Orthoconic antiferroelectric liquid crystals

The ubiquitous liquid crystal display (LCD) is based on nematic liquid crystals (LCs) and has during 40 years developed from simple few digit displays into high-resolution flat-panel displays. A last and very important step towards the present TVs was the combination with thin film transistors that also led to the introduction of several new switching modes. Despite the enormous success of this technology, there is presently a renewed interest in LCs with faster electrooptic response, especially for future 3D vision display systems and possibly for field-sequential-colour (FSC) generation displays. Here, I focus on the so-called orthoconic antiferroelectric LCs (OAFLCs), which can provide the fast switching of conventional antiferroelectric LCs, but combined with a potentially much higher optical contrast. The reason is that the dark state of orthconic materials has a homeotropic optic axis, which makes the extinction ideally complete between crossed polarisers and independent of in-plane alignment fluctuations characteristic of all antiferroelectric LCs. The basic features and device physics issues of orthoconic LCs are reviewed and the most important remaining challenges to be met in terms of materials development are discussed in this article. Furthermore, a few examples of new applications made possible with the use of present and future orthoconic materials are given.     

Studies of the alignment properties of antiferroelectric liquid crystals by X-ray diffraction

It is observed optically that in a parallel rubbed antiferroelectric liquid crystal device, the texture consists of domains with two distinct optic axes, which make equal and opposite angles with the rubbing direction. It is proposed that this is caused by a large electroclinic effect at the surfaces during layer formation in the SmA* phase. This hypothesis is verified by finding the layer structure in single, parallel and skew rubbed devices by using X-ray diffraction.     

Alignment and switching of AFLC materials using various boundary conditions

We have systematically studied the quality of bookshelf alignment and electro‐optic characteristics of two antiferroelectric liquid crystal materials in cells with various boundary conditions. The electro‐optic characteristics of the materials studied depend strongly on both the liquid crystal materials and the boundary conditions at the supporting substrates. We have compared a number of observations in these cells: the tendency to form AFLC domains in the virgin state and after switching; the surface electroclinic effect (SEC effect); the transmission–voltage characteristics (TV) when driven with triangular‐ and square‐wave voltages at various frequencies; the threshold field and the conditions for relaxation to the AFLC state. The set of samples includes specially designed and manufactured test cells with different polyimides as alignment layers, treated with varying rubbing strengths. We discuss the significance of various factors and show the importance of simultaneously optimizing both materials and cell parameters for AFLC applications.     

Simulations of energy and switching in AFLCDs with different boundary conditions

Using standard expressions for the various terms in the Gibbs free energy, the switching in antiferroelectric liquid crystal (AFLC) displays is simulated and the time evolution of various energy terms and of the liquid crystal director distributions are calculated. It is shown that when returning from a strong positive voltage to zero, one can reach two types of antiferroelectric state: the normal alternating state with the two bulk polarizations perpendicular to the electrodes and opposite to each other, and the alternative splayed symmetric state with two bulk polarizations parallel to the electrodes and again opposite to each other. The former case gives rise to tri-state switching characteristics, the latter to V-shaped switching. In general strong polar interaction with the alignment layer favours V-shaped switching while weak or no polar interaction give rise to tri-state switching characteristics. Since the V-shaped characteristic has so far only been demonstrated experimentally in ferroelectric liquid crystals (or antiferroelectric liquid crystals being in the ferroelectric state), the difference in AFLCs is discussed and the conditions for continuous switching are modelled. The simulations show that the switching characteristics of the antiferroelectric display can be controlled by the surface parameters.     

