Broadband reflective cholesteric liquid crystalline gels: volume distribution of reflection properties and polymer network in relation with the geometry of the cell photopolymerization

The ultraviolet (UV) light-absorbing properties of the liquid crystal (LC) constituent during the photo-induced elaboration of a cholesteric LC (CLC) gel may induce the broadening of the reflection bandwidth of the material, a situation that is promoted by asymmetrical irradiation conditions (only one side of the cell is irradiated). The in situ structure of the polymer network, included in the LC, was investigated by transmission electron microscopy and the temperature dependence of the reflection properties examined; it is shown that the network has a structure gradient that is at the origin of the broadening phenomenon. The smallest reflection wavelength is related to the cell side from which the UV light beam came in. A priori, this situation was unexpected since it is shown that this part of the gel is enriched with nematic (infinite-pitch CLC) network-forming material. The result is discussed in relation to the variation of the reflection band characteristics with polymer concentration, which offers the opportunity for indirect access to the volume distribution of the cholesteric periodicities. For applications, broadband reflective cholesteric gels may be of interest for reflective polarizer-free displays or for the light management with smart electrically-switchable reflective windows.     

Dépassement de la limite de réflexion de la lumière des cristaux liquides cholestériques : de Plusiotis resplendens aux gels à inversion d'hélicité

Beyond the reflectance limit of cholesteric liquid crystals: from Plusiotis resplendens to helicity-inversion gels. Due to its helical structure, a cholesteric liquid crystal (CLC) selectively reflects the light when its wavelength matches the helical pitch. The reflectance is limited to 50% of ambient, unpolarized light, because circularly polarized light of the same handedness as the helix is reflected. We report the elaboration procedure and the properties of a CLC gel for which the reflectance limit is exceeded in the infrared region. Photopolymerizable mesogens are introduced in the volume of a CLC exhibiting a thermally induced helicity inversion, and the blend is then cured with ultraviolet light when the helix is right-handed. The reflectance exceeds 50% when measured at the temperature assigned at a cholesteric helix with practically the same pitch, but a left-handed sense before reaction. From scanning electron microscopy investigations, it is shown that the organization of the mesophase is transferred onto the structure of the network. The gel structure is discussed as consisting of a polymer network with a helical structure containing two populations of LC molecules. Each of them was characterized by a band of circularly polarized light, which is selectively reflected. Novel opportunities to modulate the reflection over the whole light flux range are offered. Potential applications are related to the light and heat management for LC smart windows or reflective polarizer-free displays with a larger scale of reflectivity levels.     

Cholesteric liquid crystalline materials reflecting more than 50% of unpolarized incident light intensity

Cholesteric liquid crystals (CLCs) selectively reflect light when the wavelength matches the helical pitch. The reflectance is limited to 50% of ambient, unpolarized light because only circularly polarized light of the same handedness as the helix is reflected. Here the elaboration procedure and the properties of a CLC gel whose optical characteristics go beyond the 50% reflectance limit are reported. Photopolymerizable monomers are introduced into the volume of a CLC exhibiting a thermally induced helicity inversion and the blend is then cured with UV light when the helix is right-handed. The reflectance exceeds 50% when measured at the temperature assigned at a cholesteric helix with the same pitch but a left-handed sense before reaction. The reflection properties are investigated in the infrared region. From scanning electron microscopy investigations, it is shown that the organization of the mesophase is transferred onto the structure of the network. The gel structure is discussed as consisting of a polymer network with a helical structure containing two populations of low molar mass LC molecules. Each of them is characterized by a band of circularly polarized light which is selectively reflected. The monitoring of the optical response with temperature offers the opportunity to discriminate the respective contributions of the bound and free fractions of LC molecules to the reflectance, and to give evidence of the progressive increase of the reflected flux when the temperature decreases from the curing temperature. Novel opportunities to modulate the reflection over the whole light flux range are offered. Potential applications are related to the light management for smart windows or reflective polarizer-free displays with a larger scale of reflectivity levels.     

