The Use of Azo Dyes in Guest-Host Displays

Azo dye molecules are cylindrically shaped, and therefore, due to their resemblance to liquid crystal molecules, would seem to be suitable for use in guest-host mixtures. The dichroic ratio of a dye in a given nematic host depends on the molecular length of the dye molecules, the order parameter of the liquid crystal host and its molecular dimensions. It is possible to obtain a guest-host mixture with an order parameter which is higher than that of the pure host. Lateral substitution of mono-azo dyes lowers the order parameter, whilst lateral substitution of the corresponding bis-and tris-azo molecules results in only a slight change in their order parameter.

The stability of these compounds to light is poor, and depends on the wavelength for maximum absorption, and on the host material. Whilst lateral substitution increases the fastness of azo compounds when used for textile dying, this is not the case when they are employed with liquid crystal mixtures. The kinetics of degradation are zero order in dye concentration.

It has been found that azo dyes are not in general suited to applications where prolonged exposure to sunlight may be encountered, e.g. watch applications.     

Order Parameter and the Performance of Nematic Guest-Host Displays

A simple model of a nematic guest-host display is presented in which the limiting “on” and “off” states are considered to be uniform arrays of molecules oriented perpendicular and parallel (or at a small tilt angle), respectively, to the plane of the display. Calculated contrast ratio and brightness curves are presented for several angles of view and of all planes of view as functions of dye order parameter, pretilt andploarizer efficiency. The effects of host refractive index and front surface reflectivity are discussed.     

The Guest-Host Interaction in Liquid Crystals: 1. A New Fast Dichroic Shutter

A new fast optical shutter, based on the guest-host interaction, that uses a 2 mm optical path length, has been demonstrated. Using a suitable pleo-chroic dye as guest in a cyanobiphenyl nematic host it has been shown that the shutter can be turned on and off in a few milliseconds. The electro-optic cell uses transverse electric fields, and field strength, frequency and temperature studies have been made. It has been shown that both increases and decreases in transient light levels may be obtained by changing the polarisation state of the incident light.     

ENHANCED FLEXOELECTRIC SWITCHING BEHAVIOUR IN THE CHIRAL NEMATIC PHASE

Abstract

In order to develop materials that exhibit enhanced flexoelectric switching in the chiral nematic phase we have identified mesogenic units that display inherently strong flexoelectric coupling capabilities. Here we examine the oxycyanobiphenyl (OCB) moiety: homologues from the nOCB series exhibit significant electro-optic switching effects when doped with a highly chiral additive. Here we have examined lower dielectric anisotropy materials, since they allow the flexoelectric response to be extended to high field amplitudes. We show that dielectric coupling strength can be low in symmetric bimesogenic molecules. The flexoelectric response of such a molecular structure is tested by doping a homologue from the series CBOnOCB with a chiral additive: very significantly we find that the optic axis is rotated through 2φ = 45° in < 50 μs on reversing the polarity of the field (amplitude E = ±6 V μm^?1). Subsequently we have synthesized room temperature chiral nematic materials that exhibit 2φ > 90° at E = 10 V μ^?1.     

Calorific Effect of the Magnetically Induced Phase Transition in Induced Chiral Nematic Systems

The study of the calorific effect of the magnetically-induced phase transition in doped nematic phases is described. The systems examined consisted of PCB as a nematic host phase and S-N-1-phenylethyl-4n-alkylbenzamides as non-mesogenic optically active dopants. The calorific effect was estimated indirectly from the temperature dependence of the magnetic-field-threshold of the helical unwinding and of the reverse process; i.e. the helical winding. It appears that it is the ratio of the length of an optically active dopant and that of the nematic host which determines the temperature dependencies of such parameters as the helical pitch, microscopic twisting power, and latent heat. A comparison with the magnetocaloric effect in nematic liquid crystals¹ is also made.     

The Effect of Rhodamine 6G on Phase Transitions in Cholesteryl Ester Mixtures

Compensated cholesteric mixtures were the subject of a whole range of studies.^1-6 Due to their characteristic properties (the existence of a temperature at which compensation occurs and the dependence of the critical field on temperature), the orientation of guest molecules by compensated cholesteric hosts⁷ shows some particular features in comparison to the orienting mechanisms acting within nematic liquid crystals^8-15 or within chiral nematic mixture.^16,17 When the colour of sample varies due to the influence of the electric field and temperature the guest dye contributes to it as well the compensated cholesteric host.