V-shaped switching in binary mixtures of an achiral swallow-tailed material with the antiferroelectric liquid crystal (S)-MHPOBC

An achiral swallow-tailed material, 2-propylpentyl 4-(4'-decyloxybiphenyl-4-carbonyloxy)benzoate, p, showing SmA and SmC_alt phases was prepared for mixing (by weight percentage) with an antiferroelectric liquid crystal, (S)-MHPOBC, m, for the study. The binary mixture p15/m85 using (S)-MHPOBC (85%) as a host doped with achiral material (15%) resulted in a phase sequence SmA-SmC*-SmC*_A. The electro-optic response of this mixture in the ferroelectric SmC* phase displayed V-shaped switching, while that in the antiferroelectric SmC*_A phase displayed a double hysteresis switching. The mixture p85/m15 possessed SmA* and SmC*_A phases; V-shaped switching was found in the antiferroelectric SmC*_A phase of this mixture. These optical phenomena implied that a binary mixture containing a larger amount of achiral swallow-tailed material and/or possessing relatively lower polarization favours the occurrence of V-shaped switching in the antiferroelectric phase. The results of this work also suggested that thresholdless V-shaped switching in chiral smectic liquid crystals can be achieved by mixing an achiral swallow-tailed material with an antiferroelectric liquid crystal.     

Chirality-induced phase transitions in some liquid crystalline binary mixtures

Novel binary mixtures have been prepared between an optically active antiferroelectric liquid crystal, (S)-4-(1-methylheptyloxycarbonyl)phenyl 4'-octyloxy-biphenyl-4-carboxylate, and an optically active twin liquid crystal, (R)-3-methyladipic acid bis[4-(5-octyl-2-(pyrimidinyl)phenyl] ester, and the liquid crystalline properties investigated. The stability of each liquid crystal phase was found to decrease by mixing these two liquid crystalline materials. Furthermore, a phase diagram between these compounds showed a clear discontinuity in phase sequences. These results indicate that the liquid crystal phases are different in nature between these materials. The mixture consisting of the antiferroelectric material (40 per cent) and the twin material (60 per cent) shows an unusual liquid crystal phase, where the texture is similar to that reported for the twist grain boundary (TGB) phase. Related binary mixtures have been prepared between optically active or racemic materials, where the chirality of the system is expected to be altered systematically. The TGB phase was found to be induced only in the mixture between the optically active materials. Two kinds of effect on the appearance of the TGB phase, i.e. a strong helical structure induced by the optically active twin liquid crystal and a decrease of the smectic layer strength achieved by mixing between two types of liquid crystalline materials, are discussed.     

Analytical approach to V-shaped characteristics in antiferroelectric liquid crystal displays

Not only in ferroelectric liquid crystal displays (LCDs), but also in antiferroelectric LCDs, grey levels are possible by actively addressing the ‘continuous director rotation mode’. For ferroelectric LCDs this was shown qualitatively and quantitatively in previous articles. In this article it is shown that an exact analytical approach is also possible for antiferroelectric LCDs. In two consecutive layers the director orientations are symmetric, and at zero voltage they are in a splayed state. The conditions on alignment layer thickness and interaction coefficients are related to those of ferroelectric liquid crystal but are easier to fulfill.     

Achiral swallow-tailed materials with 'antiferroelectric-like' structure and their potential use in antiferroelectric mixtures

Achiral 'swallow-tailed' liquid crystalline materials are known to give alternating-tilt smectic C phases (S_Calt) which have structural similarities to the chiral antiferroelectric phases denoted as S*_CA. This paper describes the synthesis and characterization of three achiral branchedalkyl 4-(4'-dodecyloxybiphenyl-4-carbonyloxy)-3-fluorobenzoates. Optical microscopy and differential scanning calorimetry confirm that these materials show S_Calt and overlying S_A phases. The compounds were investigated as potential hosts which could be doped with a chiral ferroelectric liquid crystal so as to provide a viable- antiferroelectric mixture. These studies (microscopy and differential scanning calorimetry), to characterize the properties of the mixtures, show that antiferroelectric phases are induced. However, switching studies show that the antiferroelectric phases are extremely stable, a property which is almost certainly a consequence of the length of the lateral branching groups (ethyl, propyl and butyl).     

Analytical approach to V-shaped characteristics in antiferroelectric liquid crystal displays

Not only in ferroelectric liquid crystal displays (LCDs), but also in antiferroelectric LCDs, grey levels are possible by actively addressing the 'continuous director rotation mode'. For ferroelectric LCDs this was shown qualitatively and quantitatively in previous articles. In this article it is shown that an exact analytical approach is also possible for antiferroelectric LCDs. In two consecutive layers the director orientations are symmetric, and at zero voltage they are in a splayed state. The conditions on alignment layer thickness and interaction coefficients are related to those of ferroelectric liquid crystal but are easier to fulfill.     

