Azobenzene Liquid‐Crystalline Polymer for Optical Switching of Grating Waveguide Couplers with a Flat Surface

Grating waveguide couplers with a flat surface were fabricated in an azobenzene liquid‐crystalline polymer film by holographic lithography using Ar⁺ laser beams at 488 nm. When a probe beam at 633 nm was incident to one grating of a grating waveguide coupler, the beam propagated in the waveguide and an output beam came out from the other grating with the throughput coupling efficiency of ≈5%. Upon irradiation of the film between two gratings with UV light to cause trans–cis photoisomerization of the azobenzene moiety, the intensity of the output beam was repeatedly switched. It was found that the alternating irradiation at 366 and 436 nm induced reversible changes in the intensity of the guided probe beam.

     

Assembly of an Achiral Chromophore into Light‐Responsive Helical Nanostructures in the Absence of Chiral Components

The chirality found in living organisms is one of unsolved mysteries on Earth. It is crucial to understand the manner in which small achiral molecules evolve into helical superstructures in the absence of chiral components because this process can provide important insights regarding the origin of chirality in nature. 1) the uncommon helical assembly of an achiral trigonal chromophore into helical nanostructures with aggregation‐induced emission enhancement (AIEE) characteristics and 2) the tunability of the helical pitch and fluorescence intensity in response to light is reported. The Rietveld refinement of X‐ray diffraction (XRD) patterns and the growth process suggest that a striking transformation from an achiral to an asymmetric molecule can occur as a result of specific interactions with certain solvents, presumably leading to the unique helical assembly. More importantly, exposure to UV or visible light promoted not only the formation of irregular helical structures with a wide range of pitch lengths but also an increase in fluorescence intensity.     

Synthesis and properties of ferro- and antiferroelectric esters with a chiral centre based on (S)-(+)-3-octanol

A homologous series of chiral three ring esters were synthesised and their properties were studied. The materials possess an antiferroelectric phase (SmC_A*) or/and a ferroelectric phase (SmC*), which was confirmed by observations of microscopic textures using a polarising optical microscope. The phase transition temperatures and enthalpies were checked by differential scanning calorimetry. The helical pitch was measured by a spectrophotometry method. For all cases the helix is right-handed, in the antiferroelectric phase the helical pitch increases with temperature, and in the ferroelectric phase the helical pitch is short.     

Polymer-stabilized cholesteric liquid crystal microgratings: a comparison of polymer network formation and electro-optic properties for mesogenic and non-mesogenic monomers

Polymer-stabilized liquid crystal microgratings are made using a focused Gaussian UV laser beam to photopolymerize 3 wt % reactive monomer in a cholesteric liquid crystal host. In a typical case, round gratings of 300 μm diameter and 10 μm pitch are produced. The microgratings highlight interesting differences between mesogenic and non-mesogenic monomers in the assembly and spatial distribution of polymer networks formed in a cholesteric host. We also observe a corresponding variation in the electro-optical properties of the stabilized gratings. In the mesogenic case, the grating state of the liquid crystal is faithfully captured even for relatively short UV exposures and over regions only a few pitch lengths in size. These findings are consistent with phase separation of the mesogenic monomer into regular domains templated by periodic, macroscopic variations in orientational order of the host. This templating effect is significantly reduced in the non-mesogenic case.     

Polymer-stabilized cholesteric liquid crystal microgratings: a comparison of polymer network formation and electro-optic properties for mesogenic and non-mesogenic monomers

Polymer-stabilized liquid crystal microgratings are made using a focused Gaussian UV laser beam to photopolymerize 3 wt % reactive monomer in a cholesteric liquid crystal host. In a typical case, round gratings of 300 μm diameter and 10 μm pitch are produced. The microgratings highlight interesting differences between mesogenic and non-mesogenic monomers in the assembly and spatial distribution of polymer networks formed in a cholesteric host. We also observe a corresponding variation in the electro-optical properties of the stabilized gratings. In the mesogenic case, the grating state of the liquid crystal is faithfully captured even for relatively short UV exposures and over regions only a few pitch lengths in size. These findings are consistent with phase separation of the mesogenic monomer into regular domains templated by periodic, macroscopic variations in orientational order of the host. This templating effect is significantly reduced in the non-mesogenic case.     

