Daniel A. Paterson

Electrically Tunable Selective Reflection of Light from Ultraviolet to Visible and Infrared by Heliconical Cholesterics

Electrical tuning of selective reflection of light is achieved in a very broad spectral range from ultraviolet to visible and infrared by an oblique helicoidal state of a cholesteric liquid crystal in a wide temperature range (including room temperature). The phenomenon offers potential applications in tunable smart windows, lasers, optical filters and limiters, as well as in displays.

Cyanobiphenyl-based liquid crystal dimers and the twist-bend nematic phase

ABSTRACT The synthesis and characterisation of several members of the 1,ω-bis(4-cyanobiphenyl-4′-yl) alkane (CBnCB) and the 1-(4-cyanobiphenyl-4′-yloxy)-ω-(4-cyanobiphenyl-4′-yl) alkane (CBnOCB) homologous series are reported. The new odd members described CB5CB, CB13CB, CB4OCB, CB8OCB and CB10OCB all exhibit twist-bend nematic and nematic phases. The members of these series already reported in literature, CB7CB, CB9CB, CB11CB and CB6OCB, were also prepared in order to allow for a direct comparison of their transitional properties. The properties of these dimers are also compared to those of the corresponding members of the 1,ω-bis(4-cyanobiphenyl-4,-yloxy) alkanes (CBOnOCB). For any given total spacer length, for odd members of these series, the nematic–isotropic transition temperatures and associated entropy changes are greatest for the CBOnOCB dimer and lowest for the CBnCB dimer. These trends are understood in terms of molecular shape. For short spacer lengths, the twist-bend nematic–nematic transition temperature (TNTBN) is higher for the CBnOCB series than for the CBnCB series but this is reversed as the spacer length increases. Of the CBOnOCB dimers, a virtual value of TNTBN was estimated for CBO3OCB and TNTBN was measured for CBO5OCB. These values are considerably lower than those observed for the corresponding members of the CBnCB or CBnOCB series. The dependence of TNTBN on molecular structure is discussed not only in terms of the molecular curvature but also in the ability of the molecules to pack efficiently. As the temperature range of the preceding nematic phase increases, so the twist-bend nematic–nematic transition entropy change decreases and the transition approaches second order for the longer spacers. For comparative purposes, the transitional behaviour of the even-membered dimers CB6CB, CB5OCB and CBO4OCB is reported and differences accounted for in terms of molecular shape. Graphical Abstract

New insights into the liquid crystal behaviour of hydrogen-bonded mixtures provided by temperature-dependent FTIR spectroscopy

The phase behaviour of equimolar mixtures of 6-(4ʹ-cyanobiphenyl-4-yl)hexyloxybenzoic acid (CB6OBA) with either 1-(4-butylazobenzene-4ʹ-oxy)-5-(4-oxypyridine)pentane (BuABO5OPyr) or 1-(4-butylazobenzene-4ʹ-oxy)-6-(4-oxypyridine)hexane (BuABO6OPyr) is reported. CB6OBA shows a monotropic twist-bend nematic phase and an enantiotropic nematic phase whereas the two pyridyl-based components do not exhibit liquid crystallinity. Both equimolar mixtures (CB6OBA/BuABOnOPyr) show enantiotropic nematic phases. The nematic-isotropic transition temperature and associated entropy change are higher for the CB6OBA/BuABO6OPyr mixture than for the CB6OBA/BuABO5OPyr mixture. This may be accounted for in terms of the average shapes of the hydrogen-bonded 1:1 complexes formed between the two differing components in the mixtures. However, Fourier transform infrared spectroscopy reveals that this complex is not formed quantitatively, but instead a complex mixture exists over the complete temperature range studied, involving the 1:1 complex, both cyclic and open acid dimers, free acid and hence, free BuABOnOPyr molecules.

