Nematic-smectic transition under confinement in liquid crystalline colloidal shells

in Physical Review Letters (2011), 106(24), 247801

We carry out the first study of smectic liquid crystalline colloidal shells and investigate how their complex internal structure depends on the director configuration in the nematic phase, preceding the ... [more ▼]

We carry out the first study of smectic liquid crystalline colloidal shells and investigate how their complex internal structure depends on the director configuration in the nematic phase, preceding the smectic phase on cooling. Differences in the free energy cost of director bend and splay give an initial skewed distribution of topological defects in the nematic phase. In the smectic phase, the topological and geometrical constraints of the spherical shell imposed on the developing 1D quasi-long-range order create a conflict that triggers a series of buckling instabilities. Two different characteristic defect patterns arise, one driven by the curvature of the shell, the other by the strong nonuniformities in the director field in the vicinity of the topological defects. [less ▲]

On the phase sequence of antiferroelectric liquid crystals and its relation to orientational and translational order

in Liquid Crystals (2003), 30(4), 399-414

The substance MHPOBC is the oldest and still most important reference antiferroelectric liquid crystal (AFLC). There is still considerable controversy concerning the correct phase designations for this ... [more ▼]

The substance MHPOBC is the oldest and still most important reference antiferroelectric liquid crystal (AFLC). There is still considerable controversy concerning the correct phase designations for this material and, in particular, about the presence or absence of SmC* in its phase sequence. By means of dielectric spectroscopy and polarizing microscopy, we show that whereas the pure compound lacks the SmC* phase, this phase rapidly replaces the SmC*b subphase through the reduced purity resulting from temperature-induced chemical degradation which is hard to avoid under standard experimental conditions. X-ray investi- gations furthermore show that this change in phase sequence is coupled to a decrease in translational order. This explains the large variations in the reported phase sequence and electro-optic behaviour of MHPOBC, in particular concerning the SmC*b phase which has been said to exhibit ferro-, ferri- as well as antiferroelectric properties. It is likely that the sensitivity of the AFLC phase sequence to sample purity is a general property of AFLC materials. We discuss the importance of optical and chemical purity as well as tilt and spontaneous polarization for the observed phase sequence and propose that one of the key features determining the existence of the different tilted structures is the antagonism between orientational (nematic) and translational (smectic) order. The decreased smectic order (increased layer interdigitation) imposed by chemical impurities promotes the synclinic SmC* phase at the cost of the AFLC phases SmC*a , SmC*b , SmC*c and SmC*a . We also propose that the SmA* phase in FLC and AFLC materials may actually have a somewhat different character and, depending on its microstructure, some of the tilted phases can be expected to appear or not to appear in the phase sequence. AFLC materials exhibiting a direct SmA*–SmC*a transition are found to be typical ‘de Vries smectics’, with very high orientational disorder in the SmA* phase. Finally, we discuss the fact that SmC*b and SmC*c have two superposed helical superstructures and explain the observation that the handedness of the large scale helix may very well change sign, while the handedness on the unit cell level is preserved. [less ▲]

Surface- and field-induced AFLC structures detected by dielectric spectroscopy

in Ferroelectrics (2002)

In order to better understand which features in dielectric spectra of antiferroelectric liquid crystals (AFLCs) are due to the bulk director geometry and which are due to surface-induced structures, we ... [more ▼]

In order to better understand which features in dielectric spectra of antiferroelectric liquid crystals (AFLCs) are due to the bulk director geometry and which are due to surface-induced structures, we have performed dielectric spectroscopy measurements with simultaneous texture monitoring on two SmC*-exhibiting AFLC homologues (11- and 12F1M7), at varying cell gap. Such AFLCs are strongly affected by surface action even in fairly thick cells (d≈15µm), with heavy supercooling of the SmC* phase as the most obvious result. We show that the supercooled structure can be removed by AC-field treatment in the SmCa* phase, but some domains may stay in a polar geometry, as reflected in both texture and dielectric signature. On heating from the antiferroelectric SmC?* subphase into SmC*, meta-stable non-helical domains may form at cell gaps much larger than the helical pitch. These domains give rise to a lowfrequency dielectric absorption not seen in bulk SmC* samples. [less ▲]

The case of thresholdless antiferroelectricity: Polarization-stabilized twisted SmC* liquid crystals give V-shaped electro-optic response

in Journal of Materials Chemistry (1999), 9(6), 1257-1261

We have studied the three-component liquid crystal mixture reported to exhibit ‘thresholdless antiferroelectricity’ [Inui et al., J. Mater. Chem, 1996, 6, 671]. We find that the thresholdless or V-shaped ... [more ▼]

We have studied the three-component liquid crystal mixture reported to exhibit ‘thresholdless antiferroelectricity’ [Inui et al., J. Mater. Chem, 1996, 6, 671]. We find that the thresholdless or V-shaped switching is obtained in thf absence of antiferroelectricity. This analog electro-optic response is due to the field-induced switching of a twisted smectic C* structure stabilized by polar surface interactions and by electrostatic bulk polarization charge interactions. The latter confine the director twist to thin surface regions leaving the bulk of the cell uniform, which gives good extinction at zero field. In sufficiently thin cells, such thresholdless switching can in fact be followed down to much lower temperatures, where the bulk would be antiferroelectric, but is maintained in the cells in the ferroelectric state by hysteresis from surface action. [less ▲]