Alignment of liquid crystals using Langmuir‒Blodgett films of unsymmetrical bent-core liquid crystals

ABSTRACT

The properties of the thin films of liquid crystal (LC) molecules can be governed easily by external fields. The anisotropic structure of the LC molecules has a large impact on the electrical and optical properties of the film. The Langmuir monolayer (LM) of LC molecules at the air–water interface is known to exhibit a variety of surface phases which can be transferred onto a solid substrate using the Langmuir?Blodgett (LB) technique. Here, we have studied the LM and LB films of asymmetrically substituted bent-core LC molecules. The morphology of LB film of the molecules is found to be a controlling parameter for aligning bulk LC in the nematic phase. It was found that the LB films of the bent-core molecules possessing defects favour the planar orientation of nematic LC, whereas the LB films with fewer defects show homeotropic alignment. The defect in LB films may introduce splay or bend distortions in the nematic near the alignment layer which can govern the planar alignment of the bulk LC. The uniform layer of LB film facilitates the molecules of nematic to anchor vertically due to a strong van der Waals interaction between the aliphatic chains leading to a homeotropic alignment.     

Effects of substrate on the melting behavior of Cd arachidate Langmuir–Blodgett films

Nineteen monolayered Cd arachidate films were deposited on float glass substrate coated with Si and Ni over-layers. Two layers have been chosen with very different surface free energies. Melting behavior of films were studied using variable temperature X-ray specular reflectivity and Fourier transform infrared spectroscopy measurements. In conformity with earlier studies, melting of the multilayer precede by a transition from distorted hexagonal to hexaticlike phase. However, the transition temperature to hexaticlike phase as well as the melting temperature depend significantly on the type of layer. Both the transition temperatures are higher for the multilayer deposited on Ni layer as compared to those for the film deposited on Si layer. These results can be understood in terms of different surface free energies of Ni and Si layers. Further, in case of Ni layer, transition to hexaticlike phase is relatively sharper. Even in the molten state there is a significant difference in the structure of the Cd arachidate film on two layers; packing density of molecules in molten state is lower in case of substrate with higher surface free energy. These results suggest that the surface free energy of substrate plays a significant role in melting behavior of Langmuir–Blodgett films.     

Langmuir–Blodgett films of octadecanethiol on gold sols subphase

An octadecanethiol monolayer was formed on an aqueous gold sols subphase, it’s LB films were characterized by means of π-A isotherms, TEM (transmission electron microscopy), XRD (X-ray diffraction) and UV–Vis spectroscopy.     

Preparation and characterisation of monolayers and Langmuir–Blodgett films of liquid crystal mixed with cubic silsesquioxanes

Polyhedral oligomeric silesquioxanes (POSS) with eight polyether substituents were mixed with the liquid crystal (LC) 4-octyloxy-4′-cyanobiphenyl and spread at the air/water interface. The surface pressure-area and surface potential-area isotherms were recorded for different weight ratios of both components. The obtained results showed that POSS molecules had beneficial influence on LC monolayer improving its stability and rigidity. Moreover, it was found that some LC–POSS mixtures collapse reversibly and form multilayer films on the top of LC monolayer. On the other hand, interfacial dilatational and shear rheology indicated decrease of elasticity of the films after mixing. Brewster angle microscopy revealed multilayer structure of the condensed film and formation of net-like structures in the expanded film. These films were successfully transferred on solid substrates using the Langmuir–Blodgett technique. The scanning electron microscopy images confirmed the film deposition and formation of networks by POSS–LC mixtures. These findings may be useful in the fabrication of electronic devices based on LCs.     

Microcrystalline domains of monolayer and multilayer BDN-SA Langmuir–Blodgett films

Monolayer and multilayer BDN(Bis(4-diethyannodithiobenzil)nickel)-SA(stearyl alcohol) LB (Langmuir–Blodgett) films were prepared and the characteristics of microcrystalline domains were studied using UV–vis.–NIR and AFM. The results indicate that BDN-SA LB films consist of numerous ball-like microcrystalline domains at size scales from a few tens to a few hundreds of nm. AFM images of a multilayer LB film show that well-ordered molecular arrangements exist on the surface of domains which resemble a mosaic structure. The relationship between the mean size of the domain of a BDN-SA LB film with the thickness of the film was also shown.     

