Transformation of the structure of smectic liquid crystals associated with frustration and the surface of ultrathin films

Frustrations associated with competition between interlayer interactions in smectic liquid crystals and geometric frustrations are responsible for variety of interesting physical phenomena, formation of unusual structures, and transitions between them. Owing to the possibility of the preparation of ultrathin freely suspended smectic nanofilms and a single-layer change in their thickness (by one molecular layer), smectic films are unique objects for the study of ordered structures in a limited geometry. Effects associated with frustration and the nanothickness of smectic films have been discussed.     

Electroclinic effect in free-standing smectic elastomer films

The coupling of the mesogenic tilt in smectic liquid crystals to external electric fields in the layer plane (electroclinic effect) provides an opportunity to control the smectic layer thickness with electric fields. In ordered ferroelectric smectic elastomers it is possible to achieve a macroscopic electromechanical response. The effect is particularly pronounced near the smectic A-to-smectic C^* phase-transition temperature. In this work, the electrostriction of weakly cross-linked smectic elastomers is studied by means of optical interferometry of thin films. Its observed magnitude corresponds to an induced tilt of approximately 7.7°, yielding a layer contraction of 1%, in a 3 MV/m electric field. This value is in agreement with earlier measurements of tilt susceptibility in a structurally similar polymer, but is considerably smaller than previously reported data on elastomers with a comparable chemical structure. PACS 61.30.Vx; 83.80.Va; 77.65.Bn     

Tilted smectic layers of a liquid crystal between homeotropically treated plates

We investigated SmC^* films sandwiched between silane coated glass plates and observed formation of textures exhibiting a uniform tilt of the smectic layers with respect to the boundary plates. The layer tilt angle increases from zero to as the sample is cooled from the smectic A phase to room temperature. These films show linear electro-optical effects because the permanent polarization can be aligned so that it has a component parallel to the applied field without changing the layer structure. Our analysis indicates that mainly two effects determine the layer tilt. On the one hand, the surface tension tends to minimise the layer tilt. On the other hand, the surface energy promotes the director to be normal to the boundary plates. Received 17 July 1998     

Phase transition to anticlinic texture in free-standing smectic c films

Experimental data on the optical reflectance of free-standing smectic C films were analyzed within the framework of a phenomenological Landau approach. At a certain temperature T _0N (determined from experimental data), which exceeds the known temperature T _c of the volume phase transition from smectic A to smectic C state, a surface phase transition takes place whereby molecules in the surface layer become sloped relative to the normal of the smectic layers. The transition temperatures T _0N ^s,a for N-layer films possessing synclinic (symmetric) and anticlinic (antisymmetric) textures of the order parameter (tilt angle θ) were determined. A comparison of the theoretical and experimental data allowed all parameters of the model to be determined (including critical indices of the correlation length and the surface order parameter). Three possible models of the transition from the state with transverse polarization (perpendicular to the molecular tilt plane) to the state with longitudinal polarization (parallel to this plane) are analyzed. The transition takes place at low (°–°) values of the order parameter θ in the middle layer of the film.     

Optical characterization of a nanoscale incommensurate pitch in a new liquid-crystal phase

As a remarkable orientationally ordered soft-condensed matter system, the smectic-C*(alpha) phase exhibits an incommensurate nanoscale helical pitch of more than four smectic layers. Recent theoretical advances predict the existence of a new phase showing a helical pitch of less than four smectic layers (<16 nm). By applying a novel optical technique to the study of freestanding films with increments in thickness of one smectic layer, we have measured the size of this pitch using 633 nm HeNe laser light. Our results confirm the existence of the newly predicted phase in one unique compound.     

Complex dynamic behavior of fluctuating smectic- A films as studied by scattering with coherent X-rays

Coherent dynamic x-ray scattering has been used to study the thermally excited layer fluctuations in freely suspended smectic films of the compound 4O.8. Using 8-keV x rays and films with a thickness around 0.3 &mgr;m we resolve relaxation times down to a few &mgr;s. A combination of damped and oscillatory behavior is observed for the layer undulations, which can be attributed to inertial effects. These are due to the surface contribution to the free energy which cannot be disregarded for thin films.     

