Smectic Films Research Articles

Smectic block copolymer thin films on corrugated substrates.

In this work we study equilibrium and non-equilibrium structures of smectic block copolymer thin films deposited on a topographically patterned substrate. A Brazovskii free energy model is employed to analyze the coupling between the smectic texture and the local mean curvature of the substrate. The substrate's curvature produces out-of-plane deformations of the block copolymer such that equilibrium textures are modified and dictated by the underlying geometry. For weak curvatures it is shown that the free energy of the block copolymer film follows a Helfrich form, scaling with the square of the mean curvature, with a bending constant dependent on the local pattern orientation. On substrates of varying mean curvature simulations show that topological defects are rapidly expelled from regions with large curvature. These results compare well with available experimental data of poly(styrene)-co-poly(ethylene-alt-propylene) smectic thin films.

Molecular organization in freely suspended nano-thick 8CB smectic films. An atomistic simulation.

We present an atomistic molecular dynamics simulation of freely suspended films of the smectic liquid crystal 8CB formed by nl = 2, 3,…,10, 20 theoretical monolayers, determining their orientational and positional order as a function of the film thickness. We find that films are always composed by bilayers of antiparallel molecules, and that in the case of odd nl, the system prefers to self-assemble in (nl + 1)/2 bilayers, with an increase of surface tension with respect to even nl samples. We also show that external layers have higher positional and orientational order, and that upon heating the disordering of the system proceeds from the inside, with the central layers progressively losing their smectic character, while the external ones are more resistant to temperature changes and keep the film from breaking.

Surface tension, disjoining pressure and layer compression of free-standing smectic films in water

Using the extended McMillan's mean field approach with anisotropic forces a numerical study of the surface tension, disjoining pressure and layer compression of free-standing smectic film composed of decylcyanobiphenyl (10CB) molecules immersed in water has been carried out. We obtained that the smectic-A-isotropic transition occurs through a series of layer-thinning transitions causing the films to thin one layer at time, as well as a stepwise reduction and increase of the values of the surface tension and disjoining pressure per 10CB molecule as the temperature is raised to the isotropic value. Reasonable agreement between the theoretically predicted and the experimentally obtained data has been obtained.

Manifold configurations of the director field formed by topological defects in free and confined geometry in smectic films.

We study the topology of the c-director field near topological defects with point core and with a droplet in the core of the defect in nonpolar smectic-C and ferroelectric smectic-C* freestanding films using polarized optical microscopy. Free and confined geometry of topological defects and droplets with strong outer boundary condition are compared. The c-director field can be remarkably different around a point defect and a droplet with the same topological charge S=+1. In ferroelectric films, splay deformation of the c-director transforms into bend deformation after droplet nucleation. Heating a ferroelectric film with an S=+1 droplet leads to a dramatic change of the c-director topology from bend to splay. In confined geometry we found spiral structures in which the c-director has opposite direction of rotation along the inner and outer boundaries of the island. Our observations are discussed on the basis of theories taking into account both the influence of polarity and of confined geometry on elasticity and topology of the c-director field.

Transition Helmholtz free energy, entropy, and heat capacity of free-standing smectic films in water: a mean-field treatment.

Using the extended McMillan's mean field approach with anisotropic forces a study of both the structural and thermodynamic properties of free-standing smectic film (FSSF) in water on heating to the isotropic temperature is carried out numerically. By solving the self-consistent nonlinear equations for the order parameters, we obtained that the smectic-A-isotropic (AI) transition occurs through the series of layer-thinning transitions causing the films to thin in the stepwise manner as the temperature is increased above the bulk smectic-A-isotropic temperature TAI(bulk). With enhanced pair interactions in the bounding layers, the smectic-isotropic transition corresponds to smectic melting of the central layers. The effects of surface "enhanced" pair interactions in the bounding layers and of film thickness on the orientational and translational order parameters, the Helmholtz free energy and entropy, as well as the temperature dependence of the heat capacity of FSSFs, have also been investigated. Reasonable agreement between the theoretically predicted and the experimentally obtained - by means of optical microscopy and ellipsometry techniques - data of the temperature when the thin decylcyanobiphenyl smectic film immersing in water ruptures has been obtained.