Dye induced great enhancement of broadband reflection from polymer stabilized cholesteric liquid crystals

A series of polymer stabilized cholesteric liquid crystals (PSCLCs) films were prepared from cholesteric liquid crystal (Ch‐LC) mixtures containing different components such as non‐reactive LC monomer, polymerizable monomer, chiral dopant, dye, and photoinitiator upon polymerization. The influence of the polymerizable monomer and dye of Ch‐LC mixtures on the reflection properties was investigated. The reflection bandwidth for all the samples can be increased by photo‐polymerization, and the network upon polymerization derived from two different polymerizable monomers with both one and two functional groups is more effective than that from one polymerizable monomer for broadening the reflection band. Especially, a dye‐doped Ch‐LC film can reflect incident light with the bandwidth over the wavelength range of 550–2350 nm, which is due to a greater pitch gradient formed inside of Ch‐LC film. The gradient pitch network structure was firstly demonstrated by scanning electron microscopy (SEM) with the film prepared from high diacrylate monomer concentration and subsequently proved by using a wash‐out/refill method. The nematic liquid crystals monomers was infiltrated into the polymer network that was prefabricated by removing the low molar weight LCs from the original PSCLCs film, and SEM exhibited the existence of a pitch gradient across the film thickness. The refilled nematic liquid crystals film showed broadband reflection after polymerzition, too. Copyright © 2011 John Wiley & Sons, Ltd.     

Tunable chiral materials for multicolour reflective cholesteric displays

A polymerizable tunable chiral material (TCM) has been prepared for the fabrication of multicolour reflective cholesteric displays. This photosensitive chiral material, whose chirality is adjustable upon UV irradiation, enables us to adjust the pitch of a cholesteric material and thus to produce the three reflected colours (red, green and blue) for a multicolour reflective cholesteric display. Furthermore, the possibility of linking this compound to a polymer network helped to solve the problem of colour diffusion. Reflection spectra of the corresponding cells show broad reflection peaks, because of scattering from the large amount of polymerizable compound. We also report the difference of response under UV irradiation between this polymerizable tunable chiral material and a non-polymerizable material.     

Photochemical tuning capability of cholesteric liquid crystal cells containing chiral dopants end capped with menthyl groups

In order to investigate the photochemical tuning capability of chiral monomers and polymers containing end‐capped menthyl groups, a new series of chiral dopants was synthesized and added to commercially available nematic liquid crystals to induce cholesteric liquid crystal (LC) phases. The addition of chiral dopants with azo structure led to phototunability of the reflection colour of the LC cells. Photochromic variation of the LC cells due to photoisomerization of the azo compound was investigated. After photopolymerization of the monomers inside the cholesteric LC cells, the centre wavelength of the reflected band of the incident light was found to be fixed and the reflected bandwidth was broadened, resulting in a red shift. A schematic representation of both the photoisomerization of the azo dopants and its effect on variation of twisting pitches is proposed. Real image recording was performed using 365 nm UV through a mask with text. The top and side views of the morphological network structures of a fabricated cholesteric LC cell were investigated using scanning electron microscopy. The results of this investigation demonstrated that RGB reflected colours of LC cells can easily be achieved through the addition of the menthyl‐containing synthesized chiral compounds to nematic LCs. The addition of synthesized AzoM helped further in recording the patterns onto cholesteric LC films using 365 nm UV exposure.     

Double UV polymerisation with variable temperature-controllable selective reflection of polymer-stabilised liquid crystal (PSLC) composites

In this study, a method of preparing wide-band reflection cholesteric liquid crystals (CLCs) films by UV-radical polymerisation in combination with UV-cationic polymerisation is proposed. Because the helical twisting power (HTP) of the chiral dopant decreases with increasing temperature and the polymerisation rate of UV-initiated free radical polymerisation is faster than UV-initiated cationic polymerisation, by adjusting the temperature, broadband reflective films with non-uniform pitch distribution are obtained. The fractured surface of the polymer network of the broadband reflective films is observed by scanning electron microscopy (SEM), which reveals the presence of non-uniform pitch distribution. In addition, the influences of monomer concentration, UV light intensity and UV curing time on the consequent non-uniform pitch distribution have been studied.     

