Nanoparticle enabled thermal control of ions in liquid crystals

Typically, ionic species in thermotropic liquid crystals are nearly fully ionised. Therefore, the concentration of mobile ions practically does not depend on the temperature. Interestingly, the same liquid crystals doped with nanoparticles exhibit totally different behaviour. The concentration of mobile ions become temperature dependent. This paper reports the effects of the temperature on the concentration of ions in liquid crystal nanocolloids. Liquid crystals doped with both 100% pure and contaminated nanoparticles are considered. Regardless the ionic purity of nanodopants, the concentration of mobile ions in liquid crystal nanocolloids increases towards the saturation as their temperature goes up. The magnitude of this saturation level equals the initial concentration of ions in liquid crystals doped with 100% pure nanoparticles. The temperature induced release of ions by contaminated nanoparticles in liquid crystals increases the above-mentioned saturation level. While the dispersion of 100% pure nanoparticles in liquid crystals leads to the temperature-dependent purification only, the use of contaminated nanoparticles results in the temperature-driven switching between the purification and contamination regimes enabling thermal control of ions.     

Impact of contaminated nanoparticles on the non-monotonous change in the concentration of mobile ions in liquid crystals

The ionic purity of nanoparticles can affect electrical properties of liquid crystals in very unusual ways. While 100% pure nanoparticles can only decrease the concentration of mobile ions in liquid crystals by means of adsorption/desorption processes, nano-dopants contaminated with ions can lead to the increase, decrease and no change in the concentration of ions. Moreover, these changes can exhibit non-monotonous behaviour as a function of the nanoparticle loading. The level of the liquid crystal contamination or purification, achieved by doping them with nanoparticles, is always limited by the physical quantity called the critical concentration of ions. From applied perspectives, results presented in this paper can be used in the selection of nano-materials, the most suitable for the liquid crystal purification.     

Low-voltage polymer-stabilised blue-phase liquid crystals with oleic acid (OA)-modified LaF3 nanoparticles

The resultant oleic acid (OA)-modified LaF₃ (OA-LaF₃) NPs were easily dispersed well in common organic solvents or liquid crystals (LCs). Usually, the stability of BPs depends on a well-arranged double-twisted alignment and a stable defect. Theoretical simulation shows that the BPLCs is likely to trap the doped nanoparticles due to the elastic interactions.By means of the OA-LaF₃ NPs we synthesized and doping into conventional polymer-stabilized blue phase liquid crystals (PS-BPLCs), it was observed that the on-state voltage can be reduced by 41% when the PS-BPLCs doped with 0.8wt. % OA-LaF₃ NPs compared with that PS-BPLCs without OA-LaF₃ NPs. It showed significant effects on the driving voltage when doping OA-LaF₃ NPs to PS-BPLCs. Our studies will certainly provide an effective and simple method to stabilize cubic BP structures and improve the electronic-optical performances, leading to potential applications in areas of displays as well as optoelectronic devices.     

Time-dependent electrical properties of liquid crystal cells: unravelling the origin of ion generation

An understanding of possible sources of ion generation in liquid crystal materials is of utmost importance to ensure uncompromised performance of modern liquid crystal devices. In this paper, time-dependent electrical properties of filled liquid crystal cells are used to reveal important information about often overlooked source of ion generation in liquid crystals. This source of ions originates from the ionic contamination of substrates of the liquid crystal cell. Ionic contaminants can be inherently present in the alignment layers or can be induced by external factors such as mechanical rubbing or irradiation with light. The model of this ion generation process is presented and tested using existing experimental data.     

Terahertz properties of liquid crystals doped with ferroelectric BaTiO3 nanoparticles

In this paper, we present the results of the terahertz measurements of liquid crystal (LC) ferroelectric BaTiO₃ nanoparticles (nps) suspensions in the range of frequency from 0.3 up to 3.0 THz. Two different sol-gel methods and the harvesting technique were used to fabricate the nanoparticles. Five LC materials served as hosts for the suspensions: two single compounds: 6CHBT and 2,3′,5′-trifluoro-4-(4-pentylcyclohexyl)-4′-(trifluoromethoxy)-1,1′-biphenyl, and three mixtures: 1867, 2037 and 2020. We characterise, for the first time, the refractive indices and absorption parameters of suspensions with harvested nps in the terahertz range and show how the process of the nps’ preparation affects their response. We observed the increase of birefringence for few LC suspensions in comparison with the pure LCs. The highest increase of birefringence was for 2020 suspension with one kind of ferroelectric nps. On the other hand in most cases the addition of ferroelectric nps to LC causes the increase of its absorption in the THz range. The measurements of LCs terahertz properties by using time-pulsed spectrometer were performed.     

