Optical guided-wave study of a homeotropically aligned ferroelectric liquid crystal

Abstract

The excitation of optical modes is used to study the optical tensor configuration in a thin ferroelectric liquid crystal layer, cooled from the initially homeotropically aligned nematic phase. By monitoring the angular dependent reflectivity for plane polarized radiation coupled into the guided modes in the smectic C* layer and subsequently fitting the recorded data to predictions from multilayer optics theory, the optical tensor configuration in the layer is fully evaluated. Iteratively modelling the full tilt/twist profile in the cell, progressively converging the predicted reflectivity to experimental data, gives a complete and very well specified picture of the optical tensor throughout the cell. By studying the cell at various temperatures, the temperature dependence of the tilt of the major axis of the optic tensor (which may be related to the cone angle if the smectic layers are parallel to the cell surface) has been established. The temperature dependent optical dielectric constants have also been obtained.     

Experimental investigation of the compressible continuum theory of a homeotropically aligned ferroelectric liquid crystal

The optical tensor configuration in a homeotropically aligned ferroelectric liquid crystal (FLC), SCE13 cell, is investigated by means of optical excitation of half leaky guided modes. A thin slab of FLC is confined between a high index pyramid and a low index substrate whose indices bound those of the liquid crystal. In this geometry there exists a small angle range over which a series of sharp resonant modes may propagate in the liquid crystal. Detecting the angular dependent reflectivity for plane polarized radiation and subsequently fitting the data by iteratively modelling from multilayer Fresnel theory, a full characterization of the tilt and twist profile throughout the cell is achieved. The temperature dependence of the tilt of the principal director, which is related to the smectic cone angle, and of the optical permittivity, as well as the pitch have been obtained. The tilt director profile across the cell is interpreted using a compressible continuum theory for SmC* liquid crystals which includes the possibility of variable cone angle and layer spacing.     

Optic mode determination of the relaxed state configuration in a ferroelectric liquid crystal cell

Here the method of propagation of optic modes to examine the alignment in a ferroelectric liquid crystal layer is fully discussed. A sample geometry which allows the excitation of optic modes in a ferroelectric liquid crystal cell is presented and the data obtained in terms of reflectivity. The data are analysed by modelling the expected reflectivity from such a cell for a selection of proposed models for the optic tensor configuration. Models where the smectic layering lies perpendicular to the cell surfaces, or bends slowly across a cell are seen to be incorrect. It is found that a discontinuity in the smectic layering in the middle of the cell must be included to model the data well. This is consistent with the chevron structure seen in X-ray scattering work, and leads to an optic tensor alignment which is largely uniform across the ferroelectric layer. The relation between this and observation of conventional ferroelectric cells is discussed.     

The optical tensor configuration in a surface stabilized ferroelectric liquid crystal determined by using half leaky guided modes

The optic tensor configuration in a surface stabilized ferroelectric liquid crystal cell is investigated using optical excitation of half leaky guided modes. A thin ferroelectric liquid crystal layer is confined between a high index pyramid, with an index greater than the maximum of the liquid crystal, and a glass substrate having an index less than the minimum of the liquid crystal. Using standard attenuated total reflection experimental procedures, over a small angle range a series of sharp resonant peaks are recorded in the s-polarized reflectivity using p-polarized incident light. These peaks are extraordinarily sensitive to details of the optical tensor configuration within the cell. Fitting theoretically modelled reflectivities from multilayer Fresnel theory to the data allows determination of near surface alignment, bending of the chevron, surface tilt angle and biaxiality. To give a clear physical explanation for the great sensitivity of the technique, the electromagnetic field component distributions in the cell are also presented and analysed. The results confirm that the half leaky guided mode method has enormous potential for the study of the optic tensor configuration in liquid crystal layers.     

Characterization of the alignment of a nematic liquid crystal using half leaky guided modes

The excitation of half leaky guided optical modes to characterize fully the optical tensor profile in a thin liquid crystal layer has been used to evaluate the effect of rubbed polyimide aligning layers on the alignment of a nematic liquid crystal. A cell fabricated with rubbed polyimide alignment surfaces was studied at a wavelength of 632.8 nm. The liquid crystalline layer is sandwiched between a high refractive index top glass plate and a low refractive index glass substrate. Angular dependent reflectivities are recorded using a coupling prism and matching fluid with the same index as the top glass plate. Careful fitting of the predictions from multilayer optics theory to the observed angle dependent polarization conversion and reflectivity data yields the director profile within the liquid crystal layer in great detail.     