In this paper we report the modification of compensated cholesteric mixture properties due to the introduction of Rhodamine 6G as guest.     

A Positive Contrast Guest-Host Display Using a Liquid Crystal of Negative Dielectric Anisotropy

Recently we described a novel guest-host cell which exhibits a positive contrast (dark digits on a clear background) employing a mixture of a nematic liquid crystal with negative dielectric anisotropy, a chiral component, and a dichroic dye. In this cell, the cell thickness and the alignment layers are chosen such that in the absence of a field, the mixture shows a uniform homeotropic structure. When a voltage greater than the threshold value is applied, a helicoïdal structure is adopted, which absorbs the incident illumination.

In this work the expression for the threshold voltage is derived and compared with experimental results. Experimental results are also presented which indicate, for a given cell thickness, the influence of the pitch of the mixture on the contrast and the response time.     

PHOTOISOMERISING EFFECTS IN NITROAZO FLEXOELECTRIC DIMERIC NEMATIC SYSTEMS

Abstract

The photoisomerisation of a flexoelectric chiral nematic bimesogen system dyed with an azo dye has been investigated. The host material has a pitch and field dependent tilt angle that are temperature independent. Upon illumination by ultra violet, the azo dye molecules undergo a shape change from their trans to cis isomer. The effect of the shape change of the dye on the mixture is to decrease the I-N* transition temperatures, to increase the response times and to decrease the transmitted optical intensity. For the same reduced temperatures, the tilt angles, pitch and threshold voltages for the transition from focal conic to homeotropic textures are unchanged. The macroscopic parameters observed suggest that the orientational order parameter of the system is reduced by UV illumination. The cis isomers do not appear to separate from the host material or significantly change the flexoelectric coefficient.     

Orientational Order and Linear Dichroism of a Water Soluble Porphine in a Lyotropic Nematic Liquid Crystal

Aqueous lyotropic nematic liquid crystals can be homogeneously oriented by magnetic fields and are therefore well suited to be used as anisotropic solvents for optical polarization studies of water soluble dye molecules. The potassium laurate (KL)/KCl/H₂O nematic phase, composed of rod-like or cylindrical micelles, was used as a matrix for the study of orientational order and linear dichroism of a substituted free-base porphine (TPPS₄). The results indicate that a significant portion of porphine molecules are incorporated into the micelles with their planes on the average perpendicular to the optic axis of the lyotropic rods. The order parameter of TPPS₄ is much higher in this system than in other nematic lyophases such as KL/decanol/H₂O in which preferential hydrogen bonding occurs between TPPS₄ molecules and the hydroxyl groups of decanol molecules which presumably occupy the surface of the cylindrical micelles. All observed electronic transitions in the 350-700 nm range are found to be polarized in the plane of the porphine ring.     

Wavelength-tuneable laser emission from a dye-doped achiral nematic liquid crystal dispersed into a chiral polymer scaffold

ABSTRACT

We compare the emission characteristics of a thin-film liquid crystal (LC) laser created using a polymer-stabilized, dye-doped chiral nematic LC to that of an LC laser that was fabricated using an achiral, dye-doped nematic refilled into a chiral polymer scaffold that was templated from the same chiral nematic host. Both lasers exhibit wavelength tuning upon the application of an external electric field. However, for the templated sample, tuning is found to occur across a broader wavelength-range for the same electric field amplitude. We discuss the benefits of the templated approach and how it can be used to circumvent dye bleaching that may occur during photo-polymerisation.     

Dielectric Behavior of Nematic Liquid Crystals under DC Electric Field

Dielectric behavior of nematic liquid crystals of p-methoxybenzylidene-p-n-butylaniline and p-ethoxybenzylidene-p-n-butylaniline have been investigated under DC electric field in relation to their optical behavior. Both dielectric permittivity and transmitted light intensity decrease at a threshold voltage of external DC electric field, and the latter reaches a constant low value at higher field, while dielectric permittivity increases via minimum to approach a constant value at higher field strength of about 2 × 10⁴ V/cm. Such a change of dielectric permittivity under DC electric field is characteristic of nematic and supercooled states, and exhibits large dependence on both temperature and sample thickness. This dielectrical observation is discussed in terms of dielectric anisotropy of the nematic liquids oriented to the field, and the disturbance of molecular orientation due to the dynamic scattering at higher DC electric field.     

