Switching ferroelectrics

Naciri, J., Pfeiffer, S., and Shashidhar, R., Fast switching ferroelectric side chain liquid-crystalline polymer and copolymer, Uq. Cry.%t., 10, 585-591 (1991). 

Scherowsky, G., Fast-switching ferroelectric liquid-crystalline polymers. Mol. Cryst. Liq. Cry.st., 69, 87-98 (1993). 

A comparative study of ultrathin dielectric (an azo-compound) and ferroelectric (copolymer P(VDF-TrFE)) Langmuir-Blodgett (LB) films has been carried out by Electrostatic Force Microscopy (EFM). Films were poled locally by a strong d.c. field applied between a conductive tip of an Atomic Force Microscope (AFM) and the bottom A1 electrode. The electrically poled domain was studied by EFM using a weak a.c. electric field and a lock-in amplifier technique. Two modes, a contact and non-contact ones, allowed for the measurement of field a in the air gap between the film and the tip and the piezoelectric distortion of the film due to the d.c. field aligned spontaneous polarization. Simultaneously the topographic relief of the same area was imaged. The results confirm unequivocally a possibility to switch ferroelectric LB film locally by an AFM tip. 

Unwinding or suppressing the helix leads to macroscopic polaiizatioa. This has been successfully realiz in surface-stabilized thin cells with a 2- un gap. Thu invention by Qark and Lagerwall in 1980 (4 was the starting point of the development of fut-switching ferroelectric liquid cry displays. The principle of their operation is shown in Figure 3. 

J. NacirL S. Pfeiffer, and R. Shaahidhar, Fast switching ferroelectric tide-chain Uquid-crystaUinc polymer and copolymer, Uq. CrysL 10585 (1991). 

G. Scherowtky, Fast-switching ferroelectric liquid crystalline potymers containing one or two centres of chirality in the tide chain, Polymers for Advanced Technologies (M. Levin, ed.) John Wiley, New York. 1992. Md. 3. p. 219. 

G. Scherowsky, Fast switching ferroelectric liquid crystalline polymers coirtaining one or two centers of chi ty in the aide chain. Polymer Adv TechnoL 3 219-229 (1992). 

New natural polymers based on synthesis from renewable resources, improved recyclability based on retrosynthesis to reusable precursors, and molecular suicide switches to initiate biodegradation on demand are the exciting areas in polymer science. In the area of biomolecular materials, new materials for implants with improved durability and biocompatibility, light-harvesting materials based on biomimicry of photosynthetic systems, and biosensors for analysis and artificial enzymes for bioremediation will present the breakthrough opportunities. Finally, in the field of electronics and photonics, the new challenges are molecular switches, transistors, and other electronic components molecular photoad-dressable memory devices and ferroelectrics and ferromagnets based on nonmetals. 

Finally, ferroelectricity has been shown for columnar metallomesogens.35 Serrano and co-workers have shown that metal ft-diketonates, provided with chiral side chains (e.g., 32), form helical columns (vide supra), which can also be switched under an alternating electric field. 

Along with the prediction and discovery of a macroscopic dipole in the SmC phase and the invention of ferroelectric liquid crystals in the SSFLC system, the discovery of antiferroelectric liquid crystals stands as a key milestone in chiral smectic LC science. Antiferroelectric switching (see below) was first reported for unichiral 4-[(l-methylheptyloxy)carbonyl]phenyl-4/-octyloxy-4-biphenyl carboxylate [MHPOBC, (3)],16 with structure and phase sequence... 

Figure 8.12 Longitudinal sheets with antiparallel polar symmetry are illustrated for achiral SmCA and SmC phases. Since it is not possible to switch to ferroelectric state in such system upon application of electric field, these structure should not be considered antiferroelectric.

Figure 8.13 Hypothetical smectic mesogen with hinge in center of core is illustrated. Such material could in principal switch to ferroelectric state, which we term the SmAPp, upon application of electric field in plane of layers. If this state exists in well on configurational hypersurface, then ground-state structure is antiferroelectric, denoted SmAPA.

Using this method, the M6R8/PM6R8 blend showed precisely the behavior expected for the achiral SmAPA structure. Specifically, the optical properties of the films were consistent with a biaxial smectic structure (i.e., two different refractive indices in the layer plane). The thickness of the films was quantized in units of one bilayer. Upon application of an electric field, it was seen that films with an even number of bilayers behaved in a nonpolar way, while films with an odd number of bilayers responded strongly to the field, showing that they must possess net spontaneous polarization. Note that the electric fields in this experiment are not strong enough to switch an antiferroelectric to a ferroelectric state. Reorientation of the polarization field (and director structure) of the polar film in the presence of a field can easily be seen, however. 

Figure 8.17 Structure and phase sequence of first banana-phase mesogen, reported by Vorlander in 1929, is given. Liquid crystal phase exhibited by this material (actually Vorlander s original sample) was shown by Pelzl et al.36a to have B6 stmeture, illustrated on right, in 2001. Achiral B6 phase does not switch in response to applied fields in way that can be said to be either ferroelectric or antiferroelectric.

Application of an electric field to the SmCsPA phase then causes the system to switch to a ferroelectric state. This could occur in two ways. The molecules in every other layer could simply rotate about the director, leaving the layer clinicity the same but changing the chirality of alternate layers. This would require a locally diastereomeric transition structure where the polarization is not parallel to the layers. 

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