Light-rewritable geometric phase and reflectance modulations enabled by pattern-aligned photoresponsive liquid crystal superstructures

ABSTRACT

We propose a universal method of fabricating and operating a multifunctional diffractive optical element (DOE) with light-rewritable geometric phase and reflectance modulations enabled by pattern-aligned photoresponsive liquid crystal superstructures via manipulating the photoalignment layers as well as the phototunable helical pitch of the cholesteric liquid crystal (CLC) under different light stimuli, i.e. ultraviolet and visible (green) lights. The diffractive behaviour of the fabricated CLC DOE is simultaneously governed by the geometric phase induced by the pattern-aligned CLC and the reflectance (amplitude) modulation attributed to the helical pitch manipulation, endowing the proposed DOE with versatile practical light-controllable characteristics and outstanding performance.     

Photo-induced control of bubble domains in chiral–nematic liquid crystal by a violet laser beam

The stable bubble domains generated by mixing 10% of chiral molecules into an azobenzene liquid crystal (LC)-doped nematic host can be optically controlled by a violet laser beam (415 nm). The photon-induced reversible trans–cis photo-isomerisation of azobenzene changes the helical twisting power (HTP) of LC mixtures in which the HTP of cis-azobenzene LC is lower than trans-azobenzene LC. Under the irradiation of an optical field (>20 mW cm^???2), the helical pitch distance, which is inverted proportional to the HTP, increases and the bubble domains disappear. Immediate obstruction of laser light irradiation initiates cholesteric nucleation, merging of domains and the subsequent generation of stably dispersed bubble domains.     

Nanocomposites Based on Antiferroelectric Liquid Crystal (S)-MHPOBC Doping with Au Nanoparticles

Modification of the physical properties of the (S)-MHPOBC antiferroelectric liquid crystal (AFLC) by doping with low concentrations of gold nanoparticles is presented for the first time. We used several complementary experimental methods to determine the effect of Au nanoparticles on AFLC in the metal–organic composites. It was found that the dopant inhibits the matrix crystallization process and modifies the phase transitions temperatures and switching time, as well as increases the helical pitch and spontaneous polarization, while the tilt angle slightly changes. We also showed that both the LC matrix and Au nanoparticles show strong fluorescence in the green light range, and the contact angle depends on the temperature and dopant concentration.     

Biphotonic recording effect of polarization gratings based on dye-doped liquid crystal films

This study investigates a holographic recording effect of biphotonic polarization gratings (BPGs) written on dye-doped liquid crystal (DDLC) films. One linearly polarized green light (λ_G = 514.5 nm) and a polarization-modulated interference pattern formed by two mutually coherent orthogonal (±45° with respect to the polarization of the green light) polarized red lights simultaneously excite the DDLC films to generate a BPG. The formation of BPGs depends primarily on the dichroism of the dye molecules and a sequence of mechanisms: photoisomerization, anisotropic adsorption and inhibition of dye adsorption. The cis-isomer absorbance-modulated distribution associated with the red polarization-modulation pattern induces the dye adsorption-modulated pattern, in turn, yielding the permanent BPG which generates a modulated twisted nematic (TN) structure pattern in the sample. It is found that each BPG is verified to be electrically switchable and thermally erasable. The switching time is in the order of milliseconds. Additionally, the recording time to form a BPG decreases with increasing intensity of the green pump beam.     

Double UV polymerisation with variable temperature-controllable selective reflection of polymer-stabilised liquid crystal (PSLC) composites

In this study, a method of preparing wide-band reflection cholesteric liquid crystals (CLCs) films by UV-radical polymerisation in combination with UV-cationic polymerisation is proposed. Because the helical twisting power (HTP) of the chiral dopant decreases with increasing temperature and the polymerisation rate of UV-initiated free radical polymerisation is faster than UV-initiated cationic polymerisation, by adjusting the temperature, broadband reflective films with non-uniform pitch distribution are obtained. The fractured surface of the polymer network of the broadband reflective films is observed by scanning electron microscopy (SEM), which reveals the presence of non-uniform pitch distribution. In addition, the influences of monomer concentration, UV light intensity and UV curing time on the consequent non-uniform pitch distribution have been studied.     

