Image analysis method to study electro-optic parameters of nematogens

This paper demonstrated the image analysis technique for the investigation of electro-optic behaviour of homogeneously aligned nematic liquid crystals p-n alkyl benzoic acids (nBA) where n = 5 and 6 under the application of direct current (DC) electric field. Textures of the liquid crystals in the mesophase region of particular temperature were recorded in three monochromatic image planes at the wavelengths of 635 (red), 530 (green) and 475 nm (blue) as a function of applied DC voltage. Electro-optic properties such as transmittance, birefringence, phase retardation and contrast ratio were measured by analysing the optical intensities of the recorded textures using MATLAB software. The changes in the textural features and formation of new textures as a function of voltage provided information for better understanding of the electro-optic characteristics of liquid crystals. Results of this study were compared with the data of the other standard techniques: laser source (633 nm) experiment and United Detector Technology (UDT) sensor of model UV- 35P silicon photo diode which uses white light as source and filters the wavelengths using three colour filters of wavelengths 635, 530 and 475nm.     

Azo polymers for reversible optical storage. 11 poly{4,4′-(1-methylethylidene)bisphenylene 3-[4-(4-nitrophenylazo)phenyl]-3-aza-pentanedioate}

Poly{4,4′-(1-methylethylidene)bisphenylene 3-[4-(4-nitrophenylazo)phenyl]-3-aza-pentanedioate} (pMNAP) was synthesized through the condensation polymerization of 4,4′-isopropylidene-bis-phenol and N-[4-(4-nitrophenylazo)phenyl]imido diacetyl chloride. The polymer solution in tetrahydrofuran (THF) was spin-coated onto a glass substrate to form a film and the process of reversibly photoinduced birefringence was tested. The birefringence induced in the film was observed to a level of 0.04. The biexponential fitting of the birefringence growth and relaxation curves shows two kinds of processes. A fairly low birefringence relaxation occurs after the light is turned off, about 12% at room temperature and less than 50% at 138°C, close to the glass transition temperature (152°C). pMNAP decomposes at about 160°C which prevents its use as a material for optical storage. © 1996 John Wiley & Sons, Inc.     

Optical properties of a mesogen by image analysis

An image analysis technique in conjunction with polarising optical microscopy (POM) is proposed for assessment of the thermo-optical properties of homogeneously aligned chiral ester liquid crystals of the type ((S)-(-)-2-methylbutyl 4′-(4″-n-alkanoyloxybenzoyloxy) biphenyl-4-carboxylates, where n?=?16 or 18. Chiral ester textures are recorded as a function of temperature using POM provided with a hot-stage and a high-resolution colour camera. Temperature-dependent optical parameters, or thermo-optical properties such as optical transmission, degree of polarisation, absorption coefficient and birefringence are computed for chiral esters by analysing the texture of samples using MATLAB software. This is a simple experimental technique for observing how the optical parameters of liquid crystals change with temperature.     

Ultrafast switchable wide angle negative refraction in novel dual-frequency liquid crystal mixture

Ultrafast switchable wide angle negative refraction in a novel dual-frequency liquid crystal mixture is demonstrated experimentally. Laterally fluorinated isothiocyanato phenyl-tolane liquid crystal compound is doped into Merck MLC-2048 to acquire the high birefringence dual-frequency liquid crystal. The maximum negative refraction angle achieved is about 12° and the switching time is only 25 ms for a 40-μm cell which is two orders faster than switchable negative refraction achieved before in nematic liquid crystals. Such properties provide a feasible approach to design negative refraction devices based on liquid crystals.     

Simulations of some physical parameters of homologous series of nBT and nCHBT at 0.3–20.0 THz

ABSTRACT

In this work, the terahertz (THz) absorption of homologous series of isothiocyanobiphenyls (nBT) and 4-(trans-4?-n-alkylcyclohexyl)isothiocyanato-benzene (nCHBT) are simulated by using the density functional theory (DFT) method. Numerical results show that absorption of the tested nematic liquid crystals (NLCs) varies up to 0.04 in the broad range of 0.3–20.0 THz and takes maximum value in the range of 9–14 THz.

In addition, the values of molecular polarisabilities (α_o, α_e) increase with the increase in the number of carbon atoms in the alkyl chain, while refractive indices (n_o, n_e) decreases. The calculated birefringence (Δn) values for nCHBT are approximately twice as large as the birefringence value for nBT. It is crucial to examine these series of nematic liquid crystals at THz frequencies due to the role of soft matter in various switchable THz components.     