Fabrication and optical characterization of imprinted broad‐band photonic films via multiple gradient UV photopolymerization

A structured broad‐band photonic film is fabricated by a novel method using multiple gradient UV‐induced polymerization in the presence of cholesteric liquid crystals (CLCs). Here, imprinting and broadening of the reflection band of chiral nematic mesophase cells are achieved via controlled UV polymerization. The intensity gradient of UV light is modified by the distance between UV lamp and sample cell, which affects the polymerization rate and leads to the formation of imprinted helical constructions with different pitches. In this study, a comparison of new design process with traditional UV polymerization process is carried out. After seven cycles of gradient UV polymerization, the imprinted photonic construction exhibited a broadened reflection band and Bragg reflection, even for isotropic materials. Because of this, the reflection bandwidth showed a 70% improvement. Additionally, two stacked imprinted cells with different pitches can reflect incident light with a bandwidth over the visible wavelength range of 480–680 nm. A broad‐band photonic polymer film can be imprinted using multiple gradient UV photopolymerization in the presence of CLCs. Forming a UV intensity gradient and controlling the rate of photopolymerization are key factors in broadening the reflection band. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 1427–1434     

Photochemical tuning capability of cholesteric liquid crystal cells containing chiral dopants end capped with menthyl groups

In order to investigate the photochemical tuning capability of chiral monomers and polymers containing end-capped menthyl groups, a new series of chiral dopants was synthesized and added to commercially available nematic liquid crystals to induce cholesteric liquid crystal (LC) phases. The addition of chiral dopants with azo structure led to phototunability of the reflection colour of the LC cells. Photochromic variation of the LC cells due to photoisomerization of the azo compound was investigated. After photopolymerization of the monomers inside the cholesteric LC cells, the centre wavelength of the reflected band of the incident light was found to be fixed and the reflected bandwidth was broadened, resulting in a red shift. A schematic representation of both the photoisomerization of the azo dopants and its effect on variation of twisting pitches is proposed. Real image recording was performed using 365 nm UV through a mask with text. The top and side views of the morphological network structures of a fabricated cholesteric LC cell were investigated using scanning electron microscopy. The results of this investigation demonstrated that RGB reflected colours of LC cells can easily be achieved through the addition of the menthyl-containing synthesized chiral compounds to nematic LCs. The addition of synthesized AzoM helped further in recording the patterns onto cholesteric LC films using 365 nm UV exposure.     

Effect of specific rotation of chiral dopant and polymerization temperature on reflectance properties of polymer stabilized cholesteric liquid crystal cells

A series of polymer stabilized cholesteric liquid crystal (PSCLC) cells were prepared by photo‐polymerization of a cholesteric liquid crystal (Ch‐LC) mixture containing a nonreactive LC, a nematic diacrylate and a novel cholesteryl monomer. The influence of the specific rotation and concentration of the chiral dopants, and the polymerization temperature on reflection properties was investigated. The results demonstrate that the reflection band was broadened after polymerization for all the systems both left‐handed S811 and right‐handed R1011 as the chiral dopant, which is speculated to be a result of an inhomogeneous consumption of the chiral monomer within the system. Additionally, the polymer temperature plays an integral role in the observed reflection spectra, and at optimum polymerization temperature the broadband reflection effect becomes much more pronounced. Scanning electron microscopy (SEM) was used to examine the role of microscopic changes of the polymer network induced by polymerization temperature. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1562–1570, 2008     

Broadband reflection characteristic of polymer-stabilised cholesteric liquid crystal with pitch gradient induced by a hydrogen bond

A polymer-stabilised cholesteric liquid crystal (PSChLC) was fabricated by ultraviolet (UV) induced polymerisation of photopolymerisable acrylate monomers mixed in a cholesteric liquid crystal (ChLC). A polymer network with a concentration gradient, which was induced by UV light absorption of dye along the propagation direction, was formed. A hydrogen bond, arising between the polymer network with a concentration gradient containing carboxyl as proton donors and chiral dopant (CD) as proton acceptors, induced a pitch gradient in PSChLC and then, as a consequence, broadband reflection. The broadband reflection is associated with the concentration and the composition of photopolymerisable acrylate monomers, the concentration of CD and the polymerisation temperature. Examining the morphologies of the polymer network by scanning electron microscopy, the helix structure and pitch gradient were verified, confirming the pitch gradient of the PSChLC and revealing the essence of the formation of broadband reflection.     

