Fabrication of photoluminescent liquid crystal device using an in situ self-assembled molecular layer of a pyrene derivative

An in situ self-assembled molecular layer of 1-pyrenesulfonic acid sodium salt as an alignment agent was formed on indium tin oxide substrates for vertically aligning liquid crystals (LCs). The thus-aligned LCs exhibited uniform vertical alignment under crossed polarisers. The electro-optical characteristic of the LC cell fabricated using this method exhibited better performance than those of conventional LC cells with a polyimide alignment layer. Because the proposed alignment method is a simple one and involves low concentrations of the alignment agent (0.05 wt%), it is highly cost-effective. Further, the pyrene derivative, when mixed with LCs, exhibited photoluminescence (PL) under ultraviolet light. Given that the proposed method resulted in highly vertically aligned LCs and the alignment agent exhibited PL, the method should find wide use in the fabrication of colour-filter-free LC displays.     

Voltage-expandable liquid crystal surface

Based on dielectrophoretic effect, we report a novel approach which can extensively spread a liquid crystal (LC) interface. With interdigitated striped electrodes, the droplets can be stretched along the striped electrode direction; while with zigzag interdigitated electrodes, the droplets can be further stretched sidewise. In our demonstration, the occupied area of a 1.9-mm-aperture LC droplet doped with 1.2 wt% black dye could be expanded over ～3.5× at 78 V(rms). The spreading and recovering times were measured to be ～0.39 s and ～0.75 s, respectively. The slower response time confirms the extreme expanding of the LC surface. The contrast ratio is over ～120?:?1 in transmissive mode. Color light switch was also demonstrated by spreading colored-dye doped LC droplets. The mechanical stability of the device was also evaluated. Liquid devices based on this cell structure have the advantages of good stability, simple operation and low power consumption. This work opens a new gateway for voltage controllable, polarization-insensitive, and broadband liquid photonic devices which may find numerous applications in switchable windows, variable optical attenuators, and displays.     

Study of dynamic light scattering in nematic liquid crystal and its optical,electrical and switching characteristics

In the present study, the polarisation-independent dynamic light scattering (DLS) in a nematic liquid crystal (LC) with a negative dielectric anisotropy has been compared in two operating modes by applying DC voltage or AC voltage to LC cells with a vertical and hybrid alignment. The attenuation of light transmittance and the DLS optical threshold without polarizers as well as a phase retardation of LC bend–splay deformation and a Fredericks threshold voltage with polarizers have been determined. Diffuse scattering of a light beam and broadband transmittance spectra of LC cells have been examined using the DC voltage in the interval of 0–40 V. Multi-domain structures and turbulent flows in the LC cells have been observed by polarisation optical microscope. The results show that the enhancement of the diffuse scattering of light in the LC cells correlate with ion density increase. The largest attenuation of the light intensity in the LC cells with a vertical alignment was 16.4 dB at a wavelength of 650 nm with a minimum decay time equal to 2.5 ms at DC voltage of 60 V. Our study has been shown that switching from a diffuse light scattering state to a transparent state can be twice accelerated by applying AC voltage with high frequency to LC cells.     

Vertical alignment of liquid crystal on tocopherol-substituted polystyrene films

We synthesised a series of vitamin-based and renewable tocopherol-substituted polystyrene (PTOC#, # = 20, 40, 60, 80 and 100), where # is the molar content of tocopherol moiety, using polymer analogous reactions to investigate their liquid crystal (LC) alignment properties. In general, the LC cell fabricated using the polymer film having a higher molar content of tocopherol side group showed vertical LC alignment behaviour. The vertical alignment (VA) behaviour was well correlated with the surface energy value of these polymer films. For example, VA was observed when the surface energy values of the polymer were smaller than about 35.22 mJ/m² generated by the nonpolar tocopherol moiety having long and bulky carbon groups. Good electro-optical characteristics, such as voltage holding ratio and residual DC voltage, and aligning stabilities at 200°C and ultraviolet irradiation of 10 J/cm² were observed for the LC cells fabricated using PTOC100 as a LC alignment layer. Therefore, it was first found that the renewable tocopherol-based materials can produce an eco-friendly vertical LC alignment system.     

