A. M. Shatalova

Liquid-crystalline polymer composites with CdS nanorods: structure and optical properties.

We report on the structure, uniaxial orientation, and photoluminescent properties of CdS nanorods that form stable nanocomposites with smectic C hydrogen-bonded polymers from the family of poly(4-(n-acryloyloxyalkoxy)benzoic acids. TEM analysis of microtomed films of nanocomposites reveals that CdS nanorods form small domains that are homogeneously distributed in the LC polymer matrix. They undergo long-range orientation with the formation of one-dimensional aggregates of rods when the composite films are uniaxially deformed. The Stokes photoluminescence was observed from CdS NRs/LC polymer composites with emission peak located almost at the same wavelength as that of NRs solution in heptane. An anti-Stokes photoluminescence (ASPL) in polymer nanocomposites was found under the excitation below the nanoparticles ground state. The mechanism of ASPL was interpreted in terms of thermally populated states that are involved in the excitation process. These nanocomposites represent an unusual material in which the optical properties of anisotropic semiconductor nanostructures can be controlled by mechanical deformation of liquid-crystalline matrix.

Phase separation effects and the nematic–isotropic transition in polymer and low molecular weight liquid crystals doped with nanoparticles

Properties of the nematic–isotropic phase transition in polymer and low molecular weight liquid crystals doped with nanoparticles have been studied both experimentally and theoretically in terms of molecular mean-field theory. The variation of the transition temperature and the transition heat with the increasing volume fraction of CdSe quantum dot nanoparticles in copolymer and low molecular weight nematics has been investigated experimentally and the data are interpreted using the results of the molecular theory which accounts for a possibility of phase separation when the system undergoes the nematic–isotropic transition. The theory predicts that the nematic and isotropic phases with different concentrations of nanoparticles may coexist over a broad temperature range, but only if the nanoparticle volume fraction exceeds a certain threshold value which depends on the material parameters. Such unusual phase separation effects are determined by the strong interaction between nanoparticles and mesogenic groups and between nanoparticles themselves.

Development and stabilization of liquid crystalline phases in hydrogen-bonded systems

This review addresses the description of fundamental principles underlying the development of liquid crystalline phases in hydrogen-bonded complexes. Low-molecular-mass models and polymers systems are considered, where hydrogen bonding is used as an efficient means for modifying polymer structure and designing new materials.

Photoluminescence properties of cadmium-selenide quantum dots embedded in a liquid-crystal polymer matrix

The photoluminescence properties of cadmium-selenide (CdSe) quantum dots with an average size of ∼3 nm, embedded in a liquid-crystal polymer matrix are studied. It was found that an increase in the quantum-dot concentration results in modification of the intrinsic (exciton) photoluminescence spectrum in the range 500–600 nm and a nonmonotonic change in its intensity. Time-resolved measurements show the biexponential decay of the photoluminescence intensity with various ratios of fast and slow components depending on the quantum-dot concentration. In this case, the characteristic lifetimes of exciton photoluminescence are 5–10 and 35–50 ns for the fast and slow components, respectively, which is much shorter than the times for colloidal CdSe quantum dots of the same size. The observed features of the photoluminescence spectra and kinetics are explained by the effects of light reabsorption, energy transfer from quantum dots to the liquid-crystal polymer matrix, and the effect of the electronic states at the CdSe/(liquid crystal) interface.

Alignment of nanoparticles in polymer matrices

This paper briefly summarizes the state of the art in the field of designing composites containing semiconductor nanoparticles distributed in a polymer matrix. Special attention is focused on (i) nanocomposites based on block copolymers and (ii) LC polymer matrices capable of controlling the localization and alignment of nanoparticles.

Matrices based on acrylic liquid-crystalline copolymers for the design of composites with quantum dots

Acrylic ternary cholesteric copolymers that selectively reflect light in a wide temperature range and carry functional carboxyl groups are synthesized and characterized. As shown by X-ray diffraction analysis, differential scanning calorimetry, optical microscopy, spectroscopy, and transmission electron microscopy, the cholesteric structure is formed in the copolymers. The optical properties of the copolymers are investigated. It is shown that homogeneous nanocomposites, in which the liquid-crystalline order is preserved, may be created.

Role of the Polymer Matrix on the Photoluminescence of Embedded CdSe Quantum Dots

The photoluminescence (PL) of CdSe quantum dots (QDs) that form stable nanocomposites with polymer liquid crystals (LCs) as smectic C hydrogen-bonded homopolymers from a family of poly[4-(n-acryloyloxyalkyloxy)benzoic acids] is reported. The matrix that results from the combination of these units with methoxyphenyl benzoate and cholesterol-containing units has a cholesteric structure. The exciton PL band of QDs in the smectic matrix is redshifted with respect to QDs in solution, whereas a blueshift is observed with the cholesteric matrix. The PL lifetimes and quantum yield in cholesteric nanocomposites are higher than those in smectic ones. This is interpreted in terms of a higher order of the smectic matrix in comparison to the cholesteric one. CdSe QDs in the ordered smectic matrix demonstrate a splitting of the exciton PL band and an enhancement of the photoinduced differential transmission. These results reveal the effects of the structure of polymer LC matrices on the optical properties of embedded QDs, which offer new possibilities for photonic applications of QD-LC polymer nanocomposites.

Immobilization of quantum dots of cadmium selenide on the matrix of a graft liquid-crystalline polymer

A new luminescent composite based on quantum dots of CdSe immobilized on the polymer LC matrix prepared through the graft polymerization of the monomer of 4-(ω-acryloyloxyhexyloxy)benzoic acid on a fluorocarbon support after its preliminary irradiation with vacuum ultraviolet light is elaborated. The structure, composition, and optical characteristics of the prepared composite are studied via the methods of the FTIR spectroscopy, energy-dispersive and wave-dispersive analyses, and luminescence spectroscopy. The CdSe particles are shown to interact with the carboxyl groups of mesogenic fragments of the LC polymer, and this interaction leads to the integration of quantum dots into the ordered LC structure of the composite. As a result of immobilization, the luminescence peak of the quantum dots is shifted toward lower wavelengths owing to the interaction between the nanoparticles and the polymer LC matrix.

Blend Composites Based on Polystyrene–CdSe Quantum Dots and Polystyrene–Gold Nanoparticles Hybrid Systems

Polystyrenes of different molecular masses are synthesized by controlled radical polymerization via the reversible addition fragmentation chain transfer mechanism. The resulting polymers are used for designing nanocomposites based on cadmium selenide quantum dots and gold nanoparticles. It is demonstrated that the photoluminescence of quantum dots in the sol grows appreciably during continuous irradiation for 5–6 h but is reduced during the “light switching off–switching on” process. It is shown that, upon the addition of gold nanoparticles, the photoluminescence of quantum dots in the sols changes insignificantly.

Liquid Crystal Polymers as Matrices for Arrangement of Inorganic Nanoparticles

Preparation of hybrid composite materials consisting of a polymeric matrix and inorganic nanoparticles (NPs) is considered as an approach for creating new materials for photonics. The major focus of this review is on the applications of anisotropic matrices that can control the spatial arrangement of NPs. The fundamental aspects related to hybrid organic-inorganic composites with photonic properties provided by LC polymers are of great practical interest. Several approaches are considered as efficient tools for tuning the photoluminescence by means of chemical coupling (covalent or non-covalent) of polymers with NPs, mesophase structure type and NPs morphology.