On the Phase Transition Behaviour of Binary Systems: Various Non-Nematic Solutes in Nematic Solvent (EBBA)

Phase transition behaviour of the systems of EBBA with methyl alcohol (MeOH), 1.2-dibromo-ethylene (DBE), o-xylene, m-xylene, and p-xylene has been studied. The phase diagrams for each system have been determined by the polarizing microscope. The slopes, β_n and B_i, of the nematic and the isotropic phase boundary lines in each system have been qualitatively described by the molecular field treatment proposed by Humphries. The order parameters for both cis-and trans-DBE in EBBA have been obtained from analyses of ¹H-NMR spectra. In the nematic phase, they decrease with increase in temperature. In the nematic/isotropic coexisting phase (N/I phase), the order parameter for CIS-DBE is almost independent of temperature. The proton spin-lattice relaxation times (T₁) in the MeOH/EBBA system have been measured by a pulse NM R technique. Little temperature dependence of T¹ has been found in the N/1 phase region.c     

Dipole Chains in Zeolite Pores: The Effects of Symmetry Breaking

Abstract

Dipole molecules become arranged in a highly ordered manner within zeolite pores. They are oriented nearly parallel to the straight channels and aligned collectively into one specific direction. They form arrangements different from the crystallization in the free bulk as well as different from arrangements in amorphous hosts. This polar arrangement results in (i) a lowering of the symmetry of the guest-host system compared to the host, (ii) nonlinear optical effects of second order such as second harmonic generation, (iii) a macroscopic polarization giving rise to pyroelectric effects and (iv) special phase transition phenomena in these one-dimensional systems.     

Hopping conduction in Cr-doped amorphous gallium arsenide films

Amorphous Cr-doped GaAs has been prepared by rf sputtering and the dc conductivity measured at fields up to 10⁷ V/m and temperatures down to 80 K. The results are explained in terms of field-assisted hopping. Effects of isothermal annealing at temperatures up to 200°C are studied. The studies are repeated and the results compared with undoped a-GaAs. Room temperature resistivities of a-GaAs: Cr, a-GaAs and polycrystalline GaAs are also compared. The recrystallization temperature for a-GaAs films is determined to be between 320°C and 340°C.     

Synthesis of four liquid crystals and study of alkyl chain effect on the nematic range for application in GC

Four liquid crystals (LCs) compounds which contain the 1,3,4-oxadiazole group were synthesized and characterized with spectroscopic techniques (IR, ¹H- and ¹³C NMR), their thermal properties were analyzed by the Differential Scanning Calorimetry (DSC) and the polarizing microscope (POM). A comparative study of the mesomorphic properties of these LCs and three other compounds which have already been used as a stationary phase in gas chromatography (GC) was carried out. These compounds have the same main nucleus. LCs V1, LC1, LC2 and LC3 gave a nematic (N) phase to the heating, LCs V2 and V3 recorded smectic A (SmA) and N phases. However, the range (N) has disappeared in V4.     

Hopping conduction in amorphous Nb2O5 thin films

The low field conduction mechanism in amorphous Nb₂O₅ doped with Nb is investigated by measurements of the ac conductivity as a function of frequency (3 Hz?6 × 10⁶ Hz), dc conductivity as a function of temperature (100–400 K), capacitance as a function of frequency (3 Hz?6 × 10⁶ Hz) and conductance G as a function of voltage at 10³ Hz. Loss tangent and quality factor data are also given because of their technical and scientific relevance. Evidence for hopping conduction at low applied fields is presented by the following results: (1) a monotonic increase in ac conductivity σ(ω)αωⁿ where 0.5 < n < 1.0 in the range 3 Hz?6 × 10⁶ Hz; (2) a linear dependence of current on voltage at low fields; and (3) low activation energy for dc conduction with a transition at 210 K to a still lower activation energy; and (4) a decrease in polarizability with frequency. At high fields, E > 10⁵ V/cm, dc conductivity is dominated by the field emission mechanism of the Poole-Frenkel or Poole type.     

