Self-organized arrays of dislocations in thin smectic liquid crystal films.

Combining optical microscopy, synchrotron X-ray diffraction and ellipsometry, we studied the internal structure of linear defect domains (oily streaks) in films of a smectic liquid crystal 8CB with thicknesses in the range of 100-300 nm. These films are confined between air and a rubbed PVA polymer substrate which imposes hybrid anchoring conditions (normal and unidirectional planar, respectively). We show how the presence or absence of dislocations controls the structure of highly deformed thin smectic films. Each domain contains smectic layers curved in the shape of flattened hemicylinders to satisfy both anchoring conditions, together with grain boundaries whose size and shape are controlled by the presence of dislocation lines. A flat grain boundary normal to the interface connects neighboring hemicylinders, while a rotating grain boundary (RGB) is located near the axis of curvature of the cylinders. The RGB shape appears such that dislocation lines are concentrated at its summit close to the air interface. The smectic layers reach the polymer substrate via a transition region where the smectic layer orientation satisfies the planar anchoring conditions over the entire polymer substrate and whose thickness does not depend on that of the film. The strength of planar anchoring appears to be high, larger than 10(-2) mJ m(-2), compensating for the high energy cost of creating an additional 2D defect between a horizontal smectic layer and perpendicular ones of the transition region. This 2D defect may be melted, in order to avoid the creation of a transition region structure composed of a large number of dislocations. As a result, linear defect domains can be considered as arrays of oriented defects, straight dislocations of various Burger vectors, whose location is now known, and 2D nematic defects. The possibility of easy variation between the present structure with a moderate amount of dislocations and a structure with a large number of dislocations is also demonstrated.

Tailoring Anisotropic Interactions between Soft Nanospheres Using Dense Arrays of Smectic Liquid Crystal Edge Dislocations.

We investigated composite films of gold nanoparticles (NPs)/liquid crystal (LC) defects as a model system to understand the key parameters, which allow for an accurate control of NP anisotropic self-assemblies using soft templates. We combined spectrophotometry, Raman spectroscopy, and grazing incidence small-angle X-ray scattering with calculations of dipole coupling models and soft sphere interactions. We demonstrate that dense arrays of elementary edge dislocations can strongly localize small NPs along the defect cores, resulting in formation of parallel chains of NPs. Furthermore, we show that within the dislocation cores the inter-NP distances can be tuned. This phenomenon appears to be driven by the competition between "soft (nano)sphere" attraction and LC-induced repulsion. We evidence two extreme regimes controlled by the solvent evaporation: (i) when the solvent evaporates abruptly, the spacing between neighboring NPs in the chains is dominated by van der Waals interactions between interdigitated capping ligands, leading to chains of close-packed NPs; (ii) when the solvent evaporates slowly, strong interdigitation between the is avoided, leading to a dominating LC-induced repulsion between NPs associated with the replacement of disordered cores by NPs. The templating of NPs by topological defects, beyond the technological inquiries, may enable creation, investigation, and manipulation of unique collective features for a wide range of nanomaterials.

Planar anchoring and surface melting in the smectic-A phase.

We study ultrathin films of 8CB in planar anchoring on a MoS2 inorganic substrate. We evidence an anchoring breakage for 60-nm-thick films, in favor of the homeotropic anchoring at the air interface. This allows one to determine the 8CB-MoS2 smectic anchoring energy. We then demonstrate for films thinner than 60 nm that, under the homeotropic bulk, an intermediate film remains in planar anchoring, associated with a melting of the smectic layers close to the substrate. Such a melting could be general for planar or tilted anchorings and we show that, for strong anchorings, the anchoring energy can be driven by the deformations of this intermediate nematic film.

Specific ion adsorption and short-range interactions at the air aqueous solution interface.

We have investigated the surface composition of alkali-halide aqueous solutions using grazing incidence x-ray fluorescence. Using mixtures of salts as a means to enhance the short-range effects, small differences in concentration over a few angstrom could be resolved, with, for example I- or Br- > Cl-. In order to explain our data, we need to include an effective potential accounting for the short-range (A) solvent mediated couplings, responsible for specific effects together with dispersion forces. This attractive potential (few k{B}T for halides) leads to concentration profiles which are in good agreement with recent numerical simulations.

Structure of smectic defect cores: x-ray study of 8CB liquid crystal ultrathin films.

We study the structure of very thin liquid crystal films frustrated by antagonistic anchorings in the smectic phase. In a cylindrical geometry, the structure is dominated by the defects for film thicknesses smaller than 150 nm and the detailed topology of the defects' cores can be revealed by x-ray diffraction. They appear to be split in half tube-shaped rotating grain boundaries (RGB). We determine the RGB spatial extension and evaluate its energy per unit length. Both are significantly larger than the ones usually proposed in the literature.

Optical gratings formed in thin smectic films frustrated on a single crystalline substrate.

Through the combination of three different, complementary techniques (optical microscopy, x-ray diffraction and atomic force microscopy), we reveal the deformations inside thin smectic films frustrated between two interfaces imposing antagonistic anchorings. We study the model system, 4-n-octyl-4'-cyanobiphenyl (8CB) between MoS2 and air, which is characterized by the competition between homeotropic anchoring at air and planar unidirectional anchoring on the substrate, with thicknesses varying around 0.3 microm. Optical microscopy and x-ray diffraction demonstrate the continuous topology of smectic layers between the interfaces, which are stacked into periodic flattened hemicylinders. These latter are one-dimensional (1D) focal conic domains which form an optical grating in the smectic film, of a period ranging from 1 to 2.5 microm. The interpretation of our results through an energetic model, associated with the atomic force microscopy (AFM) measurements, shows the presence below a critical thickness of a new type of curvature wall between neighboring hemicylinders.

Bistable nematic and smectic anchoring in the liquid crystal octylcyanobiphenyl (8CB) adsorbed on a MoS2 single crystal.

We have studied the anchoring directions imposed on 4-n-octyl-4(')-cyanobiphenyl (8CB) smectic-A and nematic phases by a single crystal of molybdenum disulfide (MoS2). Combining optical microscopy and x-ray diffraction under grazing incidence we have demonstrated the occurrence of a bistable planar anchoring. A previous study of the two-dimensional (2D) network of adsorbed 8CB molecules under the liquid crystal film allows a direct connection to be made between the interface structure and the anchoring directions, demonstrating that bistability is induced by the presence of two dipolar groups in the skeleton of the 2D network. It is demonstrated that the Landau-de Gennes theory cannot account for the observed anchoring in the nematic phase. The Landau-de Gennes free energy has to be associated with a coupling with both the surface order and the MoS2 substrate to explain the experimental observations. The hypothesis of a nematic layer under the liquid crystal bulk is postulated in the smectic phase.