Electrical properties of liquid crystal nano-colloids analysed from perspectives of the ionic purity of nano-dopants

The concentration of mobile ions in liquid crystals doped with nano-objects is analysed in the framework of the Langmuir isotherms assuming an ionic contamination of nano-dopants. The level of the ionic purity of nano-dopants is described by means of the dimensionless contamination factor. The applicability of the proposed approach is verified by fitting the broad variety of the existing experimental data. A good agreement between theoretical predictions and experimental data indicates the feasibility of the idea to consider nano-dopants partially contaminated. In addition, it provides the way to deduce a set of important parameters (the surface density of the adsorbing sites, the contamination factor and the ratio of the adsorption constant to the desorption constant) directly from electrical measurements.     

Dielectric properties of a strongly polar nematic liquid crystal compound doped with gold nanoparticles

This study focuses on the electrical characteristics of a strongly polar nematic liquid crystal, Hexyloxy-cyanobiphenyl (6OCB), doped with a low concentration (2% by weight) of citrate buffer stabilised gold nanoparticles (GNPs) at low frequencies between 20 Hz and 35 MHz. The doped samples have lower values of nematic–isotropic transition temperature, permittivity (both parallel and perpendicular to the field direction) and dielectric anisotropy; however, relaxation time and activation energy were increased. The observed results could be explained on the basis of weakly anisotropic nature of GNPs and a local rearrangement of liquid crystal molecules surrounding the nanoparticles. Moreover, a complimentary suggestion on a possible change in the dipole–dipole correlation is made to explain the difference in changes (qualitative and quantitative) observed for permittivity of the host nematic liquid crystal doped with GNP. Temperature dependent dielectric relaxation studies indicate an increase in viscosity and potential barrier; and hence a change in strength of inter-molecular and intra-molecular interactions is suggested.     

Improvement of the electro-optical properties of nematic liquid crystals doped with strontium titanate nanoparticles at various doping concentrations

ABSTRACT

In this study, we doped homogenous aligned nematic liquid crystal (NLC) systems with strontium titanate (SrTiO₃) nanoparticles (NPs), and investigated the impact of doping concentration on the NLC’s electro-optical (EO) properties. SrTiO₃ NP-doped NLC cells maintained a high optical transmittance of 77.51% to 78.41% compared to pure NLC cells (78.09%). At a 0.1 wt.% SrTiO₃ NP doping concentration, twisted-nematic (TN)-LC cells exhibited enhanced EO performance, with a reduced threshold voltage from 1.70V to 1.61V and a shorter response time from 17.03 ms to 10.66 ms without optical defects and degradations. We also observed an improvement in thermal endurance for doping concentrations of 0.05 and 0.1 wt.%.     

Monosubstituted ferrocene liquid crystals containing click triazole with a wide nematic phase temperature range

New monosubstituted ferrocenomesogens of the 1,4-substituted-1,2,3-triazole series 3a-3d and the 5-halogen-1,4-substituted-1,2,3-triazole series 4a-4d were successfully synthesised through a facile and versatile synthetic route using click reactions with moderate yields, in different atmospheres, and catalysed by different amounts of CuX (X = Br, I). Two series of compounds exhibited a typical nematic liquid crystal texture, and the 5-halogen-1,4-substituted-1,2,3-triazole series 4 had a wider mesomorphic temperature range than the corresponding series 3 due to the effect of the halogen atom substituent on the triazole. These compounds showed similar absorption spectra, but the fluorescence emission spectra of 4 were obviously redshift relative to 3. Cyclic voltammetry investigations revealed that the redox-active ferrocenyl groups of 3 and 4 follow one-electron transfer processes.     

Memory effects in chiral nematic liquid crystals doped with functionalised single-walled carbon nanotubes

Octadecylamine-functionalised single-walled carbon nanotubes (SWCNTs) were dispersed into nematic liquid crystals (LCs) doped with chiral molecules. The collective orientation of nematic LC molecules in helical layers was manipulated by varying dopant concentration. Highly anisotropic nature of SWCNTs enhanced the anisotropy of the LC as confirmed by polarised fluorescence spectroscopy. The π–π interaction of SWCNTs present in the planar alignment layers and twisted nematic LC molecules affects the molecular relaxation process. An irreversible electro-optic memory in the material has been observed.     