Surface plasmon resonance research on photoinduced switch properties of liquid crystalline azobenzene polymer Langmuir–Blodgett films

We report a novel phenomenon of photoisomerization-induced switch properties in liquid crystalline azo-benzene polymer poly{2-hydroetheyl methacrylate}-co-{6-[4-(S-2-methyl-1-butyloxycarbonylphenylazo) phenoxy]hexyl methacrylate} Langmuir–Blodgett (LB) monolayers. These monolayers were deposited on gold film and irradiated with UV (360 nm) and blue (450 nm) light. The switch properties were investigated by the surface plasmon resonance (SPR) technique. A method called photoinduced patterning was used for the fabrication of a model molecular device. It has been found that the photoinduced process of writing and erasing in such devices can be repeated for tens of cycles.     

Analysis of organic acids and phenols of interest in the wine industry using Langmuir–Blodgett films based on functionalized nanoparticles

A chemically modified electrode consisting of Langmuir–Blodgett (LB) films of n-dodecanethiol functionalized gold nanoparticles (S_DODAuNP-LB), was investigated as a voltammetric sensor of organic and phenolic acids of interest in the wine industry. The nanostructured films demonstrated interfacial properties being able to detect the main organic acids present in grapes and wines (tartaric, malic, lactic and citric). Compared to a bare ITO electrode, the modified electrodes exhibited a shift of the reduction potential in the less positive direction and a marked enhancement in the current response. Moreover, the increased electrocatalytic properties made it possible to distinguish between the different dissociable protons of polyprotic acids. The S_DODAuNP-LB sensor was also able to provide enhanced responses toward aqueous solutions of phenolic acids commonly found in wines (caffeic and gallic acids). The presence of nanoparticles increased drastically the sensitivity toward organic acids and phenolic compounds. Limits of detection as low as 10⁻⁶ mol L⁻¹ were achieved. Efficient catalytic activity was also observed in mixtures of phenolic acid/tartaric in the range of pHs typically found in wines. In such mixtures, the electrode was able to provide simultaneous information about the acid and the phenol concentrations with a complete absence of interferences.     

Studies on morphology of polyaniline films formed at liquid–liquid and solid–liquid interfaces at 25 and 5 °C,respectively, and effect of doping

It is well accepted that the morphology of the nanomaterials has great effect on the properties and hence their applications. Therefore, morphology of materials has become a focus of research in the scientific world. The present study shows that interfacial polymerization and subsequent self-assembly provides a control over the morphology, nanorod/nanosheet, of polyaniline (PANI) films synthesized by liquid–liquid interface reaction technique and solid–liquid interface reaction technique. The synthesized PANI films and its particulate structure are characterized by using various spectroscopic techniques such as UV–visible, ATR-IR, Raman and XPS. The study confirmed the formation, the structure, the size and shape of particles and morphology of PANI by using analytical techniques namely, SAED, SEM and TEM. An important observation is that doping with HCl significantly improves the nanorod formation at the interface. The doped PANI electrode exhibits a higher area with rectangular shape in CV cycle and better cycle stability when compared with the performance of undoped PANI films. We believe that the results of these studies can give valuable leads to manoeuvre formation of PANI films with desired morphology for various applications.

