Cholesteric Liquid Crystal Polymer Research Articles

Polymer Network Film with Double Reflection Bands Prepared Using a Thermochromic Cholesteric Liquid Crystal Mixture.

Cholesteric liquid crystal polymer network (CLCN) films with a single reflection band have found applications for decoration and anticounterfeiting. The CLCN films with double reflection bands were more suitable for these applications. Herein, they were prepared by using thermochromic cholesteric liquid crystals (CLCs) through a two-step photopolymerization approach. At the first step, due to oxygen inhibition, the CLC monomers near the substrate surface were polymerized at a certain temperature. At the second step, those near the air were polymerized at another temperature. The wavelengths of these two reflection bands of the CLCN film were dominated by the two polymerization temperatures. Based on this approach, patterns with composite colors were prepared, which were suitably applied for decoration. Moreover, a double-layered CLCN film with a broad reflection band was prepared that could potentially be applied for displays.

Chiral fluorescent liquid crystal polymers containing 4-bromo-1,8-naphthalimide – synthesis and properties

ABSTRACT By introducing two cholesteric liquid crystal monomers with different chain lengths (M1 and M2) and brominated naphthalimide fluorescent monomer (M3) into polymethyl hydrosiloxane, a series of fluorescent cholesteric liquid crystal polymers (FL-LCP) was prepared, which not only have excellent performance of liquid crystal and fluorescence but also own performance of selective reflection. Their chemical structures were confirmed to be in accord with molecular design by FT-IR and 1 H NMR spectroscopy, and found them with excellent thermal stability, mesomorphic behaviour and thermal performance by TGA, POM, DSC and XRD, and confirmed all the polymers belonged to the cholesteric phase. The FL-CLCPs emitted different intensity fluorescence under UV light, and conclusions about the relationship between fluorescence and temperature had been drawn. A comparative study was conducted on the fluorescence properties of powders and films of monomers and polymers.

Circularly Polarized Luminescence of Cholesteric Liquid Crystal Polymer Networks with a Europium(III) Complex as an Emitter.

A coordination complex, Eu(C12C12dbm)3(phen), with strong emission and a high quantum yield (QY ∼ 51.9%) was synthesized. The EuIII complex, as a fluorescent emitter, was embedded in cholesteric liquid crystal polymer networks (CLCNs). A series of free-standing EuIII-CLCN films were obtained, generating a typical sharp emission band corresponding to the EuIII complex. Tunable handedness of circularly polarized luminescence (CPL) with high |glum| values (up to 0.63) was observed. A series of CPL-active CLCN-coated PET films were also prepared (|glum| values up to 0.63), which can be used for large-area preparations. Moreover, by stacking an emitter-embedded PMMA layer and a CLCN layer, a composite system was built, and a large |glum| value (∼1.42) was achieved. Fluorescence patterns were prepared, and distinct images of CLCN films were recognized under both daylight and UV light. This work not only demonstrated that coordination compounds could be incorporated with CLCN films to prepare CPL-active materials with high |glum| values but also provided a new perspective for emissive CLCN materials used for anticounterfeiting and encryption.

Liquid crystal polymers with dual properties of fluorescence and selective reflection-design, synthesis and characterisation

ABSTRACT In this paper, two series of side chain fluorescent cholesteric liquid crystal polymers (FL-ChLCPs) were prepared by one-step method with polymethyl-hydrosiloxane (PMHS) as the main chain. Two series of polymers differ in the structure of vinyl flexible chains of fluorescent monomer, the comparative study was conducted on their performance of liquid crystal and fluorescence. The compounds and polymers were characterised using conventional methods. The results indicated all polymers possessed dual optical properties of fluorescence and selective reflection, they also had excellent thermal stability. The FL-ChLCPs emitted different intensity fluorescence under UV light, the fluorescence intensity has a certain relationship with temperature and aggregation-caused quenching effect only occurs when the content of fluorescent monomer in the polymer exceeds 20%.