Structure–property relationships in twist-bend nematogens: the influence of terminal groups

ABSTRACT The synthesis and characterisation of a range of non-symmetric liquid crystal dimers designed to exhibit the twist-bend nematic phase is reported. Beginning with 1-(4-cyanobiphenyl-4′-yloxy)-6-(4-cyanobiphenyl-4′-yl) hexane, each nitrile group is exchanged systematically for a methoxy group. The behaviour of these dimers is interpreted in terms of their bent shape being the predominant driving force for the formation of the twist-bend nematic phase, and the small differences between the twist-bend nematic–nematic transition temperatures are attributed to the differences between the interaction strength parameters of the mesogenic units. The 4-alkyloxyphenyl 4-[6-(4′-cyanobiphenyl-4-yl)hexyloxy]benzoates with ethyl, butyl, hexyl and octyl chains show the twist-bend nematic phase, whereas the corresponding 4-alkyloxyphenyl 4-[5-(4′-cyanobiphenyl-4-yloxy)pentyloxy]benzoates do not. This difference in behaviour is attributed to the more bent structure of the former. Increasing the terminal chain length initially decreases the twist-bend nematic–nematic transition temperature and this suggests that the chain disrupts the interactions between the mesogenic units. Subsequent increases in chain length have a smaller effect suggesting that the chain can be accommodated within an intercalated arrangement. The transitional behaviour of 1-(4-cyanobiphenyl-4′-yloxy)-6-(4-butyloxybiphenyl-4′-yl) hexane is compared to that of 1-(4-cyanobiphenyl-4′-yloxy)-6-(4-((S)-2-methyl)butyloxybiphenyl-4′-yl) hexane, and it is shown that chain branching strongly destabilises the twist-bend nematic phase. This is attributed to difficulties associated with packing the dimers. Graphical Abstract

Electrically tunable laser based on oblique heliconical cholesteric liquid crystal

Significance Liquid-crystal lasers based on micrometer-scale self-organization of organic molecules into the so-called cholesteric liquid crystal are simple to manufacture; they are small in size and low in cost and power consumption. Their potential applications range from sensing and imaging to informational displays and miniature “lab-on-a-chip” devices. We report a cholesteric structure used as the laser’s resonator cavity that enables a continuous real-time tuning of the emitted wavelength in a very broad range by applying an electric field. The structure is heliconical, with the molecules rotating around a helical axis and being tilted toward this axis. The electric field controls the tilt and the pitch, thus changing the wavelength by at least 100 nm. A cholesteric liquid crystal (CLC) formed by chiral molecules represents a self-assembled one-dimensionally periodic helical structure with pitch p in the submicrometer and micrometer range. Because of the spatial periodicity of the dielectric permittivity, a CLC doped with a fluorescent dye and pumped optically is capable of mirrorless lasing. An attractive feature of a CLC laser is that the pitch p and thus the wavelength of lasing λ¯ can be tuned, for example, by chemical composition. However, the most desired mode to tune the laser, by an electric field, has so far been elusive. Here we present the realization of an electrically tunable laser with λ¯ spanning an extraordinarily broad range (>100 nm) of the visible spectrum. The effect is achieved by using an electric-field-induced oblique helicoidal (OH) state in which the molecules form an acute angle with the helicoidal axis rather than align perpendicularly to it as in a field-free CLC. The principal advantage of the electrically controlled CLCOH laser is that the electric field is applied parallel to the helical axis and thus changes the pitch but preserves the single-harmonic structure. The preserved single-harmonic structure ensures efficiency of lasing in the entire tunable range of emission. The broad tuning range of CLCOH lasers, coupled with their microscopic size and narrow line widths, may enable new applications in areas such as diagnostics, sensing, microscopy, displays, and holography.

Spontaneous chirality through mixing achiral components: a twist-bend nematic phase driven by hydrogen-bonding between unlike components

The spontaneous formation of a chiral phase via molecular recognition in a system consisting of achiral components is reported. Specifically, the liquid crystalline behaviour of two molecular complexes assembled by hydrogen bonding between a stilbazole-based template and alkoxybenzoic acids has been characterised. The complexes exhibit the heliconical twist-bend nematic phase (NTB) over a broad temperature range despite the hydrogen-bond acceptor not being liquid crystalline and the donor exhibiting the conventional achiral nematic phase.