A guided wave study of the voltage dependent director configuration in a nematic liquid crystal layer with finite surface tilt

Prism coupling techniques have been used to excite optical modes in a thin nematic liquid crystal with finite surface tilt in order to study the voltage dependent director profile. The surface tilts are opposite in character and it is found that at zero applied volts the stable configuration is the substantially horizontal state. On applying the field this state is broken, probably transforming to the twisted vertical state. By modelling all the data obtained, the detailed behaviour of the director profile has been fully characterized yielding much information, including the change of surface tilt with applied voltage. For the nematic liquid crystal E7, this gives a voltage induced surface tilt of approximately 0.67° V^-1 for a 5.65 μm thick cell. Also using a boundary layer model, it has been possible to analyse the free energy in the cell and hence show that the observed twisted vertical state is the expected stable state under the field applied.     

Detailing smectic SSFLC director profiles by half-leaky guided mode technique and genetic algorithm

The genetic algorithm (GA), written to allow automatic analysis of optical reflectivity data obtained from liquid crystal cells using the half-leaky guided mode technique, has been developed to the point where liquid crystal cells can be analysed successfully giving greater detail of optical parameters and director profile than yielded by any other technique. The technique models the liquid crystal layer as a set of discrete, independent sub-layers which can map out the variation of the director through the thickness of the cell. Given sufficient high quality data, it is now possible automatically and accurately to fit the parameters of a complete liquid crystal cell. Using this highly adapted GA, half-leaky guided mode optical reflectivity data from the nematic, smectic A and smectic C* phases of SCE13 in a surface stabilized ferroelectric liquid crystal have been fitted to reveal director profiles and optical parameters of the cell in each phase.     

The alignment of a liquid crystal in the smectic A phase in a high surface tilt cell

Liquid crystal alignment is studied using propagating optical mode techniques for a cell with a high surface tilt SiO alignment. The director configuration is determined for both the nematic and smectic A phases. In the nematic phase a uniform splay across the cell is demonstrated, as predicted by continuum theory. In the smectic A phase the structure is seen to be nearly uniform in the central region of the cell with large splay in boundary layers of about 0.5 μm thickness. The reason for this appears to be competition between the tilted surface alignment forces and internal forces within the bulk of the smectic A layer which would induce a homogeneous configuration.     

Direct smectic A-smectic C*A phase transition

The anticlinic smectic CA phase belongs to the class of tilted smectic phases with an azimuthal angle alternating from one direction (theta=0) to the other (theta=pi) in successive layers. It occurs in general at lower temperature than the uniformly tilted smectic C phase, but may be obtained directly from the untilted smectic A phase. We use the chiral nCTBB9* series synthesized in this laboratory, in order to obtain a phase transition as close as possible to second order, as revealed by DSC. We measure the temperature behaviour of the birefringence and of the optical rotatory power across the transition in order to characterize the tilt angle. We finally study the optical response to a periodic electric field which excites separately the smectic C* and C*A soft modes. The main conclusion is that the only order parameter governing the critica Al behaviour of the phase transition is the tilt angle theta, as we get common divergence of both soft modes at the same temperature. This confirms previous high resolution calorimetric studies by Ema et al. that saw in MHPOBC an initial mean-field second order phase transition when the tilt appears, followed by sharp first order restructuring transitions between the tilted subphases.     

Direct smectic A-smectic C*A phase transition

The anticlinic smectic CA phase belongs to the class of tilted smectic phases with an azimuthal angle alternating from one direction (theta=0) to the other (theta=pi) in successive layers. It occurs in general at lower temperature than the uniformly tilted smectic C phase, but may be obtained directly from the untilted smectic A phase. We use the chiral nCTBB9* series synthesized in this laboratory, in order to obtain a phase transition as close as possible to second order, as revealed by DSC. We measure the temperature behaviour of the birefringence and of the optical rotatory power across the transition in order to characterize the tilt angle. We finally study the optical response to a periodic electric field which excites separately the smectic C* and C*A soft modes. The main conclusion is that the only order parameter governing the critica Al behaviour of the phase transition is the tilt angle theta, as we get common divergence of both soft modes at the same temperature. This confirms previous high resolution calorimetric studies by Ema et al. that saw in MHPOBC an initial mean-field second order phase transition when the tilt appears, followed by sharp first order restructuring transitions between the tilted subphases.     

