Spontaneous ferroelectrics

Reddy, R. A. Zhu, C. Shao, R. Korblova, E. Gong, T. Shen, Y. Garcia, E. Glaser, M. A. Maclennan, J. E. Walba, D. M. Clark, N. A. Spontaneous ferroelectric order in a bent-core smectic liquid crystal of fiuid orthorhombic layers. Science 2011, 332, 72-77. 

Figure 17. Spontaneous ferroelectric domains appearing in the surface-stabilized state.

As witli tlie nematic phase, a chiral version of tlie smectic C phase has been observed and is denoted SniC. In tliis phase, tlie director rotates around tlie cone generated by tlie tilt angle [9,32]. This phase is helielectric, i.e. tlie spontaneous polarization induced by dipolar ordering (transverse to tlie molecular long axis) rotates around a helix. However, if tlie helix is unwound by external forces such as surface interactions, or electric fields or by compensating tlie pitch in a mixture, so tliat it becomes infinite, tlie phase becomes ferroelectric. This is tlie basis of ferroelectric liquid crystal displays (section C2.2.4.4). If tliere is an alternation in polarization direction between layers tlie phase can be ferrielectric or antiferroelectric. A smectic A phase foniied by chiral molecules is sometimes denoted SiiiA, altliough, due to the untilted symmetry of tlie phase, it is not itself chiral. This notation is strictly incorrect because tlie asterisk should be used to indicate the chirality of tlie phase and not tliat of tlie constituent molecules. 

The most important materials among nonlinear dielectrics are ferroelectrics which can exhibit a spontaneous polarization PI in the absence of an external electric field and which can spHt into spontaneously polarized regions known as domains (5). It is evident that in the ferroelectric the domain states differ in orientation of spontaneous electric polarization, which are in equiUbrium thermodynamically, and that the ferroelectric character is estabUshed when one domain state can be transformed to another by a suitably directed external electric field (6). It is the reorientabiUty of the domain state polarizations that distinguishes ferroelectrics as a subgroup of materials from the 10-polar-point symmetry group of pyroelectric crystals (7—9). 

Ferroelectric crystals exhibit spontaneous electric polarization and hysteresis effects in the relation between polarization and electric field, as shown in Figure 1. This behavior is usually observed in a limited temperature range, ie, usually below a transition temperature (10). 

Both the Spontaneous polarization PI and the remanent polarization P/ are strong functions of temperature, particularly near the transition temperature T in ferroelectrics (7) ... 

Barium titanate [12047-27-7] has five crystaUine modifications. Of these, the tetragonal form is the most important. The stmcture is based on corner-linked oxygen octahedra, within which are located the Ti" " ions. These can be moved from their central positions either spontaneously or in an apphed electric field. Each TiO octahedron may then be regarded as an electric dipole. If dipoles within a local region, ie, a domain, are oriented parallel to one another and the orientation of all the dipoles within a domain can be changed by the appHcation of an electric field, the material is said to be ferroelectric. At ca 130°C, the Curie temperature, the barium titanate stmcture changes to cubic. The dipoles now behave independentiy, and the material is paraelectric (see Ferroelectrics). 

Ferroelectrics. Ferroelectrics, materials that display a spontaneous polarization ia the abseace of an appHed electric field, also display pyroelectric and piezoelectric behavior. The distinguishing characteristic of ferroelectrics, however, is that the spontaneous polarization must be re-orientable with the appHcation of an electric field of a magnitude lower than the dielectric breakdown strength of the material. 

The ferroelectricity usually disappears above a certain transition temperature (often called a Curie temperature) above which the crystal is said to be paraelectric this is because thermal motion has destroyed the ferroelectric order. Occasionally the crystal melts or decomposes before the paraelectric state is reached. There are thus some analogies to ferromagnetic and paramagnetic compounds though it should be noted that there is no iron in ferroelectric compounds. Some typical examples, together with their transition temperatures and spontaneous permanent electric polarization P, are given in the Table. 

Since niobates and tantalates belong to the octahedral ferroelectric family, fluorine-oxygen substitution has a particular importance in managing ferroelectric properties. Thus, the variation in the Curie temperature of such compounds with the fluorine-oxygen substitution rate depends strongly on the crystalline network, the ferroelectric type and the mutual orientation of the spontaneous polarization vector, metal displacement direction and covalent bond orientation [47]. Hence, complex tantalum and niobium fluoride compounds seem to have potential also as new materials for modem electronic and optical applications. 

Crystals with one of the ten polar point-group symmetries (Ci, C2, Cs, C2V, C4, C4V, C3, C3v, C(, Cgv) are called polar crystals. They display spontaneous polarization and form a family of ferroelectric materials. The main properties of ferroelectric materials include relatively high dielectric permittivity, ferroelectric-paraelectric phase transition that occurs at a certain temperature called the Curie temperature, piezoelectric effect, pyroelectric effect, nonlinear optic property - the ability to multiply frequencies, ferroelectric hysteresis loop, and electrostrictive, electro-optic and other properties [16, 388],... 

The main source of spontaneous polarization in crystals is the relative freedom of cations that fit loosely into the crystal s octahedral cavities. The number of degrees of freedom of the octahedrons affects the spontaneous polarization value and hence influences the crystal s ferroelectric properties. Abrahams and Keve [389] classified ferroelectric materials into three structural categories according to their atomic displacement mechanisms onedimensional, two-dimensional and three-dimensional. 

In the operation of ferroelectric liquid crystal devices, the applied electric field couples directly to the spontaneous polarisation Ps and response times depend on the magnitude E Ps. Depending on the electronic structure (magnitude and direction of the dipole moment as well as position and polarity of the chiral species) and ordering of the molecules P can vary over several orders of magnitude (3 to 1.2 x 10 ), giving response times in the range 1-100 ps. 

A similar chiral chlorogold(I) compound [AuCl(CNC6H4C00C6H40C H-MeC6Hi3)j has been described, displaying ferroelectric SmC (152 °C), and SmA (185 °C) mesophases before decomposition occurs at the clearing temperature (285 °C). However, the spontaneous polarization could not be measured with precision due to the inherent conductivity of the compound [12]. 

Hysteresis curve of a ferroelectric crystal, v = initial (virginal) curve, Pr = remanent polarization, Ps = spontaneous polarization, Ec = coercive field... 

In addition, some liquid-crystalline elastomers are ferroelectric (possess spontaneous electric polarization) [196,197], or piezoelectric (become electrically... 

There is considerable interest in developing new types of magnetic materials, with a particular hope that ferroelectric solids and polymers can be constructed— materials having spontaneous electric polarization that can be reversed by an electric field. Such materials could lead to new low-cost memory devices for computers. The fine control of dispersed magnetic nanostructures will take the storage and tunability of magnetic media to new levels, and novel tunneling microscopy approaches allow measurement of microscopic hysteresis effects in iron nanowires. 

The earliest approach to explain tubule formation was developed by de Gen-nes.168 He pointed out that, in a bilayer membrane of chiral molecules in the Lp/ phase, symmetry allows the material to have a net electric dipole moment in the bilayer plane, like a chiral smectic-C liquid crystal.169 In other words, the material is ferroelectric, with a spontaneous electrostatic polarization P per unit area in the bilayer plane, perpendicular to the axis of molecular tilt. (Note that this argument depends on the chirality of the molecules, but it does not depend on the chiral elastic properties of the membrane. For that reason, we discuss it in this section, rather than with the chiral elastic models in the following sections.)... 

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