Liquid crystal alignment properties of 2-naphthoxymethyl-substituted polystyrenes

The liquid crystal (LC) alignment properties of LC cells fabricated with films of 2-naphthoxymethyl-substituted polystyrenes with different contents of naphthoxymethyl side groups were investigated. The polymer films exhibited good optical transparency in the visible light region (400–700 nm). The LC cells made from the unrubbed films of polymers having more than 57 mol%?of 2-naphthoxymethyl containing monomeric units showed homeotropic LC alignment with a high pretilt angle of about 90^o. Good electro-optical characteristics, such as the threshold voltage, response time, voltage holding ratio and residual DC voltage were observed for the LC cells fabricated with the polymer having 100 mol%?of 2-naphthoxymethyl containing monomeric units as an LC alignment layer.     

Self-constructed stable liquid crystal alignment in a monomer-liquid crystal mixture system

Here, we demonstrate excellent liquid crystal (LC) vertical alignment without using an alignment layer printing process by introducing octadecyltrichlorosilane (OTS) into the LC mixture. Further, we investigated the alignment mechanism by analysing the surfaces of the substrates. The optimum concentration of OTS was found to be about 0.03 wt%, which is 1/100 of that in the previously reported polyhedral oligomeric silsesquioxane (POSS)–LC system. Moreover, the OTS–LC system exhibited a more stable LC alignment compared with the POSS–LC system. These differences may arise from the different strengths of surface–dopant interactions; that is, the covalent bond in the OTS–LC system and the van der Waals interactions in the POSS–LC system. We also demonstrated that the method can be used in a capillary tube, which may serve as a new method facilitating the application of LCs with curved surfaces.     

Enhanced Photocatalytic Degradation of Synthetic Dyes and Industrial Dye Wastewater by Hydrothermally Synthesized G–CuO–Co<Subscript>3</Subscript>O<Subscript>4</Subscript> Hybrid Nanocomposites Under Visible Light Irradiation

To enhance the degradation of colour and chemical oxygen demand using photocatalytic activity, Graphene–CuO–Co₃O₄ hybrid nanocomposites were synthesized using an in situ surfactant free facile hydrothermal method. The photocatalytic degradation of synthetic anionic dyes, methyl orange (MO) and Congo red (CR), and industrial textile wastewater dyes under visible light irradiation was evaluated. The synthesized nanocomposite was characterized structurally and morphologically using X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, high-resolution transmission electron microscope, and Fourier transform infrared spectroscopy. Evaluation of the colour indicated complete removal at 15 min of irradiation for the MO and CR dyes, with 99% degradation efficiency. The reaction time for the primary effluent wastewater dye was 60 min for 81% dye removal. In contrast, a longer reaction time was required to meet the national discharge regulation for the raw wastewater dye, 300 min for 60% dye removal. The mechanism for dye degradation using the Graphene–CuO–Co₃O₄ hybrid nanocomposite was elucidated using the Langmuir–Hinshelwood model, and the rate constant and half-life of the degradation process were calculated. The results demonstrate that photocatalytic degradation using a hybrid nanocomposite and visible light irradiation is a sustainable alternative technology for removing colour from wastewater dye.     

Liquid crystal alignment behaviours on poly(methyl methacrylate) having polyhedral oligomeric silsesquioxane groups

A series of poly(methyl methacrylate) derivatives containing polyhedral oligomeric silsesquioxane (POSS) groups (MCP#) were synthesised via free radical polymerisation (FRP) using methacryl isobutyl POSS (MA-POSS) and methyl methacrylate as monomers to investigate liquid crystal (LC) alignment property of these polymer films. The LC cells made from the films of the polymers having 100 mol% of MA-POSS units (MCP100) showed vertical LC alignment having a pretilt angle of about 90°. The vertical LC alignment behaviour on the MCP100 film was ascribed to the very hydrophobic MCP100 surface having the surface energy value smaller than about 23 mJ/m² generated by the nonpolar bulky POSS group. Good electro-optical characteristics, such as voltage holding ratio (VHR) and residual DC voltage (R-DC), were observed for the LC cells fabricated using MCP100 as a LC alignment layer.     