Photochemically and Thermally Driven Full‐Color Reflection in a Self‐Organized Helical Superstructure Enabled by a Halogen‐Bonded Chiral Molecular Switch

Supramolecular approaches toward the fabrication of functional materials and systems have been an enabling endeavor. Recently, halogen bonding has been harnessed as a promising supramolecular tool. Herein we report the synthesis and characterization of a novel halogen‐bonded light‐driven axially chiral molecular switch. The photoactive halogen‐bonded chiral switch is able to induce a self‐organized, tunable helical superstructure, that is, cholesteric liquid crystal (CLC), when doped into an achiral liquid crystal (LC) host. The halogen‐bonded switch as a chiral dopant has a high helical twisting power (HTP) and shows a large change of its HTP upon photoisomerization. This light‐driven dynamic modulation enables reversible selective reflection color tuning across the entire visible spectrum. The chiral switch also displays a temperature‐dependent HTP change that enables thermally driven red, green, and blue (RGB) reflection colors in the self‐organized helical superstructure.     

Visible Light and Temperature Regulated Reflection Colors in Self-supporting Cholesteric Liquid Crystal Physical Gels

Photo-responsive cholesteric liquid crystals (CLCs) have attracted much attention in recent years due to their wide applications in filters,tunable optical lasers,dynamic display devices,etc.However,UV light is usually used as the external stimulus source,which is not environment-friendly enough.On the other hand,the mechanical properties of CLCs are not strong enough for these practical applications.Therefore,it still remains a challenge to endow the CLCs with visible light response and high mechanical properties at the same time.Herein,an axially chiral tetra-fluorinated binaphthyl azobenzene gelator (S-4F-AG) is synthesized.Upon 550 and 450 nm light irradiations,S-4F-AG exhibits excellent photo-switchable behaviors.Notably,the maximum content of cis-isomer and its half-life are as high as 35％ and 89 h in acetonitrile,respectively.A self-supporting CLC physical gel with a storage modulus around 104 Pa can be obtained when 3wt％ S-4F-AG and 12wt％binaphthyl azobenzene derivative (dopant 2) are co-doped into a nematic LC host P0616A.This CLC physical gel exhibits a temperature-driven blue,green,and red reflection colors reversibly.Importantly,such three primary RGB colors can also be realized by adjusting the exposure time of 550 nm green light.This work lays a solid foundation for the applications ranging from information storage to high-tech anticounterfeit.     

How to broaden the light reflection band in cholesteric liquid crystals? A new approach based on polymorphism

Cholesteric liquid crystals (CLCs) may selectively reflect light when the helicoidal pitch is of the order of the wavelength of the incident beam propagating along the helix axis. The reflection bandwidth is dependent on the birefringence and is limited to a few tens of nanometers, which is insufficient for applications such as white-on-black reflective displays. Recent studies have shown that CLC polymer networks with a pitch gradient induce a broadening of the reflection bandwidth over several hundreds of nanometers. Most related processes rely on photocrosslinking reactions with a UV-gradient in a mixture made of chiral and achiral monomers with different UV-reactivities. Here a new experimental route exploiting the polymorphism of the mixture is presented. The basic concept lies in a thermally-induced pitch variation simultaneously carried out with the UV-crosslinking reaction. The optical behaviour is investigated in parallel with the cross-sectional microstructure as observed by transmission electron microscopy.     

How to broaden the light reflection band in cholesteric liquid crystals? A new approach based on polymorphism

Cholesteric liquid crystals (CLCs) may selectively reflect light when the helicoidal pitch is of the order of the wavelength of the incident beam propagating along the helix axis. The reflection bandwidth is dependent on the birefringence and is limited to a few tens of nanometers, which is insufficient for applications such as white-on-black reflective displays. Recent studies have shown that CLC polymer networks with a pitch gradient induce a broadening of the reflection bandwidth over several hundreds of nanometers. Most related processes rely on photocrosslinking reactions with a UV-gradient in a mixture made of chiral and achiral monomers with different UV-reactivities. Here a new experimental route exploiting the polymorphism of the mixture is presented. The basic concept lies in a thermally-induced pitch variation simultaneously carried out with the UV-crosslinking reaction. The optical behaviour is investigated in parallel with the cross-sectional microstructure as observed by transmission electron microscopy.     