Lattice structure in liquid-crystal blue phase with various chiral concentrations

Lattice structures, including reflection lattice planes and lattice constant, of liquid-crystal blue phase I (BPI) are studied via the measurements on reflection spectrum and Kossel diagram as concentration of a chiral dopant is changed. Peaks of the reflection wavelength in BPI are mainly dominated by the lattice plane and the lattice constant, which are affected by the chiral concentration. In the chiral nematic state, as decreasing the chiral concentration the reflection peak will shift to a longer wavelength because the helical pitch linearly depends on the chiral concentration and becomes longer. However, this dependence of the chiral concentration and reflection wavelength is broken in the BPI. The reflection peak of BPI moves to a short wavelength when the chiral concentration is less due to the contraction of the lattice constant as well as helical pitch. Moreover, when the concentration of the chiral dopant increases over a certain value, a discontinuous shift in reflection peak occurs due to the production of the different lattice planes. It means that the relationship between the chiral concentration and the helical pitch in BPI is not the same as it in the chiral nematic phase and should be reconsidered.     

Helix parameters in bi- and multicomponent mixtures composed of orthoconic antiferroelectric liquid crystals with three ring molecular core

Eight types of bicomponent systems composed of antiferroelectric compounds with different polarity of achiral chain and different temperature dependence of helical pitch as well as three multicomponent mixtures composed of antiferroelectric compounds with opposite helical twist sense were studied. The phase miscibility was tested by polarising optical microscopy. The results of the helical pitch and helical twist sense measurements obtained by a spectrophotometric method of selectively reflected light and by polarimetric method, respectively, are presented. It was found that it is possible to control helical pitch length and temperature of helix twist inversion in antiferroelectric mixtures by controlling the ratio of compounds with left- and right-handed helix in such mixtures, although all of them have the same chiral terminal chain.     

Light wave propagation in periodic tilted liquid crystal structures: a periodic beam propagation method

Periodically deformed liquid crystal profiles are commonly encountered either spontaneously under the influence of an external excitation, or intentionally, with the introduction of relief type gratings on the supporting surfaces. These types of periodicity are often characterized by a pitch around one micron or less. As the pitch is directly comparable to the optical wavelength, it is necessary to develop rigorous numerical methods to predict light wave propagation within such structures. A wide angle periodic beam propagation method (BPM) is proposed for the simulation of light propagation in purely bend/splay periodic director deformations. A common occurrence of this type of deformation is encountered in smectic A materials under the Helfrich effect. More importantly, bistable nematic cells with zenithal deformation have been developed for interesting display applications. Both aforementioned deformations are examined to verify the applicability of the proposed periodic BPM.     

Helical pitch of ferroelectric liquid-crystalline polymers and copolymers

Ferroelectric liquid-crystalline polymers and copolymers were synthesized from acrylate polymers with side chains consisting of a flexible spacer unit, a mesogenic unit and an optically active substituent. In the chiral smectic C (S*_c) phases typical fan-shaped textures with equidistant lines (caused by the helical structures) were observed. It was found that the helical pitch increased with increasing polymer molecular weight. The helical pitch also increased in copolymers containing mixtures of right- and left-handed chiral side chains.     

Discontinuous change in the helical pitch of cholesteric liquid crystals by photoisomerization of a chiral azobenzene molecule

This paper describes the discontinuous change in the helical pitch of a cholesteric liquid crystal (ChLC) by means of the photoisomerization of chiral azobenzene molecules under homogenous alignment conditions. A mixture of E44, R811 and Azo was prepared in the ratio 68/28/4, respectively. R811 and Azo have opposite twisting abilities such that they induce right- and left-handed helices, respectively when added to E44. The mixture was injected into a glass cell having a 2 or 5 µm cell gap, and treated for homogeneous molecular orientation. The wavelength of selective reflection from the ChLC was shifted to shorter wavelengths by the trans-cis photoisomerization of Azo. The change in the helical pitch was not only discontinuous, but also dependent on the cell thickness. The discontinuous change in the helical pitch was estimated to be almost the same as the half turn of the helical pitch in each cell gap, and was dependent on the number of helical half pitches in the glass cell. The homogeneous alignment condition affects the photochemical change in the helical structure of the ChLC system.     