Geometric phase-encoded stimuli-responsive cholesteric liquid crystals for visualizing real-time remote monitoring: humidity sensing as a proof of concept

Liquid crystals are a vital component of modern photonics, and recent studies have demonstrated the exceptional sensing properties of stimuli-responsive cholesteric liquid crystals. However, existing cholesteric liquid crystal-based sensors often rely on the naked eye perceptibility of structural color or the measurement of wavelength changes by spectrometric tools, which limits their practical applications. Therefore, developing a platform that produces recognizable sensing signals is critical. In this study, we present a visual sensing platform based on geometric phase encoding of stimuli-responsive cholesteric liquid crystal polymers that generates real-time visual patterns, rather than frequency changes. To demonstrate this platform’s effectiveness, we used a humidity-responsive cholesteric liquid crystal polymer film encoded with a q-plate pattern, which revealed that humidity causes a shape change in the vortex beam reflected from the encoded cholesteric liquid crystal polymers. Moreover, we developed a prototype platform towards remote humidity monitoring benefiting from the high directionality and long-range transmission properties of laser beams carrying orbital angular momentum. Our approach provides a novel sensing platform for cholesteric liquid crystals-based sensors that offers promising practical applications. The ability to generate recognizable sensing signals through visual patterns offers a new level of practicality in the sensing field with stimuli-responsive cholesteric liquid crystals. This platform might have significant implications for a broad readership and will be of interest to researchers working in the field of photonics and sensing technology.

Colourful cholesteric liquid crystal polymer network gratings prepared through nanoimprinting

ABSTRACT Both the colourful cholesteric liquid crystal polymer network (CLCN) patterns and the gratings have attracted much attention for their applications as optical materials. Herein, the photochromic cholesteric liquid crystal (CLC) mixtures were prepared using a photoisomerizable chiral dopant. The structural colour of the CLC mixtures was tunable by changing the chiral dopant concentration and the intensity of the 365-nm irradiation light. The CLCN gratings with a structural colour were prepared using the UV nanoimprinting lithography method. The structural colours of the CLCN gratings originate from both the cholesteric and the grating structures. Moreover, a patterned CLCN grating was prepared using a photochromic CLC mixture, which could be applied for decoration and anti-counterfeiting.

A cinnamate liquid crystal for rapid optical recording

ABSTRACT Photorecording materials have been applied for information recording. Herein, a cinnamate liquid crystal with an enantiotropic nematic phase was synthesised, which can be isomerised and polymerised under the irradiation of the 365-nm UV light. Cholesteric liquid crystal polymer network (CLCN) films were prepared using the mixtures of it, LC242, a chiral dopant and a photoinitiator. The CLCN films possess a slight gradient helical pitch which increases from the bottom to the top of the films. The formation of this structure should be driven by the photoisomerisation of the cinnamate. Under the irradiation of 365-nm UV light with a low intensity, the CLC mixtures show a photochromic behaviour which is proposed to be driven by the formation of oligomers. Based on this, the CLC mixtures can be applied for optical recording.

Structural coloured epoxy resin patterns prepared using thermochromic epoxy liquid crystal mixtures

Chiral epoxy liquid crystals were synthesized, which could be applied for the preparation of colourful cholesteric liquid crystal polymer network patterns. These patterns were suitably applied for decoration and anti-counterfeiting.

Unveiling the potential of polymer cholesteric liquid crystal interpenetrating networks as a label-free alcohol biochemical sensor.

In this study, an optical sensor is developed, incorporating hydrogen-bonded photonic array dots containing poly(acrylic acid) (PAA) within a polymer cholesteric liquid crystal interpenetrating polymer network (PCLCIPN) framework, thereby effectively controlling porosity. This methodology involves the fabrication of a porous photonic film, subsequent infusion with a hydrogel (PAA), and precise UV-curing to generate patterned array dots. The sensor exhibits exceptional discriminatory capability between methanol and ethanol, accurately discerning their varying concentrations within alcohol solutions. The optical sensing performance of the film is rigorously evaluated through continuous monitoring of wavelength shifts in the transmission spectrum across various alcohol concentrations. Notably, the observed wavelength shifts demonstrate a linear correlation with the concentration of alcohol, thereby enabling precise quantitative analysis of the alcohol solutions. The sensor exhibits a sensitivity of 0.44 nm/% for ethanol concentrations ranging from 5% to 60%, increasing to 2.1 nm/% for concentrations between 60% and 80%. Similarly, for methanol, sensitivities of 0.68 nm/% (5-60%) and 2.2 nm/% (60-80%) are recorded. Remarkably, this sensitivity trend extends seamlessly to 1 : 1 ethanol/methanol ratios, with values of 0.49 nm/% (5-60%) and 2.25 nm/% (60-80%). Furthermore, these sensors demonstrate colorimetric response to different alcohols, rendering them accessible and cost-effective biosensors for visual detection, thus obviating the necessity for complex analytical instruments.