Hearing shapes of few electrons quantum drums: A configuration–interaction study

The – highly remarkable – existence of non-congruent yet vibrationally isospectral shapes has been first proved theoretically and then also tested experimentally – by using electromagnetic waves in cavities, vibrating smectic films or electrons in nanostructures. In this context, we address the question whether isospectrality holds if two or more electrons interact electrostatically, using the accurate configuration–interaction method, in a discrete representation of the Bilby and Hawk shapes. Isospectral pairs offer an unique possibility to test how identical sets of single-particle energies may combine differently in the few-electrons eigenmodes, due to different wave functions spatial distributions. Our results point towards the break down of isospectrality in the presence of interactions. Thus one should be able to ”hear” the shapes of few electrons quantum drums. Interestingly however, for the analyzed two and three electrons cases, there exists an interaction strength (which can be tuned by changing the size of the shapes), for which the ground states energies of Bilby and Hawk coincide, but not the excited states as well. Wigner localization is studied and shown to occur at about the same size for both Bilby and Hawk shapes. Next, an exercise is proposed to use the two-electrons charge density of the Bilby and Hawk ground states in the phase extraction scheme as proposed by Moon et al. (2008). Results show that out-of-phase regions appear if the linear size of the shapes exceeds the Bohr radius as occupation of higher Slater determinants becomes significant.

Controlling the Self‐Assembly of Periodic Defect Patterns in Smectic Liquid Crystal Films with Electric Fields

Large‐area periodic defect patterns are produced in smectic A liquid crystals confined between rigid plate electrodes that impose conflicting parallel and normal anchoring conditions, inducing the formation of topological defects. Highly oriented stripe patterns are created in samples thinner than 2 μm due to self‐assembly of linear defect domains with period smaller than 4 μm, whereas hexagonal lattices of focal conic domains appear for thicker samples. The pattern type (1d/2d) and period can be controlled at the nematic–smectic phase transition by applying an electric field, which confines the defect domains to a thin surface layer with thickness comparable to the nematic coherence length. The pattern morphology persists in the smectic phase even after varying the field or switching it off. Bistable, non‐equilibrium patterns are stabilized by topological constraints of the smectic phase that hinder the rearrangement of defects in response to field variations.

Impact and embedding of picoliter droplets into freely suspended smectic films.

We study the impact of liquid microdroplets on thin freely suspended smectic films. Such films are very thin but robust objects that can serve as model systems for quasi-two-dimensional liquids. Droplet velocities and sizes determine the character of the collisions. The dynamics of the integration of droplets into the film can be divided into three phases, starting with the impact and a dissipation of the kinetic energy, followed by a balancing of capillary forces within fractions of a second. The analysis of the droplet shape evolution with high-speed imaging allows us to study the dynamics of this process. The final phase, formation of a meniscus of smectic material, takes several seconds up to minutes.

Single-molecule diffusion in freely suspended smectic films.

We present a study of the molecular diffusion in freely suspended smectic-A liquid crystal films with thicknesses ranging from 20 down to only two molecular layers. The molecular mobility is directly probed by determining the trajectories of single, fluorescent tracer molecules. We demonstrate, using several different smectic compounds, that a monotonic increase of the diffusion coefficient with decreasing film thickness is a general phenomenon. In two-layer films, the diffusion is enhanced by a factor of 3 to 5 compared to the corresponding bulk smectic phase. Molecular dynamics simulations of freely suspended smectic films are presented which support the experimental results.

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.

Deep Holes in Free-Standing Smectic C Films

Free-standing smectic films consist of smectic layers stacked in the film plane. In equilibrium, the discrete number of layers usually guarantees a uniform film thickness over large areas. Regions with differing numbers of layers are separated by dislocation lines. Their dynamics can be studied when the surface area is rapidly reduced, whereby excess material accumulates in islands (regions with increased thickness). Alternatively, holes (regions with reduced thickness) can be created by expanding the film surface, e. g. by means of a moveable film holder barrier. We study the growth of deep holes, i. e. regions which are up to several micrometers thinner than the surrounding film, using polarizing microscopy. The formation of regular dynamic stripe structures is observed.

Surface tension and disjoining pressure of free-standing smectic films above the bulk smectic-A-isotropic transition temperature

We have carried out a numerical study of both the structural and thermodynamic properties of free-standing smectic films for the case of enhanced pair interaction in the bounding layers. Calculations, based upon the extended McMillan's mean-field theory with anisotropic forces, show that the layer-thinning transitions are characterized by abrupt drops to lower values, both for a disjoining pressure and a fluctuation-induced long-range interaction between the smectic film surfaces, and then continues to increase with a larger positive slope. Reasonable agreement between the theoretically predicted and the experimentally obtained data on the surface tension of the partially fluorinated 5-n-alkyl-2-(4-n-(perfluoroalkyl-metheleneoxy)phenyl) film has been obtained.