Composite Langmuir–Blodgett (LB) films of polyaniline and cadmium stearate

Composite monolayers of cadmium stearate and polyaniline processed with camphor sulphonic acid have been obtained at the air–water interface and subsequently transferred onto substrates as uniform Langmuir–Blodgett multilayers. Pressure–area (Π-A) isotherm studies indicated that polyaniline molecules are not squeezed out of the cadmium stearate matrix during compression or in the compressed state. Monolayer stability is seen to decrease when the polymer content is increased beyond 60% (in weight) which is probably associated with the formation of microaggregates that also affected the monolayer surface potential at large areas per molecule. With increasing amount of polyaniline in the mixture, a transition from Y-type to Z-type deposition has been observed. Transferred multilayer LB films were characterized by UV-vis, FTIR, XRD, surface potential, and dc electrical conductivity measurements. UV-vis results indicated that though the polyaniline was in the doped state in the spreading solution, the transferred films were in the emeraldine base state. FTIR studies revealed that the transferred films mainly contained cadmium stearate salt in addition to polyaniline. XRD results indicated that the stacking order is dependent on the polyaniline content in the composite films, the order was found to decrease upon increasing the polymer amount. The uniformity of transferred films was confirmed by surface potential studies. A possible packing arrangement in these composite Langmuir and Langmuir–Blodgett films has been proposed.     

Characterization of CdS nanoparticles formed and aggregated in stearic acid Langmuir–Blodgett films by atomic force microscopy

Alternate films, which are composed of stearic acid and CdS nanoparticles were synthesized by exposing Langmuir–Blodgett (LB) films of cadmium stearate (CdSt₂) to H₂S gas at a pressure of 1 Torr. The changes of surface morphology of film with the increased reaction time were directly observed by atomic force microscopy for the first time. Before being exposed to H₂S, the surface of CdSt₂ LB film was homogeneous from microscale down to nanoscale, and it was observed that CdSt₂ molecules formed a well orderly rectangular herringbone lattice structure on the molecular scale. However, after being exposed to H₂S the ordered CdSt₂ molecules gradually changed into a disordered state, and eventually the LB film surface became rough with the apparent feature of bulk structures on the nanoscale. This change in the morphology can be attributed to the aggregation of buried CdS nanoparticles within LB films, which has been confirmed by a structured UV–visible absorption spectrum where the absorption edge is red-shifted about 0.7 eV with respect to bulk CdS. Finally, the aggregation mechanism of CdS in the LB film was analyzed.     

Optical,electrical, and thermochromic properties of polyazothiophene Langmuir–Blodgett films

The conductivity and luminescence of conjugated polymers may be combined with the photoisomerization capability of azobenzene materials to achieve unique properties for a variety of applications, particularly if conjugated polymers with azobenzene side chains are processed as nanostructured films. In this study, we report on Langmuir–Blodgett (LB) films of a polythiophene-bearing azobenzene moieties, which displayed photoluminescence, thermochromism, electroactivity, and photoinduced birefringence. The latter three properties were enhanced in the LB films, as compared to spin-coated films of the polyazothiophene, and this has been attributed to differences in film morphology that could be probed with atomic force microscopy.     

Synthesis and photoreaction of Schiff bases derived from p-nitro cinnamaldehyde and diamines in Langmuir and Langmuir–Blodgett films

Monolayers of Schiff bases derived from ethylene diamine and o-phenylene diamine with p-nitro cinnamaldehyde, (compounds 1 and 2) at air/water interface have been studied. Photolysis of 1 in chloroform solution undergoes cis–trans isomerization on irradiation of white light while compound 2 does not undergo isomerization under photolytic conditions. The photolysis of 1 and 2 in Langmuir–Blodgett films (LB films) transferred to quartz plates form dimers. The change in product distribution is attributed to the influence of bridging group of the cinnamaldehyde moieties, molecular configuration and mobility of the compounds in solution, solid state and the aggregation of molecules in monolayer assemblies.     

Nonradiative energy transfer in mixed Langmuir monolayers and Langmuir–Blodgett films of compounds of different chemical composition and structure

Russian Chemical Bulletin - The efficiency of the Förster resonance energy transfer (FRET) in a monolayer film containing the energy donor and energy acceptor fluorophores is low since the...     