Optical grating recording in highly organized thin films of Disperse Red 1

Optical grating recording with submicrometer spatial resolution, which can handle grey-level patterns, has been investigated in photochromic material made of Disperse Red 1 (DR1) molecules vacuum-deposited on a glass substrate. Holographic gratings of periods Λ within the range of 0.6 μm - 12 μm were recorded by 514.5 nm light from cw Ar⁺ laser using a degenerate two-wave mixing technique. Despite the very small DR1 layer thickness (∼ 0.1 μm), the diffraction efficiency measured in a Raman-Nath scattering regime reached 2 %. The obtained amplitude gratings were analysed with an optical microscope and Fourier transforms. Grating profiles were analysed in relation to exposure conditions and in correlation with molecular organisation. Polarising microscopy studies revealed the presence of light-induced optical anisotropy. Following that, we have checked the possibility of polarisation-sensitive recording in this medium.     

On the anomalous temperature dependence of ferroelectric Sc*. liquid crystals

A biaxial elastic model for the temperature dependence of S_c* helical pitch is proposed on the basis of a phenomenological theory of S_c* liquid crystals accompanied by a biaxial molecular ordering playing an important role for the anomalous behaviour of the helical pitch near the S_c*-S_A transition point. In the S_c*. phase of p-(n-decyloxybenzylidene)-p-amino-(2-methylbuthyl)-cinnamate (DOBAMBC), a qualitative agreement with the observed helical pitch is found by choosing a few material parameters concerned with a biaxial elasticity and an anisotropy of the elastic constants.     

Discontinuous change in the helical pitch of cholesteric liquid crystals by photoisomerization of a chiral azobenzene molecule

This paper describes the discontinuous change in the helical pitch of a cholesteric liquid crystal (ChLC) by means of the photoisomerization of chiral azobenzene molecules under homogenous alignment conditions. A mixture of E44, R811 and Azo was prepared in the ratio 68/28/4, respectively. R811 and Azo have opposite twisting abilities such that they induce right- and left-handed helices, respectively when added to E44. The mixture was injected into a glass cell having a 2 or 5?µm cell gap, and treated for homogeneous molecular orientation. The wavelength of selective reflection from the ChLC was shifted to shorter wavelengths by the trans-cis photoisomerization of Azo. The change in the helical pitch was not only discontinuous, but also dependent on the cell thickness. The discontinuous change in the helical pitch was estimated to be almost the same as the half turn of the helical pitch in each cell gap, and was dependent on the number of helical half pitches in the glass cell. The homogeneous alignment condition affects the photochemical change in the helical structure of the ChLC system.     

Lateral resolution of secondary ion mass spectrometry–results of an inter‐laboratory comparison

Recently, BAM organised an inter‐laboratory comparison focussed on lateral resolution and accuracy of sub‐micron length measurements by secondary ion mass spectrometry (SIMS). Results were submitted by 16 laboratories from 10 countries. The task was to analyse a cross‐sectioned semiconductor multilayer stack. The resulting strip pattern in the surface of the sample shows narrow strips, step transitions and gratings of different periods. Imaging analysis of this pattern enables the determination of relevant parameters related to the lateral resolution: (i) The width (FWHM) of the primary ion beam, (ii) the distance between 16% and 84% intensity points in a profile across the image of a step transition and (iii) the modulation of intensity in the images of gratings with different periods. The parameter's data reported by the participants vary in a wide range. A strong variation in the data of primary ion beam width was observed for results measured with the same type of instrument. The distance between two narrow strips was measured with high accuracy. Twelve of sixteen of the submitted values are within the limits of uncertainty of the reference value 964 ± 35 nm. This result shows that the calibration of the length scale of the SIMS instruments is already rather precise in most of the participating laboratories. Copyright © 2006 John Wiley & Sons, Ltd.     

Pyroelectric investigations of polarization and charge distributions in sandwich cells containing a ferroelectric liquid crystalline polymer

With the laser intensity modulation method (LIMM), polarization and charge profiles in sandwich cells containing the ferroelectric liquid crystal side group polymer LCP1 have been investigated. In a sample with a thickness larger than the helical pitch, contributions to the polarization profile due to surface anchoring were found. Additional contributions inside the cell occurred. The validity of the results, concerning numerical deviations in the deconvolution process of the pyrospectra, has been tested by simulations. The influence of space charges for measurements with a static external electrical field is discussed, giving contributions to the profile in addition to those arising from polarization.