Diffusion of Cesium Ions Labeled with 134 Cs in Agar Gel Containing Alkali Metal Iodides: Obstruction Effect and Activation Energy

The effect of some alkali metal iodides on the obstruction effect and activation energy for tracer-diffusion of cesium ions in an agar gel medium was studied using the zone-diffusion technique. It to be observed that both the extent of obstruction (α) and the activation energy (E) decrease with the increasing charge density of the cation of the supporting electrolyte. These trends are explained on the basis of competitive hydration between ions and agar molecules and the relative distortion in the water structure that is brought about by these different ions and agar molecules, respectively.     

Enhancement of electronic excitation energy transfer in the colloidal crystals of colloidal silica suspensions doped with fluorescent dyes

The efficiency of electronic excitation energy transfer from photo-excited rhodamine 110 (Rh110, energy donor) to rhodamine B (RhB, energy acceptor) in an exhaustively deionized colloidal silica suspension has been studied. This colloidal suspension shows Bragg reflection due to the formation of colloidal crystals and the Bragg-peak wavelength is controllable by the volume fraction of the silica spheres. When the Bragg-peak wavelength matches with the fluorescence band of Rh110, a depletion was observed in the Rh110 fluorescence spectrum. This means the fluorescence of Rh110 is partially trapped due to the Bragg reflection inside the crystal lattice. In the coexistence of RhB, the enhancement of RhB fluorescence intensity was observed. These facts clearly indicate the trapped photon energy of Rh110 is efficiently transferred to RhB within the colloidal crystals. The quantitative measurements showed that the enhancement of the transfer efficiency is 20% (or slightly more) in the present experimental conditions.     

Applications of liquid crystals in biosensing and organic light-emitting devices: future aspects

ABSTRACT

This article summarises recent advances made in our laboratory towards the development of new technological applications, such as biosensors and organic light-emitting diodes (OLEDs) based on liquid crystals (LCs) other than LC displays. The study of biomolecular interaction using LC material relies on the specific interaction between the LC and the biomolecule of interest at interfaces that permit the biomolecular events to be amplified into easily measured signals for various sensing applications. In the first part, we emphases recent studies in the design and modulation of LC-based interfaces based on robust colloidal LC gels for biological amplification, qualitative and quantitative understanding of important biomolecular interactions at LC–aqueous interfaces for diagnostic and laboratory applications and design of LC droplets that hold promise to act as a marker for cells and cell-based interactions. In the second part, we described design of organic materials for application in OLEDs on various discotic monomers, dimers and oligomers. These molecules have the ability to transport charges, holes and electrons. In addition, because of the high conductivity and π–π stacking, they are considered as the advanced materials for practical applications. The technological advances in our laboratory using discotic LCs will be briefly presented in this article.     

Orientational dynamics and energy landscape features of thermotropic liquid crystals: An analogy with supercooled liquids

Recent optical kerr effect (OKE) studies have revealed that orientational relaxation of rodlike nematogens near the isotropic-nematic (I-N) phase boundary and also in the nematic phase exhibit temporal power law decay at intermediate times. Such behaviour has drawn an intriguing analogy with supercooled liquids. Here, we have investigated the single-particle and collective orientational dynamics of a family of model system of thermotropic liquid crystals using extensive computer simulations. Several remarkable features of glassy dynamics are on display including non-exponential relaxation, dynamical heterogeneity, and non-Arrhenius temperature dependence of the orientational relaxation time. Over a temperature range near the I-N phase boundary, the system behaves like a fragile glass-forming liquid. Using proper scaling, we construct the usual relaxation time versus inverse temperature plot and explicitly demonstrate that one can successfully define a density dependent fragility of liquid crystals. The fragility of liquid crystals shows a temperature and density dependence which is remarkably similar to the fragility of glass forming supercooled liquids. Energy landscape analysis of inherent structures shows that the breakdown of the Arrhenius temperature dependence of relaxation rate occurs at a temperature that marks the onset of the growth of the depth of the potential energy minima explored by the system.     