An infrared study on Langmuir–Blodgett films of octadecylammonium octadecanoate: FWHM and the vibrational coupling

The monolayer of the mixture of octadecanoic acid and octadecylamine with molar ratio 1:1 has been investigated at the air–water interface. It was found that the monolayer shows a rather stable state at the surface pressure of 30 mN/m and this monolayer can be transferred onto a CaF₂ plate by Langmuir–Blodgett (LB) technique. The infrared spectra of LB films indicated that octadecylammonium octadecanoate is formed by an intermolecular proton exchange between adjacent carboxylic and aminic groups (COO⁻ and NH₃⁺). In three-layer LB film, the CH₂ scissoring mode of the long hydrocarbon chains of octadecylammonium octadecanoate shows a broad band feature at about 1468 cm⁻¹ while this vibrational mode of three-layer LB film of the mixture (1:1) of deuterated stearic acid and octadecylamine (octadecylammonium octadecanoate-d35, C₁₈H₃₇NH₃⁺C₁₇D₃₅COO⁻) only shows a narrow band. The broad feature of the CH₂ scissoring mode in octadecylammonium octadecanoate probably originates from the coupling between the chain of stearic acid and that of octadecylamine while this kind of coupling could be completely removed in octadecylammonium octadecanoate-d35. Another conclusion presented in this paper is that there are no couplings among the chains of fatty acid or among the chains of octadecylamine in LB films of octadecylammonium octadecanoate.     

Synthesis and mesomorphic properities of some ferroelectric liquid crystals of lactate

A semiperfluorinated chain has been introduced into three series of lactate-based molecules,and their mesomorphic properities have been studied by DSC and optical polarized microscope.An abnormal phenomenon has been found that the introduction of a triple bond in the core of the molecule,which lengthened the molecule,gave rise to a decrease in the thermal stability of chiral smectic C phase and smectic A phase.2,3-Difluoro substituents of the phenylenic structure hinder the formation of the chiral smectic C phase because of the steric effect.     

Strong emitting sol–gel materials based on interaction of luminescence dyes and lanthanide complexes with silver nanoparticles

We show here how luminescence of fluorescent dyes and lanthanide complexes in sol–gel matrix can be intensified as a result of interaction of the species with silver nanoparticles. Preparation of silver nanoparticles in sol–gel composite precursor is outlined and their structural characterization are presented. Zirconia-glymo and Glymo-polyurethane-silica were used as host matrices for silver nanoparticles and the fluorescence species. The intensification of fluorescence was demonstrated by steady state spectroscopy.     

Direct colorimetric study on the interaction of Escherichia coli with mannose in polydiacetylene Langmuir–Blodgett films

The membranes of polydiacetylene backbone decorated with mannose assembled by Langmuir–Blodgett technology can interact with Escherichia coli. The interactions lead to the color transition of the membranes which was readily visible to the naked eyes and could be quantified by visible absorption spectroscopy. To understand the mechanism of the chromatic transition, the affinochromism properties of polydiacetylene were examined by resonance Raman spectroscopy. The results demonstrated that the side chains of polymer backbone performed rearrangement, and the electronic structure in the polymer backbone changed from acetylene to butatriene form when the chromatic transformation from blue to red. The direct colorimetric detection by polydiacetylene membranes not only opens a new path for the use of these membranes in the area of biosensor development but also offers new possibilities for diagnostic applications and screening for binding ligand.     

Formation and tribological properties of composite Langmuir–Blodgett films of stearic acid with molybdenum disulfide and amorphous carbon

The morphology and tribological properties of Langmuir–Blodgett mono- and bilayers of stearic acid with particles of molybdenum disulfide (MoS₂) and amorphous carbon (С), prepared on silicon and steel substrates by horizontal deposition (stearic acid–MoS₂ and stearic acid–С monolayers) and by the “roll” technique (stearic acid–MoS₂/stearic acid–С bilayers), were studied. Incorporation of C and MoS₂ particles into the structure of a stearic acid film enhances its wear resistance by a factor of 2.8 and 5.5, respectively. The presence of MoS₂ and С particles and of their aggregates of size from ~220 nm to 16.3 μm in stearic acid layers was confirmed by atomic force microscopy.