Production and Investigation of Cholesteric Liquid Crystal-Polymer Fibers by Electrospinning Method

Sıvı kristallerin ekran teknolojisi, sensör, esnek devre elamanları, ışık modülatörleri gibi uygulamalarda kullanılabildiği bilinmektedir. Kolesterik mezofaz sıvı kristaller ışığın seçici geçirgenlik özelliği ile ön plana çıkmaktalardır. Bu çalışmada, ilk defa tek-iğneli elektro-eğirme kullanılarak kolesterik sıvı kristaller-polimer kompozit liflerinin üretilmiş ve incelenmiştir. Bu bağlamda ilk olarak, mavi, yeşil ve kırmızı renkte ışığı yansıtabilecek sırasıyla 470 nm, 550 nm ve 640 nm spiral adım uzunluklarına sahip kolesterik sıvı kristaller hazırlanmıştır. Konak nematik mezofaz olarak E-7 ve yüksek burma gücüne sahip R-5011 kiral katkı maddesi kullanılmıştır. Bu kolesteriklerin yaklaşık istenilen adım uzunluklarına sahip oldukları UV-VIS spektrofotometre ölçümleri ile gösterilmiştir. Ayrıca, hazırlanan kolesteriklerin karakteristik bir tekstür olan oily-streak desenlere sahip olduğu görülmektedir. Bu kolesterikler poliakrilonitril ile karıştırılarak dimetilformamid içerisinde çözdürülmüştür. Bu çözeltiler tek-iğneli elektro-eğirme sistemi ile 16 kV, 18 kV, 20 kV, 22 kV ve 24 kV uygulama voltajları altında eğirilerek sıvı kristal polimer kompozit lifleri haline getirilmişlerdir. Eğirilen liflere katkılanan kolesterik sıvı kristallerin varlığı optik ve yapısal analizler geçekleştirilerek belirlenmiştir. Polarize optik mikroskop ile yapılan görüntülemelerde çapraz polarizörler arasındaki lifler boyunca parlamalar gözlenmiştir. Bu parlamalar lif boyunca sıvı kristallerin yerleştiğini göstermektedir. Ayrıca, yapısal analiz sonucu her bir lifte üretim parametreleri ve katkı maddelerine göre lif yapısının değişimi üzerine çalışma yapılmıştır. Tüm kolesterik örnekleri için düşük uygulama voltajlarında eğirilen lifler boyunca uzanan küresel boncuk yapılar tespit edilmişken daha yüksek uygulama voltajlarında eğirilen liflerde boncuk yapılar oldukça seyrek gözlenmiştir. Kızılötesi spektroskopisi analizleri sonucu liflerin sıvı kristallerin sergilediği titreşim pikleri ile aynı dalga sayılarında pikler vermesi lif yapılarında sıvı kristallerin varlığını göstermiştir.

Light and Humidity Dual-Responsive Anti-Counterfeiting Films Based on Hydrogen-Bonded Cholesteric Liquid Crystal Polymers with Spiropyran.

There is still significant room for improvement when combining structural color with fluorescence patterns in dual anti-counterfeiting and dynamic anti-counterfeiting labels. In this study, we achieved significant breakthroughs under dual anti-counterfeiting conditions by using the structural color properties of the hydrogen-bonded cholesteric liquid crystal (HBCLC) and combining them with the fluorescence dye spiropyran (SP) to create anti-counterfeiting patterns. The anti-counterfeiting label can only display storage information after meeting the conditions of humidity and ultraviolet light (UV) and has the functions of dynamic encryption and repeated reading. We adjusted the center of the reflection band of the HBCLC film to transition from red to infrared under 40-90% relative humidity (RH) conditions and used it as a background film to draw anti-counterfeiting patterns with SP. Since these fluorescence dyes can switch between merocyanine (MC) (red) and SP (colorless) under UV and visible light conditions, when combined with the HBCLC, orthogonal dynamic encryption was achieved. Additionally, with the adsorption of SP, the reflection band of HBCLC films under the same humidity range increased from around 160 nm to around 260 nm, greatly improving the sensitivity to humidity changes. Furthermore, under UV conditions, it can still emit red fluorescence, demonstrating a polymorphic encryption feature, which greatly increased the complexity of the anti-counterfeiting pattern with significant significance to dynamic anti-counterfeiting and information storage.

