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.     

Theoretical description of fluctuations in free-standing smectic-A films including spatial non-uniformity of their elastic characteristics

A theoretical study is reported of fluctuations in smectic layer displacements and of the correlations between them in free-standing smectic-A films formed of liquid-crystal compounds with smectic-A-isotropic liquid (Sm-A-I) and Sm-A-nematic (Sm-A-N) bulk phase transitions. The study took into account the dependence of the elastic constants for bending, K, and tension (compression), B, of smectic layers on distance to the free film surfaces. The calculations are compared with the results obtained within Hołyst’s model for spatially uniform, free-standing smectic-A films. It has been established that, below the temperature at which smectic order in the bulk of a liquid crystal disappears, taking into account the profiles of the elastic moduli K and B does not produce noticeable differences from this model. However, at temperatures considerably above the Sm-A-I and Sm-A-N phase transitions, their inclusion results in considerable discrepancies from the predictions of Hołyst’s model. Fiz. Tverd. Tela (St. Petersburg) 41, 1882–1889 (October 1999)     

Temperature-and field-induced transitions in free-standing films of an antiferroelectric liquid crystal

Thin free-standing films of a compound with the smectic-C _A ^* and smectic-C _α ^* phases were investigated by means of depolarized microscopy and optical reflectivity. In thin films, the smectic phase sequence C _A ^* ?C_α/*?A is replaced by a series of temperature-and field-induced transitions into states with the coplanar orientation of molecular tilt planes. Transitions are accompanied by a change in the direction of the electric polarization with respect to the tilt plane of molecules. The coplanar structure of these states is consistent with the Ising model.     

Surface ordering near the smectic-A-smectic-C transition in thin, free-standing, liquid-crystal films

Optical reflectivity measurements have been conducted near the smectic-A-smectic-C phase transition in free-standing films with thickness between two and eleven molecular layers. The temperature dependence of the reflectivity in thin film differs significantly from that in thick films. The optical thickness per layer increases in films with two to five layers as a result of cooling, in contrast with thick films. The average layer spacing was found to decrease with decreasing film thickness. Zh. éksp. Teor. Fiz. 111, 949–953 (March 1997) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor.     

Experimental indication of macroscopic polarization parallel to the tilt plane in free-standing films of ferroelectric liquid crystals 8SI* and DOBAMBC

Optical reflectivity and x-ray studies have been conducted on free-standing films and bulk samples of ferroelectric liquid crystals near the smectic-A-smectic-C ^* transition. A tilt plane rotation with respect to the direction of an applied electric field is found in the ferroelectric films above the bulk transition temperature. Whereas the macroscopic polarization is perpendicular to the tilt plane at low temperature, it is parallel to the tilt plane at elevated temperature. The temperature dependence of the average tilt angle is measured. Zh. éksp. Teor. Fiz. 116, 1329–1334 (October 1999) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor.     

Phase transition studies in polymesomorphic compounds(v): Density studies in N-(p-n-Octyloxy benzylidene)-p-n-butyl aniline

The density, ρ, of N-(p-n-octyloxy benzylidene) p-n-butyl aniline (OBBA) is measured as a function of temperature from the isotropic liquid to the smectic-G phase. The compound is trimorphic, exhibiting three smectic phases, smectic-G, crystal smectic-B, and smectic-A phase. The changes in density across the phase transformations and the calculated thermal expansion coefficients confirm the order of the transitions as first order. Particular importance of the smectic-A to crystal smectic-B transformation, which is of first order, is apparent from the density jump across the transition.     

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.     

Nonchiral ferroelectric smectic-C films

Free-standing films of nonchiral liquid crystal compound are studied by optical reflectivity measurements. The existence of macroscopic ferroelectric properties and orientation of the tilt plane parallel to an electric field in the temperature range above the smectic-C-smectic-A bulk transition is demonstrated. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 10, 808–813 (25 May 1998)     

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.     

Dynamics of layer-by-layer thinning of free-standing smectic films

A dynamic model has been proposed for describing the extrusion of a single layer of a liquid-crystal (LC) material into a meniscus from an N-layer circular free-standing smectic film (FSSF). In the framework of this model, the main mechanism responsible for the process of the thinning (extrusion) of the LC material from the N-layer FSSF is based on the appearance of a spatial pressure gradient directed along the radius of the circular FSSF. This gradient is formed due to the difference in the disjoining pressures on both sides of the front separating the N- and (N–1)-layer domains of the smectic film. The proposed model allows taking into account the influence of the meniscus on dynamic characteristics, such as the time required for the complete extrusion of a single layer from the N-layer FSSF and the velocity of propagation of the front separating the N- and (N–1)-layer domains in the process of the thinning of the smectic film formed by molecules of 5-n-alkyl-2-(4-n-(perfluoroalkyl-methyleneoxy))pentyl.     

Structure of π- and 2π-Walls in Smectic films

The structure of ??- and 2??-walls in smectic films was reconstructed from optical reflectivity measurements. Investigations were made in free standing films of nonpolar Smectic-C and ferroelectric Smectic-C* liquid crystals. ??-walls are observed in magnetic field and 2??-walls in electric field parallel to the film plane. For the first time the distribution of molecular orientation across the walls was determined. Peculiarities of the wall structure related to the anisotropy of the film elasticity were found. The structure of the walls is well described by the theory taking into account the anisotropy of two-dimensional elasticity of smectic films.     