ZnS nanoparticles capped with watermelon rind extract and their potential application in dye degradation

We report fabrication of stable ZnS nanoparticles (NPs) using a green chemistry concept with watermelon rind extract as capping and stabilizing agent. The cubic structure of the NPs was evidenced by X-ray powder diffraction analysis and electron diffraction studies. Dynamic light scattering and high-resolution transmission electron microscopy studies revealed that the average size of the ZnS NPs was <12 nm. The bandgap of the ZnS nanocrystals was found to be 3.42 eV using ultraviolet–visible (UV–Vis) spectroscopy studies. The energy-dispersive X-ray spectrum of the fabricated ZnS NPs confirmed the elemental Zn and S signals without peaks from any impurities. The biomolecular capping of the ZnS NPs was analyzed using Fourier-transform infrared spectroscopy. An illustrative stabilization mechanism for the ZnS NPs is given using citrulline, a major phytochemical in watermelon rind extract. The obtained ZnS NPs showed good photocatalytic activity towards methylene blue dye degradation.     

Orientational control of liquid crystal molecules via carbon nanotubes and dichroic dye in polymer dispersed liquid crystal

Polymer dispersed liquid crystals (PDLCs) using nematic liquid crystal and photo-curable polymer (NOA 65) were prepared by polymerisation-induced phase separation technique, in equal ratio (1:1) of polymer and liquid crystal (LC). We demonstrate that doping of small amount (0.125%, wt./wt.) of multiwall carbon nanotubes (CNTs) and orange azo dichroic dye in PDLC generously controlled the molecular orientation, dynamics of LC in droplet and size of droplets. The effects of multiwall CNTs and dye on PDLCs were studied in terms of transition temperature, droplet morphology, transmittance characteristic, contrast ratio and response time. The results exhibited that the values of the threshold electric fields were reduced from 8 V/µm (pure PDLC) to 1.18 and 1.72 V/µm, doped with multiwall CNTs and dye, respectively. The CNTs-doped PDLC shows faster switching response as compared with pure PDLC and dye-doped PDLC. However, dye-doped PDLC shows much higher contrast among all PDLC samples. Further, the results also illustrate that the birefringence value of LC in PDLCs was changed with doping of CNTs and dye.     

Photoluminescence tuning and electro-optical memory in chiral nematic liquid crystals doped with silver nanoparticles

The photoluminescence spectra of chiral nematic liquid crystals doped with dodecanethiol-functionalised silver nanoparticles has been investigated. The peak intensity level of the photoluminescence in PL spectra was found to be consonant with the concentration (0.005–0.020 wt%) of silver nanoparticles. An uptrend of enhancement in the peak intensity was also recorded up till 0.015 wt% of dopant concentration, above which a fall in the peak intensity was recorded. A significant shift in the peak position was also detected with chiral dopant concentration. Electrically induced optical hysteresis was observed in the doped samples, which virtually vamooses at 0.020 wt% dopant concentration. Marked improvement in the attributes of silver-doped chiral nematic liquid crystal material under investigation has ensured vital appositeness of the composite for making memory and high-contrast display devices.     

Enhancement of frequency modulation response time for polymer-dispersed liquid crystal

Through the ferroelectric nanoparticles of BaTiO₃ (BTO) doping, the response time for the frequency modulation of the polymer-dispersed liquid crystal (PDLC) was improved. The BTO-doped PDLC cells were prepared by polymerisation induced phase separation (PIPS) process using UV light. The capacitance of the PDLC composites was measured with an impedance analyzer in the frequency range of 100 Hz–1 MHz at 1 V. The dynamic signal for the response time of the PDLC devices was monitored through a digital oscilloscope. The electro-optical properties of the PDLC were found to strongly depend on the doped BTO concentration. The BTO doping caused a large increase in the capacitance. The dielectric constants were drastically decreased in the samples with rather low BTO doping ratio at a high frequency. No outstanding difference in the rising time of the LC was observed in the BTO-doped PDLC device, but the falling time was significantly decreased from 0.334 to 0.094 s. The present results imply that the nanoparticle-doping technology could improve the electro-optical performance of the PDLC requiring fast response and frequency modulation, such as optical modulators and PDLC-hybrid electroluminescence device for flexible electronic devices.     