Nanocomposites of ferroelectric liquid crystals and FeCo nanoparticles: towards a magnetic response via the application of a small electric field

ABSTRACT

We study a nanocomposite consisting of a ferroelectric liquid crystal and a magnetic nanoparticle in order to explore the possibility of using it as a magnetic resonant imaging contrast agent which will measure a field of 20 V/m. To achieve this we use the ferroic properties exhibited by the nanocomposite. We used the ferroelectric liquid crystal 2-(4-((2-fluorooctyl)oxy)phenyl)-5-(octyloxy)pyrimidine mixed with FeCo nanoparticles nominally 2–3 nm in diameter in concentrations of 0.56, 4.3 and 10.8 wt%. The 10.8 wt% sample was chosen for our study because the nanoparticles acted as a lubricant for the ferroelectric liquid crystal. This concentration yields nanoparticle clusters in about 5 ? 10 μm diameter spherulites. An electric field as low as 5V/cm is enough to turn and realign the spherulites where the particles are contained. We estimate the value of the magnetic in a spehrulite and associate it to the number of spherulites aligned as a function of electric field. We find thus that we can achieve low electric fields.     

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.     

Liquid crystalline guanidinium phenylalkoxybenzoates: towards room temperature liquid crystals via bending of the mesogenic core and the use of triflate counter ions

A series of guanidinium salts 1(C _n ) _m –4(C _n ) _m ?X bearing phenyl alkoxybenzoate cores have been synthesised and their mesomorphic properties have been investigated by polarising optical microscopy (POM), differential scanning calorimetry (DSC) and powder X-ray diffraction experiments (small-angle X-ray scattering and wide-angle X-ray scattering). While compounds 1(C₁₂)₁?X and 3(C₁₂)₁?X with one alkoxy chain showed smectic A (SmA) phases irrespective of the counter ion, compounds 1(C₁₂)₂?OTf and 3(C₁₂)₂?OTf with two alkoxy chains displayed SmA phases and the corresponding chlorides 1(C₁₂)₂?Cl and 3(C₁₂)₂?Cl displayed Col_h. Guanidinium salts 1(C _n )₃–4(C _n )₃?X with three alkoxy chains showed Col_h phases. Whereas the use of cyclic guanidinium head groups rather than acyclic ones had only a minor influence on the mesophase properties, melting points were significantly decreased by bent core units instead of linear core units. Replacement of chloride counterions by triflate lead to a further depression of the clearing points and shifted the mesophase towards room temperature.     

A comparison of temperature and mobile phase composition effects for bonded liquid crystal and polymeric stationary phases in HPLC

Summary Using two polycyclyic aromatic hydrocarbons as solutes, a comparison is made between a bonded liquid crystal stationary phase and a conventional polymeric C-18 phase. The bonded nematic liquid crystal phase was the silanized form of 4-[4-(allyloxy)benzoyl-oxy]biphenyl and the polymeric phase was Vydac 201TP. Both phases display shape and planarity selectivity as indicated by the results of the variable temperature and mobile phase composition studies. The slot theory of retention can be used to explain these results. However, the liquid crystal phase is more sensitive to molecular geometry, probably due to its more ordered structure on the surface. Variable temperature experiments which compare retention during both heating and cooling provides additional support for this conclusion. With the polymeric bonded C-18 phase, each solute had identical retention at the same temperature during both the heating and cooling cycles. On the bonded liquid crystal phase, measurable differences in retention were observed at identical temperatures depending on whether the column was heated or cooled. This effect is attributed to a degree of partially reversible disordering which occurs as the column temperature was increased. However, conditioning with the appropriate mobile phase can restore the original retention characteristics of the bonded liquid crystal phase.     

Photosensitivity,substituent and solvent-induced shifts in UV-visible absorption bands of naphthyl-ester liquid crystals: a comparative theoretical approach

The substituent- and solvent-induced shifts in UV-visible absorption bands of naphthyl-ester nematic liquid crystals, viz., 4-octylphenyl-6-octyloxy-2-naphthoate (NAPHE1) and 6-octyloxy-2-naphthylyl-4-octyloxybenzoate (NAPHE2), have been investigated using the DFT, CNDO/S and INDO/S methods. A correlation has been made between molecular charge distribution and phase stability based on Mulliken, Loewdin, AM1, PM3, MNDO, CNDO/S and INDO/S methods. The observed π→π* and n→π* electronic transitions have been reported. The substituent- and solvent-induced shifts in absorption bands, transition energies and energy gaps have been discussed. The photosensitivity of the molecules has been analysed based on these shifts. It has been observed that the substituent has a dominant role on both absorption maxima and energy band gap, whereas the solvent has a dominant role only on absorption maxima, and no effect has been observed on the energy gap. These shifts may provide beneficial consequences in determining the end use of compounds.