Characteristic dielectric parameters of para-, ferro- and antiferro-electric phases of (S)-4-(1-methylheptyloxycarbonyl)phenyl-4′-(6-pentanoyloxyhex-1-oxy)biphenyl-4-carboxylate

Frequency and temperature dependence of dielectric parameters of a liquid crystalline compound (S)-4-(1-methylheptyloxycarbonyl)phenyl-4′-(6-pentanoyloxyhex-1-oxy)biphenyl-4-carboxylate under planar orientation of the molecules have been investigated in the frequency range 1 Hz-10 MHz. This compound possesses smectic paraelectric (SmA*), ferroelectric (SmC*) and antiferroelectric (SmC_A*) phases. Dielectric spectroscopy suggests the existence of a relaxation mechanism in the SmA* phase, which behaves as a soft mode. In the SmC* phase two relaxation modes are observed. One mode continues from the SmA* phase with decreasing dielectric strength and the other has characteristics of the Goldstone mode. Two dielectric relaxation modes have been observed for the SmC_A* phase. These two modes are related to the antiferroelectric ordering and the helical structure of the SmC_A* phase.     

Nonlinear dielectric response of antiferroelectric liquid crystals in the smectic Cα * phase

Nonlinear dielectric response of antiferroelectric liquid crystals has been studied in the smectic C_α* (SmC_α*) phase. The linear dielectric spectrum shows a single relaxation of Debye type and its relaxation frequency is as high as one hundred kHz. The profile of the third-order nonlinear dielectric spectrum varies in complex fashion with temperature. In the vicinity of the SmA-SmC_α* phase transition, experimentally obtained nonlinear spectra are well described by those calculated with phenomenological theory of Landau type. The soft mode of the SmC_α* phase shows critical slowing-down near the transition temperature. In the lower-temperature region of the SmC_α* phase, the contribution from the soft mode of the SmC_α* phase reduces and the other relaxation mode with Debye-type spectrum appears at several hundred Hz in the nonlinear spectrum. The appearance of this low-frequency mode suggests that the cooperative fluctuation of directors over long range exists in the SmC_α* phase. Received 19 April 2002 and Received in final form 23 July 2002 RID="a" ID="a"e-mail: kimura@exp.t.u-tokyo.ac.jp     

Dielectric properties of LC mixture with induced antiferroelectric phase

Mixture of two liquid crystalline components exhibits the antiferroelectric phase in a broad temperature range at room temperatures, though the two components separately do not show an antiferroelectric phase in a temperature range applied. The dielectric spectroscopy technique combined with measurements of the selective light reflection was used for identification and characterization of the phases and subphases existing in the mixture. In the SmC*_A phase, the low frequency mode characteristic of antiferroelectric phase has been detected. In the broad temperature range between SmC*_A and SmA* phases, no relaxation mode has been detected. The soft mode registered near the phase transition to SmA* phase follows the Curie-Weiss law.     

Effect of multi-walled carbon nanotubes on dielectric and electro-optic properties of a high tilt antiferroelectric liquid crystal

By dispersing a small amount of multi-walled carbon nanotubes in a high tilt antiferroelectric liquid crystal, a nano composite is prepared. Though the phase sequence remains the same, the transition temperatures of the composite get changed, the stability of SmA* and SmC* phases increases whereas that of SmC_A* phase decreases. Pitch of the helicoidal structure shows a discontinuous change at SmC*–SmC_A* transition. Absorption strength and critical frequency of the anti-phase antiferroelectric mode are reduced in the composite. The dielectric increment of the Goldstone mode (GM) decreases and the critical frequency increases due to increased elasticity of the composite. A two-fold increase in the critical field for suppression of the GM is observed which signifies more stable helical structure in the composite. The switching time is reduced by 56% in the nano composite as a result of decrease in rotational viscosity but the high tilt remains intact. An observed lower value of conductivity indicates ion trapping in the composite.     