Fluorescent dye guest-host effects in advanced ferroelectric liquid crystals

Previous work has shown that guest-host ferroelectric systems incorporating dichroically absorbing dyes are suitable for use in colour display applications. These utilize either the dichroic absorption of a conventional dye, or the emission of a fluorescent dye. We present here the electrooptical properties of several advanced ferroelectric liquid crystals doped with a new fluorescent dye, coloured blue in emission. The data consists of measurements of tilt angle, response time, spontaneous polarization, and rotational viscosity, from which we conclude that certain hosts are not adversely affected by the fluorescent dopants. These results are then discussed in connection with the use of these mixtures in two novel colour display configurations, which are also presented, utilizing either the dichroic absorption or the polarized fluorescence of the fluorophore guests.     

Tunable polarised fluorescence of quantum dot doped nematic liquid crystals

The concentration, excitation photon wavelength, and polarisation dependent fluorescence of quantum dot (QD)–liquid crystal (LC) mixtures has been studied at room temperature using high-resolution, steady-state fluorescence spectroscopy. The fluorescence of QD–LC mixture increases with increasing QD’s concentration but the spectral red shift of ~10 nm relative to the stock QD–Toluene solution remains independent of concentration. In vertical switching (VS) cells, an external electric field changes the LC alignment direction and enhances the apparent fluorescence intensity. The apparent fluorescence anisotropy compared to that at zero applied electric field monotonically increases up to ~27% at an applied electric field of 0.6 V/µm. These results are consistent with the formation of disc-like assemblages of QDs oriented on planes perpendicular to the director of the nematic liquid crystal (NLC). These findings have important utility in polarisation sensitive photonic devices.     

Fluorescent dye guest-host effects in advanced ferroelectric liquid crystals

Abstract

Previous work has shown that guest-host ferroelectric systems incorporating dichroically absorbing dyes are suitable for use in colour display applications. These utilize either the dichroic absorption of a conventional dye, or the emission of a fluorescent dye. We present here the electrooptical properties of several advanced ferroelectric liquid crystals doped with a new fluorescent dye, coloured blue in emission. The data consists of measurements of tilt angle, response time, spontaneous polarization, and rotational viscosity, from which we conclude that certain hosts are not adversely affected by the fluorescent dopants. These results are then discussed in connection with the use of these mixtures in two novel colour display configurations, which are also presented, utilizing either the dichroic absorption or the polarized fluorescence of the fluorophore guests.     

Effects of the fluorinated liquid crystal molecules on the electro-optical properties of polymer dispersed liquid crystal films

The different fluorinated liquid crystal (LC) molecules doped to E8 were used as LC component to prepare polymer dispersed liquid crystal (PDLC) films. The mass fraction of the LC mixture is fixed 50.0 wt%. Results indicate that doping 8.0 wt% fluorinated LC molecule ME3CP to E8 significantly reduced the driving voltage of the PDLC films, and the driving voltage reduced with the rise of mass fraction of ME3CP. Besides, the terminal flexible chain length of the fluorinated LC molecule influenced the LC mixture properties based on E8, such as the dielectric anisotropy, birefringence and viscosity of the LC mixture, and the morphology and the electro-optical properties of PDLC films were controlled not only by the physical properties of the LC mixture, but also by the terminal flexible chain length of the fluorinated LC molecule .     