Nanoscale viscoplastic behavior of smectic liquid crystals and its application in nanolithography

We report a unique combination of properties of smectic liquid crystal films that can be described as a viscoplastic behavior on the nanoscale: On the one hand, the films preserve imprinted surface patterns despite being permeated by a directed molecular flow of the film material. On the other hand, their surface morphology can easily be manipulated using an atomic force microscopy tip. Our results demonstrate a controlled molecular-scale deposition of material on the film surface, thereby enabling nanolithographic surface modification of a fluid material.

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 KB and splay KS 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 KB/KS 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.

Rim instability of bursting thin smectic films

The rupture of thin smectic bubbles is studied by means of high speed video imaging. Bubbles of centimeter diameter and film thicknesses in the nanometer range are pierced, and the instabilities of the moving rim around the opening hole are described. Scaling laws describe the relation between film thickness and features of the filamentation process of the rim. A flapping motion of the retracting smectic film is assumed as the origin of the observed filamentation instability. A comparison with similar phenomena in soap bubbles is made. The present experiments extend studies on soap films [H. Lhuissier and E. Villermaux, Phys. Rev. Lett. 103, 054501 (2009)10.1103/PhysRevLett.103.054501] to much thinner, uniform films of thermotropic liquid crystals.

Field-induced dependence of rotational diffusion processes in smectic films deposited on a solid surface

We have carried out a numerical study of the structural, thermodynamic, and motional properties of ultra-thin smectic films deposited in vacuo on a solid surface and subjected to external electric field E. A molecular model based upon the random walk theory is applied for calculating the rotational self-diffusion (RSD) coefficient D⊥ both in the bulk of the smectic film, as well as in the vicinity of the bounding surfaces. Calculations of D⊥ require the orientational distribution function or the set of the orientational order parameters (OPs) which has been obtained by using the mean-field approach. The effects both of surface enhanced pair interactions in the bounding LC/solid and LC/vacuum layers and of E on the orientational and translational OPs, as well as on the RSD coefficient of smectic films have been investigated. A reasonable agreement between the theoretically predicted and the experimentally obtained data on the RSD coefficient in the bulk of 4-n-octyl-4′-cyanobiphenyl phase has been obtained.

Elastic mediated force between nanoparticles adsorbed on smectic films under an external field

Within the harmonic approximation, we analytically determine the elastic-mediated interaction between colloidal nanoparticles adsorbed on the surface of smectic films under the influence of an external field. Both cases of free-standing films and films deposited over a solid substrate are considered. We show that the asymptotic decay (1/R in free-standing and exponential in deposited films) is not altered by the external field. However, the external field plays distinct roles according to the film configuration, the interparticle distance, the film thickness, and the surface tension at the film-gas interface. We provide a detailed discussion under the light of the distinct mechanisms controlling the undulations of the surface layer.

Crossover From Under to Overdamped Dynamics in Free-Standing Smectic Films Close to the Smectic-A-Nematic Second Order Phase Transition

The hydrodynamic properties of free-standing smectic films close to a second order smectic-A (SmA) — nematic (N) phase transition are investigated. By using an extended McMillan model, the profiles of the smectic elastic constants are computed at different temperatures. We show that the amplitude of smectic fluctuations has a strong dependence on the film temperature. By considering the critical behavior of viscoelastic coefficients of thin films, we show that the typical underdamped relaxation of the smectic order is replaced by an overdamped behavior close to the bulk transition temperature.

Measurement of the interface tension of smectic membranes in water

A simple method is proposed to measure the interfacial tension of a smectic liquid crystal (LC) in freely suspended film geometry in aqueous environment. The method is based upon the evaluation of the deformation of smectic bubbles by the buoyancy of a trapped air volume. The advantages over classical suspended smectic droplet experiments in water are the considerably shorter equilibration times, and most important, the much larger density differences between the fluids. The latter allow a much more accurate force determination. Bulk elastic force contributions can be practically neglected in the thin smectic films. Values for a smectic C mixture of two disubstituted phenylpyrimidines are reported.

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

The structure of π- and 2π-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. π-walls are observed in magnetic field and 2π-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.