Dielectric measurements of new antiferroelectric liquid crystals

Three new pure antiferroelectric materials, synthesized at the Military University of Technology (MUT), were investigated by dielectric means. Clear relaxation modes were detected, i.e., Soft, Goldstone, low frequency in-phase (P_L) as well high frequency anti-phase (P_H) modes for paraelectric Sm A*phase, ferroelectric Sm C* phase and antiferroelectric Sm C_A* phase, respectively. Additionally, a high relaxation mode in Sm C_A* was found. The relaxation frequencies f_R of the observed modes were calculated from Cole-Cole diagrams.     

Dielectric relaxation behaviour of liquid crystals with opposite orientation of -COO ester group in molecular core

Dielectric measurements were performed for two smectogens, being structurally analogous with the opposite space orientation of the-COO ester group in the molecular core, using a HP4192A impedance analyser. Gold coated electrode cells of different thicknesses were used. Temperature dependences of the relaxation frequency fR and the inverse of the dielectric strength Δε′_┴ ⁻¹ obtained by fitting experimental values of perpendicular components, i.e., the real ε′_┴ and the imaginary ε″_┴ parts of the complex dielectric permittivity to the Cole-Cole equation as well as the investigation of modification of relaxation processes under bias were determined for the SmC_*, SmA_*, and N_* phases of studied compounds. One can conclude, on the basis of the above results, that dielectric relaxation processes observed by us in the studied compounds are similar to those of the soft and Goldstone mode typically observed by others in the SmC_*, SmA_*, and N_* phases. It is concluded from acomparison of their properties with other related compounds that the link between the biphenyl moiety and-COO ester group is closely related to the stability of smectic phases.     

Insights on some chiral smectic phases

Combining layered positional order as smectic order and chirality can generate complex architectures since twist parallel to the layers is not allowed. This paper will review some new experimental results on different phases resulting from the competition between smectic positional order and twist orientational order. It concerns the TGB_A and the NL^*, that is the liquid line phase as well as the SmQ phase. Chiral effects in the isotropic phase will also be discussed.     

Observation of relaxation modes in room temperature ferroelectric liquid crystal mixtures

The dielectric measurements in SmC* and SmA phases of a room temperature ferroelectric liquid crystal mixture FLC-6980 in the cells of different thickness in planer alignment have been carried out in the frequency range 100 Hz to 1 MHz. A relaxation mode (called NRM) whose dielectric increment is less than the Goldstone mode has been observed in the SmC* phase. This mode appears due to the surface effect. Goldstone mode and the soft mode was observable in the vicinity of SmC*-SmA transition temperature (T _C*A). The dielectric parameters of the Goldstone mode, new mode and the soft mode have been studied as a function of frequency and temperature. The calculated values for f_NRM, δε^NRM and distribution parameter α_NRM are found to be 325 kHz, 6 and 0.156 for 5μm thick planer cell at 37°C. It is seen that in the vicinity of theT _C*A, soft mode obeys the Curie-Weiss law given by mean field theory. The results have been compared with materials of large spontaneous polarization.     

Thermodynamic and bias field investigation of an antiferroelectric liquid crystal

Dielectric spectroscopy of an antiferroelectric liquid crystal material (S)-4-(1-methylheptyloxycarbonyl)phenyl-4′-(6-pentanoyloxyhex-1-oxy)biphenyl-4-carboxylate 4H6Bi(S) for its helical phases has been carried out under bias electric field in the frequency range 0.1 Hz-10 MHz. Bias field investigation has been carried out in order to explore new relaxation modes. Dielectric characterization of the material, when carried out as a function of DC bias, reveals soft mode around 350 kHz and domain mode at ∼100 Hz in the SmC^? phase as a consequence of suppression of Goldstone mode due to helix unwinding. In the SmC^?_A phase a field induced new relaxation mode has been investigated at 8.0 kV/cm having relaxation frequency from 100 Hz to 600 Hz with increasing bias electric field.     