Photo‐alignment material with azobenzene‐functionalized polymer linked in film

Application of a new azo‐polymer as a photo‐alignment material for liquid crystals (LCs) was demonstrated. 4‐(Vinyloxyethyloxy)azobenzene (VAZO), which has thermally reactive vinyl ether groups, reacted with the ? OH groups of poly(4‐hydroxystyrene) (PHS) during the baking process. The azo‐attached polymer (PHS‐VAZO) film showed anisotropic spectra after exposure to 365‐nm linear polarized light (LPL) unlike the VAZO‐doped poly(methylmethacrylate) (PMMA) film. The anisotropy of the film was small at high concentration of the azo‐chromophore because of thermal randomization of the polarized state. In the evaluation of photo‐alignment of the LC, the LC hybrid cell using the PHS‐VAZO film achieved high LC alignment. The azo‐attached polymer using the thermal reaction of vinyl ethers is useful for a photo‐alignment material. Copyright © 2002 John Wiley & Sons, Ltd.     

Synthesis of novel soluble rubbing-resistant polyimides used as liquid crystal vertical alignment layers

A novel functional diamine N12, containing triphenylamine moiety, biphenyl, tert-butyl substituents and long alkyl chain, N,N-bis(4-aminophenyl)-p-(3,5-di-tert-butyl-4-dodecyloxy phenyl) aniline (N12), was synthesised and characterised. A series of polyimides (PIs) were prepared based on 2,2?-bis(trifluoromethyl)benzidine, 4,4?-oxydiphthalicanhydride and different contents of N12 via a conventional two-step procedure that included a ring-opening polyaddition to gain polyamic acids, followed by chemical cyclodehydration. The chemical structures of the intermediates, diamines and PIs were characterised by Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. All of the PIs were amorphous and exhibited good solubility in both polar aprotic solvents and some low boiling point solvents. PIs containing different content of N12 could induce highly uniform vertical alignment of liquid crystals (LCs). More importantly, PIs derived from N12 showed a good rubbing resistance. Besides, all PI films showed high transmittance in the wavelength range 400–700 nm and good thermal stabilities. Such PIs could be suitable candidates for alignment layers used in the manufacture of high-performance vertical alignment mode LC displays.     

Light‐Driven Reversible Alignment Switching of Liquid Crystals Enabled by Azo Thiol Grafted Gold Nanoparticles

Stimuli‐directed alignment control of liquid crystals (LCs) with desired molecular orientation is currently in the limelight for the development of smart functional materials and devices. Here, photoresponsive azo thiol (AzoSH) was grafted onto gold nanoparticles (GNPs). The resulting hybrid GNPs were able to homogeneously mix with a commercially available nematic LC host, as evidenced by Cryo‐TEM. Interestingly, the LC nanocomposites were found to undergo reversible alignment transition upon light irradiation as a consequence of the trans–cis photoisomerization of the azo groups on the GNP surface. LC molecules in either planar or bare glass cells were able to change their alignment to vertical upon UV irradiation, while the vertically aligned LC molecules returned to the planar or random orientation under visible irradiation. Neither the azo thiol molecules nor the unfunctionalized GNPs alone promoted the alignment of the LC molecules in the system upon light irradiation. The photoinduced vertical alignment without applied electric or magnetic field was very stable over time and with respect to temperature. Furthermore, an optically switchable device based on the photostimulated reversible alignment control of LCs was demonstrated.     

Polarisation switching and molecular relaxation behaviour of anthraquinone dye-dispersed polymer-stabilised ferroelectric liquid crystal composites

Guest–host polymer-stabilised ferroelectric liquid crystal (GH-PSFLC) composite films have been prepared with dispersion of small concentration (0.1, 0.25 and 0.5 wt%) of anthraquinone blue dye in PSFLC host matrix via a polymerisation-induced phase separation (PIPS) process. The variation in alignment and size of twisted fibril has been observed in the optical textures of the guest–host composites with different wt/wt ratio of anthraquinone dye. The electrical and dielectric properties of PSFLC mixture and its guest–host derivatives are studied. Our results showed that an optimum amount of dye concentration (0.1 wt%) enhances the dielectric permittivity as well as the spontaneous polarisation of the GH-PSFLC material in the SmC* phase.