Lasing chirality control of thin-film defect-mode lasers based on cholesteric liquid crystal polymer mirrors: publisher’s note

This publisher’s note contains a correction to Opt. Mater. Express 13, 1616 (2023).10.1364/OME.492254

Multilayer, Broadband Infrared Reflectors Based on the Photoinduced Preparation of Cholesteric Liquid Crystal Polymers.

This paper focuses on preparing broadband reflective liquid crystal films through the diffusion of monofunctional and bifunctional monomers in a photoinduced trilayer system. By combining the hydrophilic and hydrophobic liquid crystal glass surface treatment technologies, the polymer network of polymer-stabilized cholesteric liquid crystal (PSCLC) itself serves as a diffusion channel to form a trilayer cholesteric liquid crystal composite system containing bifunctional monomers, a nematic liquid crystal composite system, and a cholesteric liquid crystal composite system containing monofunctional monomers. Utilizing the difference in the polymerization rates of monofunctional and difunctional polymerizable monomers, the monomers and chiral compounds diffuse relative to each other, so that the liquid crystal pitch exhibits a gradient distribution, and the broadened reflective width can reach up to 1570 nm. There is no doubt that new and improved processes and technologies offer important possibilities for preparing and applying PSCLC films.

Synthesis and mesomorphic properties of novel multi-arm side-chain liquid crystal polymers with different terminal substituents

ABSTRACT In this study, two novel aromatic ester multi-arm liquid crystal monomers M 1 and M 2 with different terminal substituents centred on 3,4,5-trihydroxybenzoic acid, and a rod-shaped chiral liquid crystal monomer N were designed and synthesised. The synthesised liquid crystal monomers M and N were grafted and copolymerised with polymethylhydrosiloxane (PMHS). The structural characterisation of the synthesised liquid crystal compounds was carried out by FT-IR and 1H-NMR. The mesomorphic properties of the synthesised liquid crystal compounds were characterised by POM and DSC, and the results showed that the multi-arm liquid crystal monomers M 1 and M 2 are typical enantiotropic nematic liquid crystal compounds and N is typical thermotropic enantiotropic cholesteric liquid crystal. Polymers P 1 and P 2 are both cholesteric liquid crystal polymers. The glass transition temperatures and liquid crystal isotropic transition temperatures of polymers P 1 and P 2 series both tend to increase with the increase of multi-arm liquid crystal monomer M.

The directed self-assembly of reflective liquid crystalline polymer films to form polarization-independent diffractive optical elements

The directed self-assembly of liquid crystal polymers enables significantly enhanced optical properties compared to conventional isotropic optical materials. The transmissive properties of these thin polymeric films have been extensively studied, but the exploration of reflective liquid crystalline polymeric materials films has received little attention due to challenges in producing large, high-quality self-assembled films. We explore here for the first time stacked polymer cholesteric liquid crystal thin films as a pathway to generate reflective diffractive optics that act on both hands of circularly polarized light independently. We present 3 unique exemplar cases with increasing design complexity to communicate the widespread potential of these unique thin polymer films.

Tuning the Reflection Bandwidth of Polarization Volume Gratings by Guest Material Penetration

Polarization volume gratings (PVGs) based on polymerized cholesteric liquid crystal (CLC) films can potentially be applied as optical combiners in augmented reality (AR) smart glasses. The reflection bandwidth of PVGs is determined by the helical pitch and birefringence of the CLC, which must be tuned to match the desired color for reflection, but tuning the material properties is challenging as the materials must also be polymerizable. Here, we report a postprocessing method based on guest material penetration for the tuning of the reflection bandwidth of CLC polymer films. Solution coating of a high-birefringence guest liquid crystal on a CLC film modifies the birefringence as well as elongates the helical pitch. Penetration of a high-birefringence 5CT liquid crystal was found to cause a birefringence increase of the CLC film by approximately 18%.