Ferroelectric smectic phase formed by achiral straight core mesogens

We report electro-optic experiments in liquid crystalline freestanding films of achiral hockey stick shaped mesogens with a straight aromatic core. The material forms two smectic mesophases. In the higher temperature phase, a spontaneous polarization exists in the smectic layer plane and the films show polar switching in electric fields. It is the first example of a ferroelectric phase formed by nearly rodlike achiral mesogens. Mirror symmetry of the phase is spontaneously broken. We propose a molecular configuration similar to a synclinic ferroelectric (C(S)P(F)) high temperature phase and an anticlinic, probably antiferroelectric (C(A)P(A)) low temperature phase.     

Thinning transitions in free-standing liquid-crystal films as the successive formation of dislocation loops

We describe a model for the layer-thinning transition in free-standing liquid-crystal films based on the successive, spontaneous formation of dislocation loops. As the film temperature increases and the smectic order and layer compressional modulus decrease, the condition for creating a dislocation loop of critical radius is met and a thinning is nucleated. The resulting equation for N, the number of smectic layers, as a function of temperature yields good fitting results to the thinning transitions obtained from several fluorinated compounds.     

Corona patterns around inclusions in freely suspended smectic films

We discuss the structure and physical origin of corona patterns observed around solid or liquid spherical inclusions in freely suspended smectic films. Such patterns are observed when droplets or solid beads of micrometer size are sprayed onto the films. They are found in the smectic C phase and in the smectic A phase above such a smectic C phase, but disappear, for example, at the transition into a lower-temperature smectic B phase. We show that these structures are equivalent to splay domains found in the meniscus of freely suspended films, originating from surface-induced spontaneous splay.     

On the molecular structure of thin molten polyethylene films

Observations by transmission electron microscopy and electron diffraction suggesting that thin molten polyethylene films have a smectic liquid crystal structure consisting of layers of folded molecules are reported. The thickness of each layer is observed to be about 400 to 500 Å.     

Thermal fluctuations in smectic-<Emphasis Type="Italic">A</Emphasis> films on the surface of solid substrates

The static and dynamic characteristics of layer displacement fluctuations in smectic-A films supported on the surface of a solid substrate are calculated with due regard for the profiles of the flexural and tensile (compressive) moduli of smectic layers. The difference in the surfaces bounding the film and the asymmetry of the profiles of the elastic moduli with respect to the central layer of the film are taken into account. The profiles of fluctuations of smectic-layer displacements and the correlations between these fluctuations are determined for the films formed by liquid-crystal compounds that can undergo a bulk smectic-A-nematic phase transition. The dynamic correlation functions derived for these fluctuations are used for calculating the correlations between the intensities of x-ray scattering by a film at different instants of time. It is demonstrated that, in smectic-A films supported on the surface of a solid substrate, unlike free-standing smectic-A films, the effect of temperature on the dynamics of layer displacement fluctuations can be observed in experiments on dynamic x-ray scattering from films that are not very thick (the number of layers N ～ 20) and at considerably smaller recoilmomentum components in the film plane.     

“Elastic” fluctuation-induced effects in smectic wetting films

The Li-Kardar field theory approach is generalized to wetting smectic films and the “elastic” fluctuation-induced interaction is obtained between the external flat bounding surface and distorted IA (isotropic liquid-smectic A) interface acting as an “internal” (bulk) boundary of the wetting smectic film under the assumption that the IA interface is essentially “softer” than the surface smectic layer. This field theory approach allows calculating the fluctuation-induced corrections in Hamiltonians of the so-called “correlated” liquids confined by two surfaces, in the case where one of the bounding surfaces is “rough” and with different types of surface smectic layer anchoring. We obtain that in practice, the account of thermal displacements of the smectic layers in a wetting smectic film reduces to the addition of two contributions to the IA interface Hamiltonian. The first, so-called local contribution describes the long-range thermal “elastic” repulsion of the fluctuating IA interface from the flat bounding surface. The second, so-called nonlocal contribution is connected with the occurrence of an “elastic” fluctuation-induced correction to the stiffness of the IA interface. An analytic expression for this correction is obtained.     

Plateau borders of smectic liquid crystalline films

We investigate the geometrical properties of Plateau borders in an arrangement of connected smectic A free standing films. The geometry is chosen such that a circular Plateau border surrounds a planar smectic film and connects it with two smectic catenoids. It is demonstrated that, similar to soap films, the smectic film geometry can be described by a negative line tension of the circular contact region. Thus, the equilibrium angle between the films depends upon the liquid content in this region, and with increasing liquid content, deviations from Plateau's rule are observed. The experimental results are qualitatively comparable to soap films. A possible origin of slight quantitative differences is discussed.     