The director structure and electroclinic fast optical switching in a grating-coupled ferroelectric smectic liquid crystal cell

Optical excitation of guided modes in a liquid crystal layer using grating-coupling gives sharp features in the angle-dependent reflectivity data. These features are strengthened by using a metallized grating to enhance coupling to the guided modes in the liquid crystal. In the present study the liquid crystal has a smectic A phase which exhibits fast electroclinic switching. Combining the sharp features in the reflectivity together with the electroclinic effect leads to fast, high contrast, optical switching which may open up potential for novel device structures.     

The director structure and electroclinic fast optical switching in a grating-coupled ferroelectric smectic liquid crystal cell

Optical excitation of guided modes in a liquid crystal layer using grating-coupling gives sharp features in the angle-dependent reflectivity data. These features are strengthened by using a metallized grating to enhance coupling to the guided modes in the liquid crystal. In the present study the liquid crystal has a smectic A phase which exhibits fast electroclinic switching. Combining the sharp features in the reflectivity together with the electroclinic effect leads to fast, high contrast, optical switching which may open up potential for novel device structures.     

On the origin of high optical director tilt in a partially fluorinated orthoconic antiferroelectric liquid crystal mixture

We have investigated the orthoconic antiferroelectric liquid crystal mixture W107 by means of optical, X-ray and calorimetry measurements in order to assess the origin of the unusally high tilt angle between the optic axis and the smectic layer normal in this material. The optical birefringence increases strongly below the transition to the tilted phases, showing that the onset of tilt is coupled with a considerable increase in orientational order. The layer spacing in the smectic A* (SmA*) phase is notably smaller than the extended length of the molecules constituting the mixture, and the shrinkage in smectic C* (SmC*) and smectic C_a* (SmC_a*) is much less than the optical tilt angle would predict. These observations indicate that the tilting transition in W107 to a large extent follows the asymmetric de Vries diffuse cone model. The molecules are on average considerably tilted with respect to the layer normal already in the SmA* phase but the tilting directions are there randomly distributed, giving the phase its uniaxial characteristics. At the transition to the SmC* phase, the distribution is biased such that the molecular tilt already present in SmA* now gives a contribution to the macroscopic tilt angle. In addition, there is a certain increase of the average tilt angle, leading to a slightly smaller layer thickness in the tilted phases. Analysis of the wide angle scattering data show that the molecular tilt in SmC_a* is about 20° larger than in SmA*. The large optical tilt (45°) in the SmC_a* phase thus results from a combination of an increased average molecule tilt and a biasing of tilt direction fluctuations.     

On the origin of high optical director tilt in a partially fluorinated orthoconic antiferroelectric liquid crystal mixture

We have investigated the orthoconic antiferroelectric liquid crystal mixture W107 by means of optical, X-ray and calorimetry measurements in order to assess the origin of the unusally high tilt angle between the optic axis and the smectic layer normal in this material. The optical birefringence increases strongly below the transition to the tilted phases, showing that the onset of tilt is coupled with a considerable increase in orientational order. The layer spacing in the smectic A* (SmA*) phase is notably smaller than the extended length of the molecules constituting the mixture, and the shrinkage in smectic C* (SmC*) and smectic C_a* (SmC_a*) is much less than the optical tilt angle would predict. These observations indicate that the tilting transition in W107 to a large extent follows the asymmetric de Vries diffuse cone model. The molecules are on average considerably tilted with respect to the layer normal already in the SmA* phase but the tilting directions are there randomly distributed, giving the phase its uniaxial characteristics. At the transition to the SmC* phase, the distribution is biased such that the molecular tilt already present in SmA* now gives a contribution to the macroscopic tilt angle. In addition, there is a certain increase of the average tilt angle, leading to a slightly smaller layer thickness in the tilted phases. Analysis of the wide angle scattering data show that the molecular tilt in SmC_a* is about 20° larger than in SmA*. The large optical tilt (45°) in the SmC_a* phase thus results from a combination of an increased average molecule tilt and a biasing of tilt direction fluctuations.     

NEXAFS measurements of the molecular ordering in the boundary layers of liquid crystalline free standing films

By near edge X-ray absorption fine-structure (NEXAFS) spectroscopy a finite molecular tilt angle in the surface layer of a free standing film in the liquid crystalline smectic A phase of C7 was directly detected. Analysis of the angular dependent intensities of the oxygen K edge NEXAFS spectra leads to an average tilt angle of the molecules in the surface layer of about 34°, which is characteristic for the bulk smectic C* phase of C7.     