Lasing chirality control of thin-film defect-mode lasers based on cholesteric liquid crystal polymer mirrors

This work investigates the emission chirality of a chiral distributed Bragg reflector (DBR) laser, which is composed by incorporating an isotropic medium containing laser dye between two cholesteric liquid crystal polymer films. The emitted laser showed different ratios of circularly polarized states corresponding to different pitch numbers of the chiral mirror. Through Berreman matrix numerical calculations and experimental results, we validated the variations of the emission chirality coupling in the defect resonance mode as a function of pitch numbers, as well as the effect of the defect layer thickness on the wavelength and mode number of the emitted laser. We also observed the cone-shape emission and examined the threshold of the lasing. The results successfully demonstrated the realization of DBR laser with controllable orthogonal circular polarization ratios in the emitted laser light. These results offer considerable potential for the development of micro-laser sources with different emission chirality and wavelengths for various applications.

Synthesis and characterisation of novel aromatic ester swallow-tailed cholesteric liquid crystal polymers

ABSTRACT In this paper, two novel aromatic ester swallow-tailed liquid crystal monomers M1 and M2 and a straight chain cholesteric liquid crystal monomer M3 were designed and synthesised. Two series of liquid crystal polymers, P1 series and P2 series, were graft-copolymerised with M and polymethylhydrosiloxane (PHMS). All the synthesised liquid crystal monomers and polymers were characterised by IR and 1H NMR and confirmed to the predicted molecular structure. The liquid crystal and thermal properties of the synthesised compounds were tested by DSC, POM, TGA and optical rotation. The results show that the monomer M1 is a monotropic nematic liquid crystal, and the Schlieren texture appears during the cooling process. M2 is an enantiotropic nematic liquid crystal with filamentous and schlieren texture. M3 is a thermotropic enantiotropic cholesteric phase with oily streak and focal cone texture. Both polymers P1 and P2 show typical Grand-Jean texture, and with the increase of monomer M3 content, the polymer clearing point temperature Ti increases continuously, the liquid crystal mesophase range widens, and the specific rotation value increases.

Fluorescent cholesteric liquid crystal polymers with dual properties: design, synthesis and characterisation

ABSTRACT In this study, we have synthesised fluorescent liquid crystal polymers with good fluorescence and optical properties through effective molecular design. Firstly, two series of cholesteric liquid crystal polymers (PN and PS series) were prepared by graft copolymerisation of cholesteric monomer(N1), monomer containing cyanobiphenyls with different length of carbon-chain (N2 and N3) and monomer containing bromine (6-Br) with polymethylhydrosiloxane chain as the polymer backbone. Secondly, we obtained fluorescent polymers RPN and RPS series by etherification reaction of PN and PS series with fluorescent monomer (F). The molecular structures and mesomorphic behaviour of monomers and polymers were characterised by usual ways. All the polymers are confirmed to consist with molecular design. The fluorescence of the polymers was investigated by fluorescence spectroscopy and fluorescent images. The fluorescence intensity of polymers is highly dependent on temperature. Fluorescent cholesteric liquid crystal polymers emitted different intensity fluorescence under ultraviolet irradiation and some regularities were summarised. RPN series with short carbon-chain meets our expectations for performance with dual effects of fluorescence and selective reflection, which were well verified. The effect of monomers with different chain lengths on the properties of fluorescent polymers has been described.

Dual-Wavelength Lasing with Orthogonal Circular Polarizations Generated in a Single Layer of a Polymer–Cholesteric Liquid Crystal Superstructure

We investigate the laser emission from a polymer-cholesteric liquid crystal superstructure with coexisting opposite chiralities fabricated by refilling a right-handed polymeric scaffold with a left-handed cholesteric liquid crystalline material. The superstructure exhibits two photonic band gaps corresponding to the right- and left-circularly polarized light. By adding a suitable dye, dual-wavelength lasing with orthogonal circular polarizations is realized in this single-layer structure. The wavelength of the left-circularly polarized laser emission is thermally tunable, while the wavelength of the right-circularly polarized emission is relatively stable. Due to its relative simplicity and tunability characteristics, our design might have broad application prospects in various fields of photonics and display technology.