New isothiocyanatotolane liquid crystals with terminal but-3-enyl substitute

Four kinds of new but-3-enyl-based isothiocyanate liquid crystals composed of tolane core and but-3-enyl terminal group (A1–A4) were synthesised via seven step reactions based on 2-(4-bromophenethyl)-1,3-dioxolane, and four n-butyl analogues B1–B4 as comparison structures were also prepared. The mesomorphic properties and physical properties of the compounds were investigated. Single fluorinated compounds A2 and A3 exhibit monotropic nematic phase, and they have lower melting enthalpy and higher clearing points than those of the comparison compounds B2 and B3. The non-fluoro-substituted compound A1 and difluorinated compound A4 exhibit no nematic phase. Replacement of n-butyl chain by but-3-enyl as terminal group is enabled to increase birefringence (Δn ~ 0.394–0.430) and reduce rotational viscosity. These isothiocyanatotolanes with terminal but-3-enyl substitution have potential application for high birefringence mixtures.     

Synthesis and evaluation of dinaphthylacetylene nematic liquid crystals for high-birefringence materials

We synthesised 1,2-bis(6-alkoxy-2-naphthyl)acetylene as a new dinaphthylacetylene liquid crystal (LC) compound with alkoxy tails of length m (DNA–OCm) and characterised their phase behaviour by polarising optical microscopy and differential scanning calorimetry, where all compounds exhibited a nematic phase. Also, we measured the actual, and not extrapolated, Δn values of this target compound, and our results show the birefringence potential of the pure LC compound. They have high birefringence values, with the highest value of approximately 0.5 obtained for DNA–OC2 at 550 nm at 10°C above the nematic?crystal transition temperature.     

Heterocyclic pyridine-based liquid crystals: synthesis and mesomorphic properties

A series of new calamitic liquid crystals, 4-{[(pyridin-4-yl)methylidene]amino}phenyl 4-alkoxybenzoates comprising a heterocyclic (pyridine) and two phenyl rings core system, terminal alkoxy chain, imine and ester linkers were synthesised and characterised. This series consists of nine members wherein the members differ by the length of alkoxy chain (C_nH_2n+1O–, where n = 2, 4, 6, 8, 10, 12, 14, 16, 18). Spectral analysis results were in accordance with the expected structure. Their thermotropic behaviours were studied by using differential scanning calorimetry, optical polarising microscopy and powder X-ray diffraction techniques. A single mesophase (nematic) was observed for the first three members of the series (n = 2, 4 and 6). As the alkoxy chain increased to n = 8 and n = 10, the nematic phase appeared together with an additional smectic A (SmA) phase. When moving from n = 12 until the highest members (n = 18), the nematic phase disappeared and these compounds only exhibited a single mesophase (SmA).     

Synthesis and mesomorphic evaluation of new calamitic liquid crystals containing benzothiazole core

The design and synthesis of new calamitic benzothiazole-based liquid crystals,2-[4-（4-alkyloxybenzoyloxy）-phenyl]ben-zothiazoles are presented.The target compound was characterized using spectroscopic techniques,such as FT-IR,NMR(¹H and ¹³C),microanalysis and EI-MS.The liquid crystalline behaviours of these compounds were thoroughly examined by differential scanning calorimetry and polarizing optical microscope techniques.These materials exhibited enantiotropic nematic phase with high thermal stability（>168℃）.Smectic A phase starts to emerge as monotropic（metastable） phase from C10 member and changes into enantiotropic（stable） phase from C12 and persists up to C16 members.     

Terahertz properties of fluorinated liquid crystals

In this article, optical properties of four fluoro-substituted 4-propyl-4′-[(4-ethylphenyl)ethynyl] biphenyls and liquid crystal mixture A are presented in the terahertz (THz) range. Birefringence, refractive indices and absorption coefficients for ordinary and extraordinary ray of liquid crystals are described in the range of 0.3 to 3.0 THz. It shows that the measured parameters are dependent on the number and placement of fluorine atoms in the molecules. Measurements have been performed using time-pulsed spectroscopy.     

Novel high birefringent isothiocyanates based on quaterphenyl and phenylethynyltolane molecular cores

We report the synthesis of new laterally alkyl substituted high birefringent quaterphenyl and phenylethynyltolane liquid crystals with isothiocyanate terminal group. The thermal and optical properties such as birefringence are measured and discussed based on their molecular structures. The compounds exhibit birefringence (Δn) in the range of 0.44–0.63, and are expected to be appropriate components of high birefringent nematic mixtures for various applications.     