Dielectric spectroscopy of liquid crystals. Electrodes resistivity and connecting wires inductance influence on dielectric measurements

Dielectric spectroscopy is a very useful experimental method for liquid crystal investigation. Electrodes made from indium tin oxide (ITO) or gold are widely used in measuring cells. During the dielectric spectroscopy measurements performed for smectic liquid crystalline mixture it was found that detection of some important relaxation modes in paraelectric SmA*, ferroelectric SmC* and antiferroelectric SmC_A* phases for frequencies higher than 0.2–0.5 MHz is not possible. The measuring setup does not allow us to measure such relaxations due to its own dielectric response covering the dielectric response of liquid crystalline medium. One can observe the spurious contribution for high frequency part of the dielectric spectrum, due to non-zero resistivity of electrode material or non-zero inductivity of connecting wires. In this paper, the new model was introduced. Its final equations show how to calculate parameters of relaxations observed in liquid crystals, from dielectric response of the empty and filled measuring cell. The experimental proof of strong influence of measuring setup properties on effective (measured) values of dielectric permittivities was shown.     

X-ray scattering study of the electric-field-induced layer deformations of an antiferroelectric Liquid Crystal

The effect of an external electric field on the local layer structure is investigated in the SmC^* _A, SmC^* _FI and SmC^* phases using X-ray diffraction. X-ray scattering and spontaneous polarization measurements are performed under several increasing (and decreasing) steps of AC applied voltage. The effects of the electric field differ significantly from one phase to the other. The chevron-to-bookshelf transition occurs abruptly at a high field value in the SmC^* _A phase whereas layer deformations are more progressive and occur at lower field values in the other phases. Comparison of the different behaviours suggests that the destruction of the chevron structure is mainly affected by the local molecular order. Received 16 July 2001 and Received in final form 7 December 2001     

Dielectric spectroscopy of liquid crystals. Theoretical model of ITO electrodes influence on dielectric measurements

Indium tin oxide (ITO) layers are widely used to make electrodes in measuring cells, because these layers are transparent and electrooptical investigations can be performed using such prepared cells. It was found during the dielectric spectroscopy measurements, performed for smectic liquid crystalline mixture, that it is not possible to detect some important relaxation modes in paraelectric SmA*, ferroelectric SmC*, and antiferroelectric SmC_A* phases for the frequencies higher than 300 kHz. The measuring cell does not allow to measure relaxations, because its own dielectric behaviour covers the dielectric response of a liquid crystalline medium. One can observe the spurious contribution for high frequency part of the dielectric spectrum, due to the finite resistance of ITO layers. The theoretical model was introduced, which shows how to calculate relaxations related to liquid crystals from dielectric response of the empty and filled measuring cell. The proof of strong influence of cell properties on effective (measuring) values of dielectric permittivities was shown.     

Dielectric spectroscopy of a high-polarization ferroelectric liquid crystal

Dielectric spectroscopy investigations in the frequency range 50?Hz to 1?MHz have been carried out on a new ferroelectric liquid-crystalline material (S-(-)-4-(2-n-hexylpropionyloxy)biphenyl-4′-(3-methyl-4-decyloxy)benzoate) possessing a relatively large spontaneous polarization (P _s?～?240?nC?cm^?2) and containing a lateral methyl group on the aromatic ring of the alkoxybenzoate unit. The effect of temperature on the dielectric relaxation modes has been investigated in the SmC* and N* phases. From dielectric dispersion data, relaxation frequency and dielectric strength of all detected relaxation modes have been evaluated and discussed. A new surface-like mode of relaxation frequency ～11?kHz and dielectric strength 3.8, is seen to appear in the SmC* phase.     

Induced ferrielectricity in antiferroelectric liquid crystals

The behaviour of the antiferroelectric SmC_A liquid crystal phase under applied electric field is discussed theoretically. The phase diagram involving the SmA, SmC_A and SmC _A ^* phases is worked out and shown to exhibit a Lifshitz critical point. The deformation of the bilayer structures induced by the field transforms the SmC_A phases into a ferrielectric phase whose specific configuration is described. Received: 23 October 1997 / Revised: 8 April 1998 / Accepted: 14 July 1998     

Frustration between syn- and anticlinicity in mixtures of chiral and non-chiral tilted smectic-C-type liquid crystals

