3 sample.

Observation of saturated polarization and dielectric anomaly in magnetoelectric BiFeO3 thin films

Magnetoelectric compounds with the general formula, ${\mathrm{Bi}}_{09\ensuremath{-}x}{R}_{x}{\mathrm{La}}_{01}{\mathrm{FeO}}_{3}$ $(R=\mathrm{Gd},$ Tb, Dy, etc), have been synthesized These show the coexistence of ferroelectricity and magnetism, possess high dielectric constant and exhibit magnetoelectric coupling at room temperature Such materials may be of great significance in basic as well as applied research

Magnetoelectricity at room temperature in the Bi 0.9 − x Tb x La 0.1 FeO 3 system

We report a detailed study of the size dependence of the ferroelectric transition in an ensemble of ${\mathrm{PbTiO}}_{3}$ nanoparticles produced by coprecipitation. The phase transition was monitored by dielectric measurements, variable temperature x-ray diffraction, and differential scanning calorimetry (DSC). Size effects were found to become important only below \ensuremath{\approxeq}100 nm (coherently diffracting x-ray domain size). The tetragonal distortion of the unit cell (which is related to the spontaneous polarization) decreases exponentially with size and vanishes at 7 nm. The ${\mathit{T}}_{\mathit{c}}$ decreases gradually but the transition becomes increasingly diffuse with a decrease in the size from 80 to 30 nm, below which there is no peak in the dielectric constant or the heat flow (DSC), though ferroelectric ordering probably persists down to \ensuremath{\approxeq}7 nm.

Size-induced diffuse phase transition in the nanocrystalline ferroelectric PbTiO 3

Size-induced changes in the crystal symmetry have been observed in ${\mathrm{Al}}_{2}$${\mathrm{O}}_{3}$, ${\mathrm{Fe}}_{2}$${\mathrm{O}}_{3}$, ${\mathrm{PbTiO}}_{3}$, ${\mathrm{PbZrO}}_{3}$, ${\mathrm{La}}_{1.85}$${\mathrm{Sr}}_{0.15}$${\mathrm{CuO}}_{4}$, ${\mathrm{YBa}}_{2}$${\mathrm{Cu}}_{3}$${\mathrm{O}}_{7\mathrm{\ensuremath{-}}\mathrm{\ensuremath{\delta}}}$, and ${\mathrm{Bi}}_{2}$${\mathrm{CaSr}}_{2}$${\mathrm{Cu}}_{2}$${\mathrm{O}}_{8}$. In these systems---and presumably in a large majority of partially covalent oxides---the crystal lattice tends to transform into a structure of higher symmetry with a decrease in the crystal size. We also find that the size dependence of many important physical properties can be ascribed directly to the lattice distortion. The physical mechanism responsible for these phenomena is intriguing and their complete understanding essential since they effectively define the practical lower limit to the miniaturization of devices based on these materials.

Effect of crystal size reduction on lattice symmetry and cooperative properties.

Microcrystalline particles of Fe2O3 having different sizes (varying between 70 and 5 nm) have been synthesised using a novel three-component micro-emulsion technique. A succession of crystal-size-induced structural transitions was observed. While alpha -Fe2O3 was found to nucleate for a particle size above 30 nm, gamma -Fe2O3 was preferentially formed for a size below 30 nm, whereas amorphous Fe2O3 was formed at a particle size of 5 nm. These structural transformations have been related to the increase in the unit-cell volume that occurs as the particle size is decreased. The size dependence of the lattice parameter is shown to arise from a coupling of the surface energy to the dilatational lattice mode. A model Hamiltonian which incorporates this interaction and displays size-induced phase transitions is defined. The Mossbauer hyperfine field in the microcrystalline samples at 4.2 K was found to be substantially smaller than in the 'bulk'. The hyperfine parameters of the amorphous sample were found to be similar to those pertaining to samples prepared by conventional techniques such as melt quenching. A large anisotropy in the ionic vibrational amplitudes was detected in samples with particles smaller than about 10 nm.

https://iopscience.iop.org/article/10.1088/0022-3719/21/11/014/pdf

V. R. Palkar

Papers

Observation of saturated polarization and dielectric anomaly in magnetoelectric BiFeO3 thin films

Magnetoelectricity at room temperature in the Bi 0.9 − x Tb x La 0.1 FeO 3 system

Size-induced diffuse phase transition in the nanocrystalline ferroelectric PbTiO 3

Effect of crystal size reduction on lattice symmetry and cooperative properties.

Size-induced structural phase transitions and hyperfine properties of microcrystalline Fe2O3