Sub‐millisecond response phase modulator using a low crossover frequency dual‐frequency liquid crystal

A high birefringence (Δn = 0.292 at λ = 633 nm, 25°C) and low crossover frequency (<1 kHz at T = 25°C) dual‐frequency liquid crystal (DFLC) mixture was developed. The high birefringence enabled us to use a thin liquid crystal cell, which is helpful for fast response time and low operating voltage. The initially low crossover frequency allowed us to operate the DFLC device at an elevated temperature, which significantly lowers the viscosity while keeping the crossover frequency in an acceptable range (<10 kHz). We demonstrated a 2π phase shifter at λ = 633 nm using such a DFLC and obtained a sub‐millisecond response time at T～45°C. This type of DFLC mixture together with elevated temperature operation opens a new way for achieving fast response time.     

Improved thermal stability of an organic zeolite by fluorination

The thermal stability of an organic zeolite material, namely 2,4,6-tris(4-bromo-3,5-difluorphenoxy)-1,3,5-triazin (Br-3,5-DFPOT), was improved by fluorination of 2,4,6-tris(4-bromophenoxy)-1,3,5-triazin (BrPOT). The open pore structure (van der Waals diameter of 10.5 Å) of the modified zeolite was observed up to 110 °C in comparison to 70 °C for BrPOT. Nitrogen sorption at low temperature showed a type I isotherm and derived pore volumes thereof are in agreement with structural data. It was observed here that Br-3,5-DFPOT crystals preserving the open pore structure could only be obtained below a typical size of about 50 μm. The improved thermal stability of the fluorinated system is attributed to an enhancement of the strength of the Br₃-synthon.     

Analysis of tunable characteristics of liquid-crystal-based hyperbolic metamaterials

We propose a voltage-tunable hyperbolic dispersion metamaterial (HDM) consisting of silver nanowires and nematic liquid crystals (NLCs). The metamaterial shows a novel electro-optic effect, in which the dispersion relation switches between elliptic and hyperbolic dispersions at the visible waveband with an external electric field. HDM functionality is analysed in detail based on the effective medium theory. 5CB NLC is chosen for the simulation, and tunability is achieved between 454 and 475 nm. The effects of filling ratio on tunability are also analysed. Tunable bandwidth widens from 21 to 45 nm with decreased filling ratio from 0.27 to 0.09. Finally, the effects of birefringence (Δn) are considered. Tunable bandwidth widens from 21 to 63 nm as Δn changes from 0.2 to 0.6. These novel tunable performances of the HDM can be applied to optical devices and optical systems.     

Synthesis of novel (-)-menthol-based azobenzene chiral liquid crystals and effect of terminal alkyl chains on mesomorphic behaviour

ABSTRACT

A series of novel azobenzene chiral liquid crystals (Mt4AZOnB) containing (-)-menthyl were successfully synthesised. Terminal alkyl chains of the molecules varied from methyl to hexyl. The chemical structures were characterised by Fourier transform infrared and ¹H-NMR spectra. Liquid crystalline behaviour of the chiral liquid crystals was characterised by differential scanning calorimetry and polarising optical microscopy. The effect of terminal alkyl chains on mesomorphic and photoisomerisation behaviour of azobenzene-based liquid crystals is discussed. The lower members (n = 1, 2, 3, 4) are monotropic and only the higher members (n = 5, 6) show enantiotropic behaviour. These compounds show a distinct odd-even effect for the phase transition temperature when the parity of the terminal chain is varied.     

Development of ferroelectric liquid crystals with low birefringence

We propose an approach for development of ferroelectric liquid crystals (FLC) with low birefringence Δn. Two basic principles have been used to get lowering of Δn: selection of molecules with short chains of conjugation as components for achiral matrix and averaging of local refractive indices by FLC helical structure. FLC mixtures with low birefringence (0.07 < Δn < 0.10 at wavelength 589.3 nm of sodium line) were elaborated and investigated. They consist of an achiral matrix including both nematic and smectic liquid crystal components and of phenylpyrimidine derivatives as chiral dopants. The materials developed can be used for all basic electro-optical FLC modes such as surface stabilised FLC (SSFLC), deformed helix ferroelectrics (DHF) and electrically suppressed helix (ESH). The mixtures developed allow to reduce the FLC cells chromatic retardance variation due to the weaker birefringence dispersion as compared with the known FLC materials to date.     

