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

In 1978 it was discovered, largely through the work of Fleischmann, Van Duyne, Creighton, and their coworkers that molecules adsorbed on specially prepared silver surfaces produce a Raman spectrum that is at times a millionfold more intense than expected. This effect was dubbed surface-enhanced Raman scattering (SERS). Since then the effect has been demonstrated with many molecules and with a number of metals, including Cu, Ag, Au, Li, Na, K, In, Pt, and Rh. In addition, related phenomena such as surface-enhanced second-harmonic generation, four-wave mixing, absorption, and fluorescence have been observed. Although not all fine points of the enhancement mechanism have been clarified, the majority view is that the largest contributor to the intensity amplification results from the electric field enhancement that occurs in the vicinity of small, interacting metal particles that are illuminated with light resonant or near resonant with the localized surface-plasmon frequency of the metal structure. Small in this context is gauged in relation to the wavelength of light. The special preparations required to produce the effect, which include among other techniques electrochemical oxidation-reduction cycling, deposition of metal on very cold substrates, and the generation of metal-island films and colloids, is now understood to be necessary as a means of producing surfaces with appropriate electromagnetic resonances that may couple to electromagnetic fields either by generating rough films (as in the case of the former two examples) or by placing small metal particles in close proximity to one another (as in the case of the latter two). For molecules chemisorbed on SERS-active surface there exists a "chemical enhancement" in addition to the electromagnetic effect. Although difficult to measure accurately, the magnitude of this effect rarely exceeds a factor of 10 and is best thought to arise from the modification of the Raman polarizability tensor of the adsorbate resulting from the formation of a complex between the adsorbate and the metal. Rather than an enhancement mechanism, the chemical effect is more logically to be regarded as a change in the nature and identity of the adsorbate.

Surface-enhanced spectroscopy

Magnetism and ferroelectricity are essential to many forms of current technology, and the quest for multiferroic materials, where these two phenomena are intimately coupled, is of great technological and fundamental importance. Ferroelectricity and magnetism tend to be mutually exclusive and interact weakly with each other when they coexist. The exciting new development is the discovery that even a weak magnetoelectric interaction can lead to spectacular cross-coupling effects when it induces electric polarization in a magnetically ordered state. Such magnetic ferroelectricity, showing an unprecedented sensitivity to ap plied magnetic fields, occurs in 'frustrated magnets' with competing interactions between spins and complex magnetic orders. We summarize key experimental findings and the current theoretical understanding of these phenomena, which have great potential for tuneable multifunctional devices.

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Multiferroics: a magnetic twist for ferroelectricity

The historical beginnings of photosensitivity and fiber Bragg grating (FBG) technology are recounted. The basic techniques for fiber grating fabrication, their characteristics, and the fundamental properties of fiber gratings are described. The many applications of fiber grating technology are tabulated, and some selected applications are briefly described.

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Fiber Bragg grating technology fundamentals and overview

FERROELECTRIC materials are characterized by a switchable macroscopic polarization. Most technologically important ferroelectrics are oxides with a perovskite structure. The origin of their ferroelectric behaviour is unclear, however, and there is incomplete understanding of why similar, but chemically different, perovskites should display very different ferroelectric behaviour. The great sensitivity of ferroelectrics to chemistry, defects, electrical boundary conditions and pressure arises from a delicate balance between long-range Coulomb forces (which favour the ferroelectric state) and short-range repulsions (which favour the nonpolar cubic structure). To model the transition accurately, total-energy techniques are required which incorporate the effects of charge distortion and covalency. Here I report results of electronic-structure calculations on two classic examples of ferroelectric perovskites, BaTiO3 and PbTiO3, and demonstrate that hybridization between the titanium 3d states and the oxygen 2p states is essential for ferroelectricity. The different ferroelectric phase behaviour of the two materials is also clear: in PbTiO3, the lead and oxygen states hybridize, leading to a large strain that stabilizes the tetragonal phase, whereas in BaTiO3 the interaction between barium and oxygen is completely ionic, favouring a rhombohedral structure.

Origin of ferroelectricity in perovskite oxides

The book develops the modern theory of ferroelectricity in terms of soft modes and lattice dynamics and also describes modern techniques of measurement, including X-ray, optic, and neutron scattering, infra-red absorption, and magnetic resonance. It includes a discussion of the related phenomena of antiferroelectricity, pyroelectricity, and ferroelasticity and seconds on domains, thin films, ceramics, and polymers, leading on to a comprehensive survey of potential and actual device capabilities for pyroelectric detection, memories, display, and modulation. It should provide an authoritative account for those engaged in research or graduate ferroelectric or pyroelectric devices.

Principles and Applications of Ferroelectrics and Related Materials

Photocurrents in doped LiNbO3 crystals are shown to be due to a bulk photovoltaic effect with saturation voltages in excess of 1000 V (∼105 V/cm). This effect accounts for the light‐induced index changes in LiNbO3. An explanation of the photovoltaic effect, based on the asymmetry of the lattice, is proposed.

High‐voltage bulk photovoltaic effect and the photorefractive process in LiNbO3

Permanent reversible changes of the refractive index of pure and doped LiNbO3 have been obtained by multiphoton absorption. Greatly increased sensitivity over the linear process enables holograms to be recorded even in high‐purity LiNbO3, with a diffraction efficiency of 25% with less than 0.4 J/cm2. These holograms can be read nondestructively, eliminating the need for fixing processes while the versatility of optical erasure is maintained.

Multiphoton photorefractive processes for optical storage in LiNbO3

Absorption, luminescence, and excitation luminescence studies of dye molecules adsorbed onto ultrathin, variable-thickness silver films show strong coupling of the particle plasma resonances to the molecules. Luminescence from the dye is increased by excitation transfer from the silver particles for certain film thickness. Increased luminescence has also been observed from dyes on Au and Cu films.

Interaction of metal particles with adsorbed dye molecules: absorption and luminescence.

Enhanced second-harmonic generation is observed from silver and gold island films, and from regular arrays of Ag particles produced by microlithographic techniques. Enhancements are interpreted in terms of an electromagnetic model involving localized surface-plasma oscillations. The regular arrays allow the separation of fundamental and second-harmonic beams by a novel grating effect.

Alastair M. Glass

Papers

Principles and Applications of Ferroelectrics and Related Materials

High‐voltage bulk photovoltaic effect and the photorefractive process in LiNbO3

Multiphoton photorefractive processes for optical storage in LiNbO3

Interaction of metal particles with adsorbed dye molecules: absorption and luminescence.

Surface second-harmonic generation from metal island films and microlithographic structures