Previous results from Kundu using dielectric relaxation have suggested a reentrant antiferroelectric-ferroelectric-antiferroelectric transition in the compound LN36. Our comprehensive studies of this compound using differential optical reflectivity, nonadiabatic scanning calorimetry, null transmission ellipsometry, and resonant x-ray diffraction show that in fact LN36 exhibits the usual phase sequence for chiral smectic liquid crystals: SmA*-SmC*alpha-SmC*-SmC*FI1-SmC*A . Moreover, the SmC*alpha-SmC* transition is a first-order transition, characterized by a discontinuous change in the helical pitch. At temperatures just above the SmC*alpha-SmC* transition, two different values for the helical pitch are simultaneously observed for the first time.

A detailed study of a novel material exhibiting antiferro-, ferri-, and ferroelectric phases has been undertaken. The tilt angle, spontaneous polarisation and the dynamics of the helical unwinding have been examined as a function of temperature and voltage in all the phases of interest. The material exhibits large tilt angles (similar to 31 degrees) and values of spontaneous polarisation (similar to 100nCcm(-2)) in cases where the helix is totally unwound. The behaviour of tilt angle as a function of applied electric field is examined in the ferri- and antiferro-electric phases. A stepwise increase in tilt angle as a function of applied voltage in the ferri-electric phase is presented, as well as unusual behaviour in the antiferro-electric state. In addition, a preliminary investigation of the change in spontaneous polarisation as a function of pressure is presented. It is shown that the dependence of spontaneous polarisation in the ferroelectric phase is relatively weak.

Analysis of the reflection spectra of chiral smectic liquid crystal phases is used to provide detailed information on physical parameters, including refractive indices, helicoidal pitch and tilt angle. Numerical models of the antiferroelectric and ferroelectric phases are constructed, based on a 4 × 4 matrix technique, and a downhill simplex algorithm is employed to fit the model to reflection spectra measured from free-standing films of the materials of interest. The temperature dependence of the refractive indices, dispersion, tilt angle and pitch are reported for three different liquid crystalline materials. The accuracy of the fitting method is around 1%, better than the experimental error, and this is confirmed by comparison of the parameters determined by the fitting program with those measured by independent methods.

The synthesis and characterization of organic semiconductors is being pursued in three primary structure formats: single crystal, liquid crystal and organic-inorganic hybrid. The strategy here is to share common structures, synthesis methods and fabrication techniques across these formats and to utilize common characterization tools such as the time of flight technique. The single crystal efforts concentrate on aromatic and heteroaromatic compounds including simple benzene derivatives and derivatives of the acenes. The structure-property relationships due to incorporation of small substituents and heteroatoms are being examined. Crystals are grown by solution, melt or vapor transport techniques. The liquid crystal studies exploit their self-organizing properties and relative ease of sample preparation. Though calamitic systems that deliver the largest mobilities are higher order smectics, even some unusual twist grain boundary phases are being studied. We are attempting to synthesize discotic acene derivatives with appropriate substitution patterns to render them mesogenic. The last format being examined is the hybrid organic-inorganic class. Here, layered materials of alternating organic and inorganic composition are designed and synthesized. Typical materials are conjugated aromatic compounds, usually functionalized with an amine or a pyridine and reacted with appropriate reactive metal derivatives to incorporate them into metal oxide or sulfide layers.

The temperature and frequency dependent dielectric relaxation behavior of a liquid crystalline (S)-(+)-1-methylheptyl 4-[2-(4-alkoxyphenyl) thiophene-5-carbonylthiooxy] benzoate system is reported. Interesting successive antiferroelectric-ferroelectric-antiferroelectric (AF-FE-AF) phase transitions are observed in this system resembling the successive phase transitions observed in crystalline Rochelle salt. The smectic-C* (SmC*) to AF1 phase transition (around 103.0 degrees C) is first order in nature, predicted from the use of Orihara and Ishibashi theory. It is also found that a contribution of the ferroelectric SmC* phase ordering penetrates even in the antiferroelectric AF1 (SmC(*)(A)) and AF2 (SmC(*)(A)) phases very close to the SmC*-AF1 and SmC*-AF2 phase boundaries (critical regions). It is suggested that this type of mixing of AF and FE phases might cause surface induced ferroelectric- or ferroelectric-type ordering near the AF-FE phase transitions. A soft mode with Debye-type dispersion was observed in the SmA phase. The thermal behaviors of dielectric dispersion, absorption, and dielectric strength in different phases are also reported and discussed.