The Structure of Lyotropic Nematic Decylammoniumchloride and Bromide Systems by PMR of Monomethyltin Complexes and by Microscopic Studies

The pmr spectrum of methyltintrichloride in aqueous micellar solutions of decylammoniumchloride and KCl, and of decylammoniumbromide and KBr was investigated. The large scalar SnH couplings of 134.0 Hz and 130.2 Hz respectively indicate the formation of six coordination complexes CH₃SnCl₅ ^{- -} and CH₃SnBr₅ ^{- -} in the micellar solutions, but the geometrical structure of the CH₃Sn moiety is little affected by the complex formation. The complexes orient with their symmetry axis preferably parallel to the nematic axis.

In microscopic studies on selected mixtures a reversible first order phase transition was observed between nematic and isotropic micellar solution at about 45°C and a reversible transition between a lamellar smectic phase and the nematic phase at about 30°C that appears to be of second order. The optical observations and the orientation of the methyltin complex indicate that the nematic solutions have micelles of a bilayer structure.     

Modifications of epitaxy in evaporated films by electric charge effects

Modifications of epitaxy in Ge, Si, CdS, β-Sn, and α-Fe films, 100–600 Å in thickness, evaporated onto air-cleaved and vacuum-cleaved (001) NaCl substrates under electron bombardment (∽10¹⁵ electrons/cm² sec, at 200–400 V) or an electric field (dc 100–300 V/cm) applied to the substrate surface were investigated by reflection electron diffraction, transmission electron microscopy and selected-area diffraction. Results indicated that epitaxial temperatures of Ge and Si films were considerably lowered, and a monocrystalline β-Sn film was produced by the application of electron bombardment. The application of electric field resulted in the formation of an epitaxial cubic CdS phase, and a single orientation in an α-Fe film. These results are discussed in terms of current speculation concerning the electric charge effects on alkali halide substrates.     

Synthesis and supramolecular interactions involved in the crystal structure of (2,4,10,12-tetrabromo-6,7,14,15-tetrahydro-6, 14-thiacycloocta[1,2-b:5,6-b’]diquinoline)2·(1,1,2,2-tetrachloroethane) inclusion compound

The tetrahalo aryl inclusion host 2,4,10,12-tetrabromo-6,7,14,15-tetrahydro-6,14-thiacycloocta[1,2-b:5,6-b’]diquinoline 3 was re-synthesized to explore its ability to trap toxic polychlorinated hydrocarbons such as 1,1,2,2-tetrachloroethane (TCE) in the form of host–guest compound. Host 3 crystallizes from a fresh sample of TCE to form an inclusion compound of the formula (3)₂·(TCE) in triclinic system, space group P-1, with a = 7.7732(16) Å, b = 10.739(2) Å, c = 14.816(3) Å, α = 97.329(4)°, β = 98.619(4)°, γ = 103.359(4)°, V = 1172.7(4) ų, and Z = 2. The X-ray crystal structure of the (3)₂·(1,1,2,2-TCE) is described and analyzed in terms of crystal engineering and supramolecular chemistry. The hosts assemble by means of different types of packing motifs. The included TCE molecules are enclosed within host molecular pens. Novel halogen···halogen intermolecular interactions as well as other non-covalent intermolecular interactions involved in the crystal structure are presented and proved to play an important role in linking these host–host, host–guest, and guest–guest building blocks.     

Investigation of the Solubility of Pleochroic Dyes in Liquid Crystals

A precise, inexpensive and relatively fast method for determining the solubility of pleochroic dyes in liquid cyrstals is described. The method has been used to investigate the solubility of two anthraquinone dyes in liquid crystals of different molecular structure. The solubility of the dye is found to be strongly dependent on the molecular structure of the dye and that of the host liquid crystal. Also the temperature dependence of the solubility in the nematic phase has been found to be different from that in the isotropic phase of the liquid crystals. At the nematic isotropic phase transition temperature a discontinuity in the solubility curve has been observed.