The effect of chiral doping in achiral smectic liquid crystals on the de Vries characteristics: smectic layer thickness,electro-optics and birefringence

An addition of chiral dopant to two achiral smectic liquid crystals from a homologous series, by varying weight percentages with known low values of layer shrinkage, leads to chiral smectic-C* phase with a finite value of the spontaneous polarisation. The electro-optical response arising from changes in the induced apparent tilt angle brought about by a weak electric field in the SmA* phase gives rise to power law dependency on the reduced temperature. The critical exponent γ of the power law depends on the dopant concentration but its value is found to be greater than the typical value of 1.32. This implies that the short-range correlation extends from two dimensions to three dimensions in these materials in the SmA phase. The layer thickness of smectic layers in the guest–host system remains unaltered up to the 15 wt % addition of the chiral dopant to two achiral smectics. The system thus retains the low layer shrinkage of the achiral smectic as evidenced by measurements of the layer thickness from X-ray scattering and thickness measurements from optical interferometry. Results on the optical birefringence and the apparent tilt angle lead us to the conclusion of having successfully obtained chiral smectic materials for devices with de Vries characteristics by chiral doping.     

First Examples of de Vries‐like Smectic A to Smectic C Phase Transitions in Ionic Liquid Crystals

In ionic liquid crystals, the orthogonal smectic A phase is the most common phase whereas the tilted smectic C phase is rather rare. We present a new study with five novel ionic liquid crystals exhibiting both a smectic A as well as the rare smectic C phase. Two of them have a phenylpyrimidine core whereas the other three are imidazolium azobenzenes. Their phase sequences and tilt angles were studied by polarizing microscopy and their temperature‐dependent layer spacing as well as their translational and orientational order parameters were studied by X‐ray diffraction. The X‐ray tilt angles derived from X‐ray studies of the layer contraction and the optically measured tilt angles of the five ionic liquid crystals were compared to obtain their de Vries character. Four of our five mesogens turned out to show de Vries‐like behavior with a layer shrinkage that is far less than that expected for conventional materials. These materials can thus be considered as the first de Vries‐type materials among ionic liquid crystals.     

A high resolution temperature scanning technique for optical studies of liquid crystal phase transitions

A temperature scanning attachment for the polarizing microscope is described that offers a simple but powerful technique with which to detect even subtle paramorphotic phase transitions in liquid crystals with high temperature resolution. This technique was applied to CE8, a well known reference compound exhibiting rich mesomorphism. All smectic transitions in CE8 were clearly detected by distinct singularities in the temperature dependence of the transmitted light intensity. Repeated temperature scans across the second order ferroelectric smectic A*-C* transition with various orientations of polarizer and analyser provide high resolution data of optical birefringence and optical tilt angle. These data confirm a mean-field to tricritical crossover in the power law exponent of the optical tilt.     

An unusual chevron structure in an achiral smectic C liquid crystal device

The layer structure that occurs in an achiral smectic C liquid crystal device has been investigated as a function of temperature using the small angle X-ray scattering facility at the Synchrotron Radiation Source, Daresbury UK. The material studied shows a direct phase transition from the nematic to the smectic C phase. The layer structure proposed on the basis of the diffraction data is relatively complex, containing regions with chevron, quasi-bookshelf and curved structures. A rationale for the formation of the structure is presented, relying on both the phase transition characteristics of the system and the anisotropic layer elasticity in the smectic C phase. Qualitative analysis indicates that the layer constant A is greater than A 21, i.e. layer flexing is easier perpendicular to the plane of the director than parallel to it. It is also demonstrated that the surface chevron angle is several degrees different from the tilt angle of the smectic C phase at temperatures well below the smectic C to nematic phase transition. 12     

A modified Langevin-Debye model for investigating the electro-optic behaviour of de Vries smectic liquid crystals

An external electric field applied across a planar-aligned cell in Smectic A* phase of de Vries smectic liquid crystal induces director redistribution over a cone, resulting in a substantial increase in the birefringence and the apparent optical tilt angle. Such an electro-optic response is modelled by Shen et al. [Y. Shen et al., Phys. Rev. E 88, 062504 (2013)], who modified their previous hollow cone with a diffuse cone model by introducing the molecular distribution function limited over a range of tilt angles, that lie in between θ_min and θ_max. The limits in these two tilt angles are assumed to be temperature independent though the tilt angle in between the two values can be temperature dependent. However, the high resolution measurements of birefringence and the layer thickness indicate the presence of temperature dependent diffuse cone angle in SmA* phase.. In the proposed model, we replace θ_min by θ_T, a temperature dependent fitting parameter and the change shows that a better fit of the experimental data to the model is obtained. We determine the temperature dependence of θ_min and show that this angle increases as SmA* to SmC* phase transition temperature is approached.