Ferroelectrics organic crystals

Pyroelectric detectors depend on the use of a thin slice of ferroelectric material (deuterated triglycine sulfate [DTGS], Figure 5.6, is the standard example) - in which the molecules of the organic crystal are naturally aligned with a permanent electric dipole. The thin slab is cut and arranged such that the direction... 

The paper is organized as follows. Sect. 2 describes the general principles and recent results for the synthesis of cyclotriveratrylenes Sect. 3 describes some applications of these compounds to host-guest chemistry. This latter section is devoted principally to the cryptophanes, and to host molecules containing one CTV unit that have recently been described. Sec. 4 presents some prospective work in the field of material sciences, i.e., ferroelectric liquid crystals and organic three-dimensional charge transfer salts. 

It is difficult to grow a good organic crystal film and a Langimur-Blogette film of up to 1 micron thickness. However, polymers have a wide choice and can be tailored to meet the above requirements. The polymers may be side chain liquid crystalline polymers, ferroelectric liquid crystalline polymers and amorphous polymers. Among them the side chain liquid crystalline polymers have drawn more attention. 

The chapter is organized as follows The second section discusses the prototype polar smectics the ferroelectric liquid crystals. We discuss the structure of the ferroelectric phase, the theoretical explanation for it and we introduce the flexoelectric effect in chiral polar smectics. Next we introduce a new set of chiral polar smectics, the antiferroelectric liquid crystals, and we describe the structures of different phases found in these systems. We present the discrete theoretical modelling approach, which experimentally consistently describes the phases and their properties. Then we introduce the discrete form of the flexoelectric effect in these systems and show that without flexoelectricity no interactions of longer range would be significant and therefore no structures with longer periods than two layers would be stable. We discuss also a few phenomena that are related to the complexity of the structures, such as the existence of a longitudinal, i.e. parallel to the... 

Ferroelectric liquid crystals were first synthesized in 1974 after a discussion between theorists, chemists and experimentalists dm-ing a queue for lunch. The theoretical idea proposed by Meyer that chiral molecules organized in the SmC structure should have polar layers with a polarization perpendicular to the tilt and the layer normal, was almost immediately realized by the chemist Strzelecky. The era of polar liquid crystals began. 

In the Landolt-Bdmstein data collection, ferroelectric and antiferroelectric substances are classified into 72 families according to their chemical composition and their crystallographic structure. Some substances which are in fact neither ferroelectric nor antiferroelectric but which are important in relation to ferroelectricity or anti-ferroelectricity, for instance as an end material of a solid solution, are also included in these families as related substances. This subsection surveys these 72 families of ferroelectrics presented in Landolt-Bornstein Vol. III/36 (LB III/36). Nineteen of these families concern oxides [5.1,2], 30 of them concern inorganic crystals other than oxides [5.3], and 23 of them concern organic crystals, liquid crystals, and polymers [5.4]. Table 4.5-1 lists these families and gives some information about each family. Substances classified in LB 111/36 as miscellaneous crystals (outside the families) are not included. 

Walba, D. M., Keller, P., Parmar, D. S., Clark, N. A., and Wand, M. D., Design and synthesis of new ferroelectric liquid crystals. 9. An approach to creation of organic polymer thin films with controlled, stable polar orientation of functional groups, J. Am. Chem. Soc., Ill, 8273-8274 (1989). 

Ferroelectric materials are a subclass of pyro- and piezoelectric materials (Fig. 1) (see Piezoelectric Polymers). They are very rarely foimd in crystalline organic or polymeric materials because ferroelectric hysteresis requires enough molecular mobility to reorient molecular dipoles in space. So semicrystalline poly(vinylidene fluoride) (PVDF) is nearly the only known compoimd (1). On the contrary, ferroelectric behavior is very often observed in chiral liquid crystalline materials, both low molar mass and poljuneric. For an overview of ferroelectric liquid crystals, see Reference 2. Tilted smectic liquid crystals that are made from chiral molecules lack the symmetry plane perpendicular to the smectic layer structure (Fig. 2). Therefore, they develop a spontaneous electric polarization, which is oriented perpendicular to the layer normal and perpendicular to the tilt direction. Because of the liquid-like structure inside the smectic layers, the direction of the tilt and thns the polar axis can be easily switched in external electric fields (see Figs. 2 and 3). 

The committee also organized the 4th International Conference on Ferroelectric Liquid Crystals in Tokyo in 1993. Many Japanese companies were very active in ferroelectric liquid crystals materials, especially a smectic C liquid crystal phase in which is growing globally against a background of the next nematic liquid crystal, and the meeting was a great success. 

Sato H, Fujikake H, Lino Y, Kawakita M, Kikuchi H (2002) Flexible grayscale ferroelectric liquid crystal device containing polymer walls and networks. Jpn J Appl Phys 41 5302-5306 Sato H, Fujikake H, Kikuchi H, Kurita T (2003) Rollable polymer stabilized ferroelectric liquid crystal device using thin plastic substrates. Opt Rev 10(5) 352-356 Schrader DM, Jean YC (1988) Positron and positronium chemistry. Elsevier, Amsterdam Shinkawa K, Takahashi H, Fume H (2008) Ferroelectric liquid crystal cell with phase separated composite organic film. Ferroelectrics 364 107-112 Simha R, Somcynsky T (1969) On the statistical thermodynamics of spherical and chain molecule fluids. Macromolecules 2 342-350... 

To understand how chirality is expressed, it is important to first describe the different thermotropic mesophase assemblies which can be formed by chiral discotics. Even though expression of chirality has been observed in thermotropic mesophases, the chiral expression occurs in a rather uncontrolled manner, and systems which are suitable for applications, for example, easily switchable columns/ferroelectric discotic liquid crystals, consequently have not yet been developed. Hence, the assembly of discotics in solution has received considerable attention. Supramolecular assemblies of discotic molecules in solution are still in their infancy and have not yet found commercial application, but they are of fundamental importance since they allow a detailed and focused investigation of the specific interactions that are required to express chirality at higher levels of organization. As such, the fundamental knowledge acquired from supramolecular assemblies in solution might formulate the design criteria for thermotropic chiral discotic mesophases and provide the necessary tools for the creation of functional systems. 

Cu(II)-Doped Organic Ferroelectric Crystals Cu(II)-Doped Triglycine Sulfate... 

Collet E, Lemee-Cailleau MH, Buron-Le Cointe M, Cailleau H, Wulff M, Luty T, Koshihara S, Meyer M, Toupet L, Rabiller P, Techert S (2003) Laser-induced ferroelectric structural order in an organic charge-transfer crystal. Science 300 612-615... 

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