Resonant x-ray diffraction was carried out at the Se K edge in thick free-standing films of a selenophene liquid crystalline material, revealing detail of the structure of the ferro-, ferri-, and antiferroelectric phases. The ferrielectric phase was shown to have a three-layer superlattice. Moreover, the structure of a lower temperature hexatic phase was established. For the antiferroelectric phase, investigations were also carried out in a planar device configuration. The device allowed resonant scattering experiments to be carried out with and without the application of an electric field and resonant data are compared with electro-optic measurements carried out on the same device.

The layer structure in the antiferroelectric, ferrielectric, and ferroelectric phases of a liquid crystal device is reported, together with its electric field-induced deformation. The field-free chevron angle is comparable to the steric tilt angle, but differs significantly from the optical tilt angle. A sharp field threshold is observed for the chevron to bookshelf transition in the antiferroelectric phase at 1.3 V/μm, while layer deformations occur at much lower fields (0.3 V/μm) in the other subphases. Models are proposed for the layer deformations.

Optical reflectivity studies have been conducted on freely suspended films with synclinic and anticlinic structures. For the first time quantitative data were obtained on orientational ordering in films with anticlinic structure. In the same wide temperature range of more than 30 K we observed both transverse and longitudinal ferroelectricity in the films of the same thickness. Equilibrium transition temperatures between structures with transverse and longitudinal polarization were above the bulk transition temperature to the SmC \(\) phase. The molecule tilt was determined in superthin films with synclinic and anticlinic ordering.

X-ray and optical techniques have been employed to study six materials that exhibit frustrated chiral smectic phases across the entire tilted phase range. The layer spacings are used to deduce the steric tilt angle of the systems which are compared with optical tilt of the phases. In general, the steric tilt is lower than the X-ray tilt, as would be expected. There is evidence of conformation driven inversion phenomena in three of the materials. The ratio of the tilts is strongly temperature dependent in all but two of the materials, and in three of the materials the x-ray tilt is higher than the optical tilt over part of the SmC* phase. The results are discussed in terms of molecular conformations.

We report polarization-analyzed, resonant x-ray diffraction at the sulfur K edge performed upon free-standing liquid-crystal films. Our studies of the thiobenzoate liquid-crystal enantiomer 10OTBBB1M7 yield the polarization states of resonant satellite peaks arising from characteristic superlattices in the chiral smectic-C (SmC(*)) variant phases, including the antiferroelectric SmC(*)(A), ferrielectric SmC(*)(FI1) and SmC(*)(FI2), as well as SmC(*)(alpha). The observed polarizations agree with the clock model of chiral smectic-C variants, and rule out other proposals made to date for these structures. Data from the 10OTBBB1M7 racemate also support the clock model. Our resonant diffraction results from a thiophene liquid-crystal compound reveal the same superlattice periodicities seen in corresponding antiferroelectric and ferrielectric phases of 10OTBBB1M7.

The so-called chiral smectic C-beta (SmCbeta*) phase has been reported as distinct from the SmC* phase in several materials that exhibit antiferroelectric liquid crystal mesophases and subphases. The SmCbeta* phase is known to be chiral, tilted and to exhibit ferrielectric switching, but no structure had been suggested which explains these effects. This paper presents a possible structure for the SmCbeta* phase which can explain the ferrielectric properties. The model is proposed on the basis of complementary optical, electric and X-ray diffraction studies of a chiral liquid crystal. The layer spacing, optical and steric tilt and spontaneous polarization over the temperature range of the SmCbeta* phase are described. The complementary experimental techniques used reveal the occurrence of inversion phenomena, on which this model is based.

A series of highly chiral hetrocyclic esters have been studied. The effect that the choice of hetroatom has on the linearity of the molecules and hence the mesomophism of the materials has been investigated. Measurements of the spontaneous polarisation, tilt angle, current response time and rotational viscosities of the materials are reported. At 30 degrees C below the transition from the SmA phase all members of the series show a Ps of similar to 100nCcm(-2) and a high tilt angle of about 30 degrees. These physical measurements confirm the presence of a higher order antiferroelectric phase in the selenophene derivative in this series.

We report results of detailed investigations of the dielectric response of two antiferroelectric liquid crystal materials over a wide range of frequencies as a function of bias voltage and of temperature. On the basis of extensive measurements of the tilt angle, the spontaneous polarization, and the optical transmittance as a function of voltage, we conclude that there appears to exist a previously undetected, new field-induced phase (referred to as the X phase) with uniform monodomain structure. This new phase seems to be stable over a wide range of applied voltages and possesses effective values of spontaneous polarization and tilt angle within 70-80% of their maximum values. Although the results appear to rule out the presence of the SmCalpha * phase, nevertheless, the new phase has some characteristics similar to those of the SmCalpha * phase. The differences between the characteristics of the two phases are detailed.