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.     

Discrete thinning of free-standing smectic films in the de Gennes “pre-smectic liquid” model

It is shown that the successive discrete thinning of free-standing smectic films (FSSFs), which is observed when the films are heated above the temperature of the smectic A-nematic bulk phase transition, has a natural explanation in terms of the de Gennes “pre-smectic liquid” model, provided that a sufficiently large external compressive force is applied to the free surfaces of the FSSF. In a real situation this force stems from the curvature of the surrounding miniscus, which plays the role of a volume reservoir. In this model a superheated FSSF is stabilized by balancing the external compressive and elastic forces. When heating takes place the bulk modulus of the pre-smectic lattice decreases, and when the superheating reaches a critical value, the FSSF is subject to a long-wavelength instability in thickness beause the external compressive and elastic forces can no longer be balanced for a fixed number of smectic layers. If a superheated FSSF possesses adequate stability against disruption, the balance of forces, which was disrupted, and hence the stability of the FSSF can be restored as a result of spontaneous thinning of the film to a thickness corresponding to a smaller number of smectic layers. In general, heating of a superheated FSSF is accompanied by a series of such thinning transitions. Near the critical points where the balance of the forces breaks down, the dislocation mechanism of spontaneous thinning, which could be responsible for the stratified nature of the progressive discrete thinning of real FSSFs, can become dangerous. Zh. éksp. Teor. Fiz. 115, 61–69 (January 1999)     

Spectral investigations of surface ordering in ultrathin molecular films

Surface molecular ordering in ultrathin molecular films is investigated. The optical transmission spectra of molecular films ranging in thickness from 2 to 13 smectic layers (6.7–43 nm) in the region of the electronic absorption bands in the smectic A phase of cyanobiphenyl CB9 are measured. The thickness and temperature dependences of the permittivity are determined. It is found that the orientational ordering of the molecules depends on the film thickness. The penetration depth of the surface molecular orientational order does not exceed two smectic layers (<7 nm). Zh. éksp. Teor. Fiz. 115, 1833–1842 (May 1999)     

The effect of spontaneous polarization on two-dimensional elasticity of smectic liquid crystals

The influence of polarity on orientational elasticity and on structures formed in the director field is studied in free-standing smectic films. Periodic stripe patterns and 2π-walls in a magnetic field are investigated. Measurements are performed on a nonpolar racemic mixture, on an optically pure ferroelectric compound, and in mixtures with different concentrations of the chiral isomers of opposite signs. The structure of periodic stripes changes drastically with the polarity of the film. The ratio of the bend K _B and splay K _S elastic constants for smectic films is determined as a function of polarization from the structure of periodic stripe patterns and 2π-walls. We find that the elastic anisotropy K _B /K _S increases essentially with increasing the polarity of the film. Changes of the elasticity and the structure of periodic stripes are explained by polarization charge effects.     

Microrelief dependent on the temperature and external field on the free surface of a smectic-<Emphasis Type="Italic">A</Emphasis> liquid crystal

A homeotropically oriented smectic-A film on the surface of a solid substrate with a periodic microrelief is considered. Relationships are derived for describing the dependences of the microrelief-induced deformation of the free surface of the film on the film thickness, the temperature, and the external magnetic (electric) field strength. It is shown that, for a specific choice of the microrelief shape on the substrate surface, a variation in the sample temperature and the external magnetic (electric) field strength makes it possible to control not only the microrelief depth but also the shape of the microrelief formed on the free surface of the smectic-A film.     

Rayleigh scattering induced by static bends of layers in a smectic A liquid crystal

We observe the anisotropy and the polarization properties of the Rayleigh scattered light for a planar smectic A texture of butoxyl benziledene-p-n anilino-acetophenone (BBAA). This scattering is attributed to static bends of the smectic layers, with wave vectors parallel to the smectic planes. This effect gives a simple method to measure the ratio of the extraordinary to the ordinary indices: n_e/n₀ = 1.18 at 89°C.     

Stability of a free-standing liquid-crystal film: The measurement of the interaction between the film surfaces

The interaction energy of the surfaces of a free-standing liquid-crystal film has been determined. The measurements are performed in a smectic phase below the melting temperature of a bulk sample T _C, in the temperature range of structural instability of thin films at T > T _C, and in a quasi-smectic phase at T > T _C. Two modes of smectic-layer motion in the film are detected: they lead to film thinning at T > T _C and film thickening at a low temperature. The measurement results are discussed in terms of recent theoretical concepts.     

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.     

Unusual thickness-dependent thermal behavior and anticlinic coupling in chiral smectic free-standing liquid-crystal films

We observe, in free-standing films of a chiral smectic liquid crystal, a series of discrete transitions in the relative orientation of the tilt of the interior and surface layers. These transitions include a remarkable reentrant synclinic-anticlinic-synclinic ordering sequence of the film surfaces in the presence of an electric field upon cooling. The profiles of the associated heat-capacity anomalies are found to be strongly thickness dependent and exhibit a novel crossover behavior in reduced dimensions. We measure the anticlinic coupling between tilted surface layers in the smectic- A phase.