具有宽波反射特性的胆甾相液晶固体薄膜材料的研究

采用两步聚合法得到了具有宽波反射特性的固体胆甾相液晶薄膜,首先通过聚合物稳定胆甾相液晶制备了螺旋结构的高分子网络,然后灌入具有不同螺距的可聚合的胆甾相小分子液晶单体混合物,经紫外光照射聚合后获得了能够反射可见光区(450～780 nm)覆盖红蓝绿三色光的胆甾相液晶固体薄膜.扫描电镜测试结果表明,胆甾相液晶固体薄膜的断面...     

Effects of polymer network on electrically induced reflection band broadening of cholesteric liquid crystals

The reflection band of polymer stabilized cholesteric liquid crystals with negative dielectric anisotropy can be broadened by DC electric fields, which was ascribed to the pitch gradient caused by the motion of the structural chirality, that is, the polymer network. They systematically varied the mixture components, such as the photo‐initiator concentration, the monomer functionality, and the chiral dopant, to explore their influences on the reflection band broadening behavior. They learned how to control the polymer network morphology and ion density, which in turn determined the reflection bandwidth. By optimizing the mixture, they have greatly enhanced the broadening effect and achieved large bandwidth at low voltages. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 835–846     

Printable optical sensors based on H-bonded supramolecular cholesteric liquid crystal networks

A printable H-bonded cholesteric liquid crystal (CLC) polymer film has been fabricated that, after conversion to a hygroscopic polymer salt film, responds to temperature and humidity by changing its reflection color. Fast-responding humidity sensors have been made in which the reflection color changes between green and yellow depending on the relative humidity. The change in reflection band is a result of a change in helix pitch in the film due to absorption and desorption of water, resulting in swelling/deswelling of the film material. When the polymer salt was saturated with water, a red-reflecting film was obtained that can potentially act as a time/temperature integrator. Finally, the films were printed on a foil, showing the potential application of supramolecular CLC materials as low-cost, printable, battery-free optical sensors.     

Light energy accumulation by cholesteric liquid crystal layer at oblique incidence

Oblique propagation of light through a planar layer of a cholesteric liquid crystal (CLC) is solved by Ambartsumian’s modified layer addition method. Two cases are considered, namely, the case when dielectric boundaries have a minimum influence on light transmission and the case when the CLC layer is in a vacuum. It is shown that in the first case a total internal reflection can happen for the fast eigen-mode at large incidence angles. New important features of light reflection (transmission) spectra, photonic density of states and accumulated energy density in the CLC layer are studied. The light localisation peculiarities in the CLC layer at oblique incidence is investigated too. It is shown that the light localisation for both the long-wavelength edge mode and the short-wavelength edge mode changes differently when the incidence angle changes. The obtained results can be used in the design of low-threshold lasers, in solar cell systems, in chiral photonics, in systems strongly absorbing light at certain wavelengths and when designing systems with absorption suppression created on the base of absorbing media, etc.     

Gel formation and photoactive properties of azobenzene-containing polymer in liquid crystal mixture

For the first time, a photochromic azobenzene-containing liquid crystalline (LC) acrylic polymer was used for gelation of low-molar-mass nematic mixture (LMNM). Dissolution of LC polymer in amount of only 2.5 wt.% in LMNM at 120°C (isotropic state) followed by cooling down results in formation of the solid-like photochromic LC gel. Gelation is associated with a phase separation and formation of microsized LC polymer domains, which form a physical “network” containing encapsulated nematic host. Textural changes of mixture during gel formation were analyzed, and absorbance spectra were measured. A special attention was paid to the kinetic study of photoinduced E-Z and Z-E isomerization of azobenzene side groups of polymer in gel. It was shown that ultraviolet (UV)-irradiation and E-Z isomerization processes are accompanied by disruption of H-aggregates of azobenzene moieties and partial dissolution of polymer.