In the presence of oriented smectic liquid crystal defects, hybrid systems of nanoparticles/liquid crystals form straight chains of nanoparticles of length longer than tens of micrometers and width equal to one single nanoparticle. The interparticle distance in a chain can be varied between a few micrometers and 1.5 nm, highlighting the control of optical absorption by light polarization monitored by gold nanoparticle concentration.

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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.

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.

We use arrays of liquid crystal defects, linear smectic dislocations, to trap semi-conductor CdSe/CdS dot-in-rods which behave as single photon emitters. We combine measurements of the emission diagram together with measurements of the emitted polarization of the single emitters. We show that the dot-inrods are confined parallel to the linear defects to allow for a minimization of the disorder energy associated with the dislocation cores. We demonstrate that the electric dipoles associated with the dotin-rods, tilted with respect to the rods, remain oriented in the plane including the smectic linear defects and being perpendicular to the substrate, most likely due to the dipole/dipole interactions between the dipoles of the liquid crystal molecules and the dot-in-rods ones. Using smectic dislocations, we can consequently orient nanorods along a unique direction for a given substrate, independently of the ligands' nature, without any induced aggregation, leading as well to a fixed azimuthal orientation for the associated dot-in-rods' dipoles. These results open the way for a fine control of nanoparticle anisotropic optical properties, in particular a fine control of single photon emission polarization.Control of single photon emitters is a major objective in the field of nanophotonics.[1] The synthesis of colloidal semiconductor inorganic nanocrystals having specific light-emission properties has been providing important advances in this field. In particular, recent developments in synthesis methodologies, fully compatible with standard nanofabrication technologies have enabled a superior 3 control on nanocrystals composition and morphology.Rod-shaped nanocrystals showing pronounced polarization, behaving as emitting linear dipoles, have been obtained. [2][3][4] The encapsulation of a spherical core into a rod-like shell [5] resulted in non-blinking inorganic single photon emitters, [6] hereafter referred to as dot-in-rods (DRs). Moreover it has been recently shown that, by increasing the thickness of the shell, it is possible to greatly suppress photoluminescence blinking and to improve DRs overall photo-stability, while keeping a low probability of multi-photon emission. [7] Such features are of primary importance when nanocrystalsare used in applications demanding a control of photons'polarization, such as coupling with complex photonic cavities [8][9] or quantum cryptography.[10] The control of the polarization of the emitted light also requires the capacity to control the particle orientation. Howevertechnologies aimed at guiding nanocrystal orientation at the single particle level are still poorly discussed in literature.Alignednanoparticleshave been obtained through mechanical rubbing, [11] short-range interactions [12][13] or patterned substrates. [14] Liquid crystal-like structures, composed of alarge number of elongated nanocrystalsassembled in multi-layers have also been evidenced on both solid substrates [15][16][17][18] and water films. [18][19][20] Orientation and positional ordering of CdS and CdSe...

International audienceWe show that the study of gold nanoparticle self-assemblies induced by a liquid crystal matrix reveals the intimate distorted structure of the liquid crystal existing prior to nanoparticles incorporation. We also show how this intimate structure monitors the spacing between nanoparticles in the self-assemblies. We have created hybrid films of cholesteric liquid crystal (CLC) and gold nanoparticles, the CLC being deformed by competing anchorings at its two interfaces. Whereas previous results have evidenced formation of only slightly anisotropic clusters of large nanoparticles (diameter 20nm), we now demonstrate for smaller nanoparticles (diameter 4.2nm) formation of long needles of length larger than 50 nanoparticles and width smaller than 5 nanoparticles, on average oriented perpendicular to the anchoring direction. The difference between the two kinds of nanoparticle aggregations is interpreted by a modification of the balance between aggregation between nanoparticles and trapping by the defects, favoured by the disorder induced by the alkylthiol molecules grafted around the nanoparticles. This leads to a well-defined, anisotropic Localized Surface Plasmonic Resonance (LSPR) of the 4.2nm embedded nanoparticles. Interpretation of these optical properties using generalized Mie theory allows for a comparison between CLC/gold nanoparticles and the same nanoparticles trapped within smectic topological defects or deposited on the same substrate without liquid crystal. A smaller spacing between nanoparticles is demonstrated in the CLC system with an attraction between nanoparticles induced by the CLC matrix, related to the additionnal disorder associated with the nanoparticles presence. The experimental observations allow us to estimate the disordered size of the liquid crystal shell around the nanoparticles in the CLC to be of some nanometers. They also suggest that the CLC distorted by competing anchorings is characterized by the presence of arrays of defects with topological cores of width smaller than 5nm that act as efficient anisotropic traps for the nanoparticles

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Local full Mueller matrix measurements in the Fourier plane of a microscope lens were used to determine the internal anisotropic ordering in periodic linear arrays of smectic liquid crystal defects, known as 'oily streaks'. We propose a single microstructure-dependent model taking into account the anisotropic dielectric function of the liquid crystal that reproduces the smectic layers orientation and organization in the oily streaks. The calculated Mueller matrix elements are compared to the measured data to reveal the anchoring mechanism of the smectic oily streaks on the substrate and evidence the presence of new type of defect arrangement. Beyond the scientific inquiry, the understanding and control of the internal structure of such arrays offer technological opportunities for developing liquid-crystal based sensors and self-assembled nanostructures.