Shear instabilities of freely standing thermotropic smectic- A films

In this Letter we discuss theoretically the instabilities of thermotropic freely standing smectic- A films under shear flow [3]. We show that, in Couette geometry, the centrifugal force pushes the liquid crystal toward the outer boundary and induces smectic layer dilation close to the outer boundary. Under strong shear, this effect induces a layer buckling instability. The critical shear rate is proportional to 1/sqrt[d], where d is the thickness of the film.     

Solid-state morphology of aromatic-aliphatic polyester crystallized from smectic liquid crystal

The solid-state morphology of poly(hexamethylene p,p'-bi-benzoate) (BB-6) and its dependence on the texture of the smectic liquid crystal state from which it crystallized were studied using electron microscopy, polarizing optical microscopy, and small-angle x-ray diffractometry. Thin films of BB-6 suitable for the microscopy were prepared by casting a hot solution of the polymer in tetrabromoethane onto mica at 150°C. The as-cast film of BB-6 was first heated to 260°C, maintained in the smectic range (210°C), and then cooled gradually to room temperature. A number of types of defect structures—such as Dupan cyclides, edge dislocation, tilt walls, and disclinations — were observed in the solid BB-6 formed from the smectic melt. On the basis of the electron microscopy and small-angle x-ray diffractometry, it is suggested that folded-chain crystals are formed during the crystallization from the smectic melt. Electron microscopic observations of the solid BB-6 and its orientation behavior under shear can be reasonably explained by assuming the presence of a precursory chain-folded layer structure in the smectic liquid crystal of BB-6.     

Disjoining pressure in free-standing smectic-A films and its influence on their reflectivity

This paper reports the results of calculating the disjoining pressure and average thickness of smectic layers in free-standing liquid-crystal films heated above the temperature of breakdown of the smectic order in the bulk of the mesogens. The effect of the disjoining pressure on the reflectivity of free-standing smectic-A films with different numbers of smectic layers has been studied. The results of the calculations agree with the experimental study of the reflectivity of free-standing smectic-A films in the optical wavelength range.     

Molecular models for ferroelectric liquid crystals with conventional and anomalously weak layer contraction

A molecular theory of the ferroelectric smectic C* phase has been developed using the simple model of a chiral molecule composed of a uniaxial core and a pair of off-center nonparallel dipoles which determine molecular chirality and polarity. The interaction between uniaxial cores is modeled by a rather general effective potential which can be used to describe smectic materials with both conventional and anomalously weak layer contraction in the smectic C* phase. Spontaneous polarization, tilt, and layer spacing are calculated numerically as functions of temperature, and it is shown that the variation of the polarization generally deviates from that of the tilt angle. It is shown that this deviation is more pronounced in smectic materials tilting with low layer contraction which corresponds to existing experimental data. The model has been used to reproduce qualitatively the experimental data for polarization, tilt and layer spacing for two similar mixtures exhibiting conventional and anomalously weak layer contraction. The polarization and the tilt are also calculated in the case when the smectic A-smectic C* transition is characterized by the biaxial primary order parameter.     

Studies of thin smectic C films by X-ray reflectivity

The smectic order in thin and ultra thin films (150–600Å) of the chiral ferroelectric liquid crystal mixture ZLI-3654 is studied using the X-ray reflectivity technique. The spin cast films on various substrates (float glass, Si wafer, polymer coated glass, etc.) order spontaneously with smectic layering parallel to the substrate surface. A simple model which assumes a sinusoidal density modulation can describe well the experimental reflectivity profiles. The X-ray reflectivity provides a method to evaluate the phases of the structure factor. We demonstrate, for the first time, that is possible to extract the molecular tilt angle, , in ferroelectric liquid crystals from X-ray reflectivity measurements of ultra thin films. The temperature dependence of the tilt angle in the smectic C^* phase are almost independent of the film thickness (down to 200 Å) and are similar to those in the bulk.     

Length scale dependence of chiral symmetry breaking in free-standing films of achiral smectic C

The textures of a smectic C phase in free-standing films of the Schiff base 5O.6 are studied as a function of the number of layers and temperature. Periodic stripes with alternating contrast are observed in SmA boundary layers. On further cooling a transition to the splay stripes occurs in the smectic A temperature interval. In the smectic C phase all the periodic textures disappear, whereas in films with one free boundary a periodic arrangement of splay stripes is found. Mechanisms of symmetry breaking are discussed. Pis'ma Zh. éksp. Teor. Fiz. 64, No. 1, 29–32 (10 July 1996) Published in English in the original Russian journal. Edited by Steve Torstveit.