Azobenzene-based liquid crystal dimers and the twist-bend nematic phase

ABSTRACT The synthesis and characterisation of two new sets of non-symmetric liquid crystal dimers is reported, the 1-(4-substitutedazobenzene-4′-yloxy)-6-(4-cyanobiphenyl-4′-yl)hexanes (CB6OABX) and 1-(4-substitutedazobenzene-4′-yloxy)-6-(4-cyanobiphenyl-4′-yloxy)pentanes (CBO5OABX). The terminal substituents are methyl, methoxy, butyl, butyloxy, nitrile and nitro. All the CB6OABX dimers exhibit twist-bend nematic (NTB) and nematic (N) phases. The CBO5OABX dimers also all show an N phase but only the butyl and butyloxy homologues exhibit the NTB phase. The transitional behaviour of the non-symmetric dimers is compared to that of the corresponding symmetric dimers, the 1,5-bis(4-substitutedazobenzene-4′-yloxy)pentanes (XABO5OABX) and either 1,7-bis(4-cyanobiphenyl-4′-yl)heptane or 1,5-bis(4-cyanobiphenyl-4′-yloxy)pentane. The XABO5OABX dimers all show a nematic phase and in addition, the butyl homologue exhibits a smectic A phase. The difference in transitional behaviour between the CB6OABX and CBO5OABX dimers is attributed to the difference in their molecular shapes arising from different bond angles between the para axis of the cyanobiphenyl unit and the first bond in the spacer. Specifically, the all-trans conformation of a CBO5OABX dimer is more linear than that of the corresponding CB6OABX dimer. Differences within each set of dimers are attributed to changes in the average molecular shape and the strength of the mixed mesogen interaction on varying the terminal group. Crystal structures are reported for CB6OABOMe, CBO5OABNO2 and MeOABO5OABOMe. Graphical Abstract

Tunable backflow in chiral nematic liquid crystals via twist-bend nematogens and surface-localised in-situ polymer protrusions

ABSTRACT Dynamic electro-optic response of the liquid crystal (LC) director shows a backflow effect that is manifested as an optical bounce in chiral nematic LCs (N*LC) during field-induced homeotropic-twisted transition. The bend elastic constant (K33) strongly influences the dynamics of backflow at the N*LC in homeotropic-twisted transition. The cyanobiphenyl LC dimers – CB7CB, CB9CB and CB11CB – possess a unique characteristic of inherent bend molecular configuration that lowers K33. With the modulation of the effective K33 in dimer-doped N*LCs, we report the tunability of the optical bounce that decreases with the increase in the length of flexible spacers in LC dimers. The doped LC dimers with short spacer lengths not only generate a strong backflow with an enhanced twist degeneracy of the LC director across the cell, but also prolong the time of disappearance of the optical bounce. Furthermore, we demonstrate the suppression of the optical bounce with surface localised polymer protrusions having 50–100 nm diameters, which allow faster dynamic relaxation process and reduced backflow. We envision a novel design of a tunable microfluidic device for precise flow control of organic or inorganic matter in LC medium that exploits the tunable backflow in LC dimer-doped N*LCs. Graphical Abstract

Formation of periodic zigzag patterns in the twist-bend nematic liquid crystal phase by surface treatment

ABSTRACT Zigzag patterns were successfully generated in the twist-bend nematic (NTB) phase of 1-(4-cyanobiphenyl-4′-yl)-6-(4-cyanobiphenyl-4′-yloxy)hexane (CB6OCB) via simple surface treatment. A detailed microscopy study using polarised optical microscopy and fluorescence confocal polarising microscopy was performed to observe the director arrangement in the zigzags, where distinctive periodic patterns were found to be aligned perpendicular to the rubbing direction. These patterns originate from the structural instability and generation of splay deformation with focal conic domain-like structures that are typically found in smectic phases, revealing that the NTB phase has physical properties similar to those of the smectic phase. Observation of these unusual zigzag patterns in the NTB phase opens an avenue for use of this phase in potential applications such as optical modulators and gratings. GRAPHICAL ABSTRACT

Optimizing 3D image quality and performance for stereoscopic gaming

The successful introduction of stereoscopic TV systems, such as Samsungs 3D Ready Plasma, requires high quality 3D content to be commercially available to the consumer. Console and PC games provide the most readily accessible source of high quality 3D content. This paper describes innovative developments in a generic, PC-based game driver architecture that addresses the two key issues affecting 3D gaming: quality and speed. At the heart of the quality issue are the same considerations that studios face producing stereoscopic renders from CG movies: how best to perform the mapping from a geometric CG environment into the stereoscopic display volume. The major difference being that for game drivers this mapping cannot be choreographed by hand but must be automatically calculated in real-time without significant impact on performance. Performance is a critical issue when dealing with gaming. Stereoscopic gaming has traditionally meant rendering the scene twice with the associated performance overhead. An alternative approach is to render the scene from one virtual camera position and use information from the z-buffer to generate a stereo pair using Depth-Image-Based Rendering (DIBR). We analyze this trade-off in more detail and provide some results relating to both 3D image quality and render performance.