V-shaped switching in binary mixtures of an achiral swallow-tailed material with the antiferroelectric liquid crystal (S)-MHPOBC

An achiral swallow-tailed material, 2-propylpentyl 4-(4′-decyloxybiphenyl-4-carbonyloxy)benzoate, p, showing SmA and SmC_alt phases was prepared for mixing (by weight percentage) with an antiferroelectric liquid crystal, (S)-MHPOBC, m, for the study. The binary mixture p/15/m85 using (S)-MHPOBC (85%) as a host doped with achiral material (15%) resulted in a phase sequence SmA-SmC*-SmC*_A. The electro-optic response of this mixture in the ferroelectric SmC* phase displayed V-shaped switching, while that in the antiferroelectric SmC*_A phase displayed a double hysteresis switching. The mixture p85/m15 possessed SmA* and SmC*_A phases; V-shaped switching was found in the antiferroelectric SmC*_A phase of this mixture. These optical phenomena implied that a binary mixture containing a larger amount of achiral swallow-tailed material and/or possessing relatively lower polarization favours the occurrence of V-shaped switching in the antiferroelectric phase. The results of this work also suggested that thresholdless V-shaped switching in chiral smectic liquid crystals can be achieved by mixing an achiral swallow-tailed material with an antiferroelectric liquid crystal.     

Thresholdless switching induced by polar anchoring in antiferroelectric liquid crystals

We present a novel thresholdless switching mode in an antiferroelectric liquid crystal cell which is stabilized by the presence of polar anchoring at the cell surfaces and the antiferroelectric nature of the material. We also suggest other possible configurations which are induced by strong polar anchoring and possess quite different director structures and optical characteristics.     

Thresholdless switching induced by polar anchoring in antiferroelectric liquid crystals

We present a novel thresholdless switching mode in an antiferroelectric liquid crystal cell which is stabilized by the presence of polar anchoring at the cell surfaces and the antiferroelectric nature of the material. We also suggest other possible configurations which are induced by strong polar anchoring and possess quite different director structures and optical characteristics.     

A novel liquid crystal showing antiferroelectric smectic C* and twist grain boundary phases

A novel antiferroelectric liquid crystal, 4-[5-(4-octyloxyphenyl)-2-pyrimidinyl]phenyl 4,4,4-trifluoro-3-(4-methoxyphenyl)butanoate (TFMB) showing twist grain boundary phases was found and investigated. In optically active TFMB, a diffuse liquid-liquid transition was observed above the clearing point. TFMB exhibited a stable antiferroelectric smectic C* phase. The relationship between antiferroelectricity and the molecular structure is discussed.     

New AFLC: a trimesogen presenting antiferroelectric smectic C phase (SmCA) and twist grain boundary smectic A phase (TGBA)

A first oligomeric antiferroelectric liquid crystal, a cyclohexane based trimesogen, was synthesized. It was characterized by microscopic observation, differential scanning calorimetry, helical pitch measurement, X-ray diffraction and electro-optical study. A large domain of antiferroelectric phase (DeltaT 55 C) and a very rich polymorphism (SmC*, SmC*, SmC* , A FI SmC*, TGBA, BP) are exhibited by the trimesogen.     

Metastable states in antiferroelectric liquid crystalline mixtures

We report on the observation of relaxation phenomena with extremely long relaxation times, amounting to several hours. These effects take place in some liquid crystal mixtures exhibiting ferroelectric and antiferroelectric dipole order. The observed phenomena are connected with the transformation from the supercooled ferroelectric state to another, metastable state. This transition may be described using a Debye type relaxation formula. At low temperatures, a second slow transition takes place: from the metastable intermediate state to the antiferroelectric phase. This transition is characterized by unidimensional growth of the antiferroelectric domains with a constant velocity. Close to the lower temperature limit of existence of the ferroelectric phase, a direct transition from the ferroelectric to the antiferroelectric phase takes place. This transition is described by an Avrami model, hence it is governed by the creation and growth of nuclei of the antiferroelectric phase.     