We study the effects of mixing ferroelectric and antiferroelectric liquid-crystal compounds (FLCs and AFLCs) when the former are strictly synclinic and the latter strictly anticlinic, i.e. one mixture component exhibits only SmC* and the other only SmC a* as tilted phase. Three different paths between syn- and anticlinicity were detected: transition directly between SmC* and SmC a*, transition via the SmC_β* and SmC_γ* subphases, or by “escaping” the clinicity frustration by reducing the tilt to zero, i.e. the SmA* phase is extended downwards in temperature, separating SmC* from SmC a* in the phase diagram. The most common path is the one via the subphases, demonstrating that these phases appear as a result of frustration between syn- and anticlinic and, consequently, between syn- and antipolar order. For assessing the role of chirality, we also replaced the FLC with non-chiral synclinics. With one of the AFLCs, the route via supbhases was detected even in this case, suggesting that chirality --although necessary-- does not have quite the importance that has previously been attributed to the appearance of the subphases. The path chosen in the mixture study seemed to be determined mainly by the synclinic component, the subphase induction occurring only when the SmA*-SmC* transition was second order.     

Effect of graphene oxide dispersion in antiferroelectric liquid crystal mixture in the verge of SmC* to SmCA* phase transition

The continuous growing demand for nanoscience applications and the improvement in the performance of liquid crystal based devices has been extensively required by the technological world. Recent progress in the field of liquid crystals has found its practical implementation in various display and non display devices which experiences obstacle due to impurity effects that reduces its performance. The dispersion of nanoparticles in liquid crystal medium helps in the reduction of impurity ions and thus improving the performance of liquid crystal based devices. The present work is based on the collective dielectric relaxation processes that have been observed in antiferroelectric liquid crystal (AFLC) mixture W1000 dispersed with 0.1% wt/wt and 0.3% wt/wt concentrations of graphene oxide. Graphene oxide itself favors vertical alignment and the coupling of AFLC W1000 mixture with graphene oxide affects its molecular ordering. This has been confirmed from the polarizing optical micrographs. The dielectric relaxation modes have been observed with and without the application of bias voltage in SmC* to SmC_A* phase transition during cooling cycle. The appearance and disappearance of P_L, P_H and X modes have been observed and are explained on the basis of molecular interactions. Graphene oxide dispersed system favors homeotropic alignment (dark state) and the application of bias field will convert it into homogenous alignment (bright state). Graphene oxide dispersion find prospective applications in good contrast display devices, supercapacitors, electronic gadgets, rechargeable batteries. Electro optical results unveil the faster response time, decreased rotational viscosity and spontaneous polarization with no change in tilt angle for the dispersed system. These observations can be exploited in photonic switches with sub millisecond response time which are required for fabricating faster liquid crystal devices.     

Dielectric and orientational properties of nematogenic 4-<Emphasis Type="Italic">n</Emphasis>-octyl(4′-cyanophenyl)benzoate

Experimental studies of the dielectric properties in the nematic and isotropic phases of 4-cyanophenyl-4′-n-octylbenzoate (8CPB) have been performed in the frequency range from 50 kHz to 100 MHz. The relaxation process related to the rotation around the short molecular axis has been analysed. The results obtained have revealed that in the vicinity of the I-N phase transition, the molecular subdiffusional rotation process occurs. It is connected with the pretransitional effects which are observed both in the static and dynamic dielectric measurements. On the basis of the temperature dependence of the relaxation time in the nematic and isotropic phases, the orientational order parameter 〈P₂〉 has been determined. The values of 〈P₂〉 obtained in this way have been compared with those evaluated from the measurements of the polarized electronic absorption of the dichroic dye, dissolved as guest probe in the mesogenic host.     

Dielectric investigations in the nematic and hexatic smectic B phases of 4-hexyl-4′-[2-(4-isothiocyanatophenyl)ethyl]-1,1′-biphenyl

Temperature-dependent dielectric characterization of 4-hexyl-4′-[2-(4-isothiocyanatophenyl)ethyl]-1,1′-biphenyl (HIEB), which exhibits smectic B and nematic phases, has been carried out over the frequency range of 1 Hz to 10 MHz for homeotropic and planar alignment of sample molecules. This compound shows positive dielectric anisotropy (Δε = ε _∥ ? ε _⊥ > 0) in the nematic (N) phase. One mode of dielectric relaxation showing Arrhenius behaviour has been detected in the hexatic smectic B (SmB) phase. Various electrical parameters, namely, dielectric anisotropy, relaxation frequency and activation energy, have been determined in the N and SmB phases.