新型含萘基和二乙炔基高双折射液晶分子的合成及光电性能

通过多步Sonogashira偶联反应成功合成分子结构中含萘环的不对称二乙炔衍生物:4-(4-(4-(6-(己氧基)-2-萘基)-1-(1,3-丁二炔基))-3-乙烯基-苯乙炔基)-N,N-二甲基苯胺。 通过核磁共振和元素分析对其结构进行了表征,通过差式扫描量热分析(DSC)、偏光显微镜(POM)和阿贝折射仪研究了其液晶性和双折射特性;通过紫外-可见吸收光谱仪和荧光分光光度计测得其吸收-发射光谱。 测量发现该化合物具有热致型向列相液晶特性和很高的双折射值(Δn=0.47)。 化合物溶液荧光发射波长为470 nm,荧光量子产率高达97%。 应用旋转涂膜的方法制作的双层器件ITO/PEDOT/liquid crystal compound/Mg:Ag(10:1)/Ag(ITO:氧化铟锡,PEDOT:聚3,4-乙撑二氧噻吩),电致发光波长为503 nm,器件显示了较好的电致发光稳定性和二极管整流特性,启动电压较低(6.75 V),在14.75 V时达到最大亮度150 cd/m²。 该化合物有望作为一种潜在的液晶显示材料和电致发光材料。     

Novel method for order parameter of ferroelectric liquid crystals by image analysis

A novel method for temperature dependence of order parameter calculations at different wavelengths through birefringence measurements for ferroelectric liquid crystals (S)-(-)-2-methylbutyl 4′-(4″-n-alkanoyloxy benzoyloxy) biphenyl-4-carboxylates (where n?=?16 and 18) has been proposed using image analysis and linear regression method of Kuczynski equation. Measurements are made for its liquid crystal phases (SmecticC*, SmecticA) to the isotropic phase of the sample. The birefringence values of the samples at different wavelengths are obtained from the textural analysis of liquid crystal as a function of temperature using MATLAB software.     

Surface-mediated photoalignment of discotic liquid crystals on azobenzene polymer films

This paper describes a simple strategy for the formation of photoaligned and micropatterned discotic liquid crystal (DLC) film on the surface of photoirradiated azobenzene-containing polymer thin film. The key material for the surface-mediated photoalignment of the DLCs was poly[4-(4-cyanophenylazo)phenyl methacrylate] (pMAzCN). Optical anisotropy was generated in a pMAzCN film by oblique exposure to nonpolarized light which resulted in angle-selective photoisomerization and reorientation of the azobenzenes. Subsequent annealing of the film at 240 degrees C enhanced the photoaligned state of the p-cyanoazobenzenes due to strong intermolecular dipole-dipole interaction and semicrystalline nature of the pMAzCN. This combination of photoirradiation and subsequent annealing of the pMAzCN film made it possible to realize the surface-assisted orientation control of a DLC molecule, which displays both columnar (Col) and discotic nematic (N(D)) phases over 152 degrees C. When the pMAzCN film was exposed to linearly polarized light from the surface normal, the DLC molecules showed homeotropic orientation with the director perpendicular to the substrate surface. In the contrast, oblique irradiation of the pMAzCN film with nonpolarized light gave rise to tilted DLC orientation with well-ordered optical birefringence at the N(D) phase. Rapid cooling from the N(D) phase produced a well-aligned glassy N(D) state at room temperature, which was adequately stable for 10 months even though no covalent cross-linking among the DLCs was performed. The spatial orientation of photoaligned DLCs in both their bulk film and in their interface region was characterized by means of optical birefringence, X-ray diffraction, and fluorescence measurements. At the N(D) phase, the DLC molecules were aligned in a hybrid manner such that their tilt angles varied throughout the thickness of DLC film. The direction of tilted DLCs was opposite to the propagation of the actinic nonpolarized light. The photoaligned DLC films exhibited polarized fluorescence emission with an s-polarized/p-polarized intensity ratio of 4.1, despite the nonpolarized excitation of only DLC at outmost surface. These results indicate that the three-dimensionally aligned azobenzene moieties of the pMAzCN thin film were transferred to the tilted DLC molecules at air/DLC interface. Finally, we demonstrated micrometer-scale photopatterned orientation of DLC molecules on the pMAzCN surface by oblique nonpolarized irradiation of the film through a photomask.     

Synthesis and the effect of 2,3-difluoro substitution on the properties of diarylacetylene terminated by an allyloxy group

A series of 2,3-difluoro tolane allyloxy-based liquid crystals (LCs), which are composed of the tolane unit, lateral fluoro substituents, alkoxy and allyloxy terminal groups, were synthesised with 4-bromo-2,3-difluorophenol as the starting material via a five-step reaction. Their structures were confirmed by infrared spectroscopy (IR), mass spectroscopy (MS) and nuclear magnetic resonance (NMR). The mesomorphic properties were investigated by differential scanning calorimetry (DSC) and polarising optical microscopy (POM). The dielectric measurement was performed using an independent analyser EC-1 and the birefringence was determined using an Abbe refractometer. The results reveal that LCs have large negative dielectric anisotropy and high birefringence, which are potentially important for the fast response displays and liquid crystal photonic devices (LCDs).