Ferroelectric and antiferroelectric low molar mass organosiloxane liquid crystals

The present paper is a study of the ferroelectric and antiferroelectric behaviour in low molar mass organosiloxane liquid crystal materials classed as mono-mesogens (AB type) and bi-mesogens (ABA type). A systematic study of series of materials all based on the same chiral mesogenic moiety is presented. The mesogen is a biphenylyl benzoate with a halogen X attached laterally to the benzoate ring which is closest to the chiral centre. Three homologous series, where the halogen is either fluorine, chlorine or bromine, are investigated. The number of silicon atoms in the linkage or end group is varied between two and nine. It is found that the materials have a broad (40 C) ferroelectric or antiferroelectric phase with a high P s (90nC cm2). The siloxane moiety forces the tilt angle to a temperature independent value close to 45. The antiferroelectric order is observed only in bi-mesogens with an odd number of silicon atoms in the siloxane link. The antiferroelectric order is attributed to the conformation of the molecule rather than to antiferroelectric interactions between layers.     

Metastable states in antiferroelectric liquid crystalline mixtures

We report on the observation of relaxation phenomena with extremely long relaxation times, amounting to several hours. These effects take place in some liquid crystal mixtures exhibiting ferroelectric and antiferroelectric dipole order. The observed phenomena are connected with the transformation from the supercooled ferroelectric state to another, metastable state. This transition may be described using a Debye type relaxation formula. At low temperatures, a second slow transition takes place: from the metastable intermediate state to the antiferroelectric phase. This transition is characterized by unidimensional growth of the antiferroelectric domains with a constant velocity. Close to the lower temperature limit of existence of the ferroelectric phase, a direct transition from the ferroelectric to the antiferroelectric phase takes place. This transition is described by an Avrami model, hence it is governed by the creation and growth of nuclei of the antiferroelectric phase.     

Dielectric spectroscopy of an antiferroelectric liquid crystal showing an antiferroelectric–ferrielectric transition

We report the dielectric relaxation behaviour in the antiferroelectric SmC_A* and ferrielectric SmC_γ* phases of the antiferroelectric liquid crystal 4-[5-(4-octloxyphenyl)-2-pyrimidinyl]phenyl 4,4,4-trifluoro-3-(methoxyphenyl)butanoate which shows an antiferroelectric transition at around 88±0.1°C. In the SmC_A* phase, two dielectric relaxation modes have been found, namely the usual antiferroelectric Goldstone mode and another arising from molecular rotation around its short axis. In the SmC_γ* phase, one dielectric relaxation mode has been observed due to the ferrielectric Goldstone mode. Dielectric increments and relaxation frequencies of the antiferroelectric and ferrielectric phases are estimated from the fits of the Cole–Cole function of the dielectric spectrum. The dependence of the bias field in the ferrielectric phase is also discussed.     

Dielectric spectroscopy of an antiferroelectric liquid crystal showing an antiferroelectric-ferrielectric transition

We report the dielectric relaxation behaviour in the antiferroelectric SmC_A* and ferrielectric SmC_γ* phases of the antiferroelectric liquid crystal 4-[5-(4-octloxyphenyl)-2-pyrimidinyl]phenyl 4,4,4-trifluoro-3-(methoxyphenyl)butanoate which shows an antiferroelectric transition at around 88±0.1°C. In the SmC_A* phase, two dielectric relaxation modes have been found, namely the usual antiferroelectric Goldstone mode and another arising from molecular rotation around its short axis. In the SmC_γ* phase, one dielectric relaxation mode has been observed due to the ferrielectric Goldstone mode. Dielectric increments and relaxation frequencies of the antiferroelectric and ferrielectric phases are estimated from the fits of the Cole-Cole function of the dielectric spectrum. The dependence of the bias field in the ferrielectric phase is also discussed.