Liquid Crystalline Films Research Articles

Multiphoton‐And SHG‐Active Pyrimidine‐Based Liquid Crystalline Thin Films Toward 3D Optical Data Storage

AbstractAn original asymmetric achiral pyrimidine core molecule, with long carbon chains on one side and a coumarin fragment on the other, is designed. This advanced molecular structure enabled the spontaneous emergence of crystalline and liquid crystalline thin films with strong 2nd harmonic generation (SHG) without any corona polishing process or tedious deposition techniques. Moreover, pin‐pointed multiphoton absorption in the liquid crystalline phase effectively switches off the SHG signal locally and permanently, underlining its interest in 3D data storage. This prototypical material, which can be fully addressed by NLO processes, multiphoton writing, and SHG reading, paves the way for the development of efficient flexible materials for 3D optical data storage.

Enhanced intrinsic thermal conductivity of liquid crystalline polyester dispersed films through hydrogen bond interaction

Polymer-dispersed liquid crystal (MHxFy) films comprising liquid crystal polymer (LCPH and LCPF) were successfully obtained by the method of solution casting & thermal compressing. At a LCPH mass fraction of 67 %, thermal conductivity (λ) value in through-plane (λ⊥) and in-plane (λ∥) direction of MH2F1 films reach up to 0.305 W/(m·K) and 2.879 W/(m·K), respectively. In comparison to pure LCPF, the thermal conductivity of MH2F1 exhibited an increase of 4.42 times, which is 14.4 times than that of conventional thermoplastics. Meanwhile, the crystallinity of MHxFy films around 50 % which is indicate the crystal phase become more integrated and regular. The FTIR spectra reveals a significant blue shift (3432 cm−1 to 3421 cm−1) in the absorption peak of the –OH group in MH2F1, suggesting a robust interaction between LCPF and LCPH. The primary cause of elevated thermal conduction in these films was determined to be the consistent presence of “thermal bridges” and a high degree of crystallinity. Furthermore, the T5%, Tmax and residual carbon at 800 °C of MH2F1 were 347.8 °C, 409.4 °C and 8 %, respectively. This is attributed to the ordered distribution of LCPH in LCPF matrix through hydrogen bonding interaction, forming an interpenetrating network of LCPF-LCPH. The result show that MHxFy films demonstrating superior intrinsic thermal conductivities, thermal stabilities, and mechanical properties.

Line tension and line entropy associated with the monolayer/trilayer boundary of smectic liquid crystal at the air-water interface.

Molecularly thin films of the smectic liquid crystal 4'-octyl-4-biphenylcarbonitrile (8CB) at the air-water interface phase separate into regions with different numbers of layers, in analogy with freestanding smectic liquid crystalline films. This paper reports the line tension associated with the boundary of coexisting trilayer and monolayer phases of in Langmuir films of 8CB at the air-water interface as a function of temperature and humidity and infers information on the boundary profile between the coexisting phases. Two complementary techniques are used to characterize the 8CB thin films: surface pressure-area isotherm and Brewster angle microscopy (BAM). We determine the line tension by stretching isolated domains from their equilibrium circular shape and analyzing the free relaxation with a hydrodynamic model. Then, we interpret the line tension vs temperature data in terms of an excess line entropy for the domain boundary, which requires careful consideration of the thermodynamics of inhomogeneous monolayer systems.

Tunable polarization holographic gratings obtained by varying the ratio of intensities of the recording beams

Polarization holography has been extensively applied in many fields, such as optical science, metrology, and biochemistry, due to its property of polarization modulation. However, the modulated polarization state of diffracted light corresponds strictly to that of incident light one by one. Here, a kind of tunable polarization holographic grating has been designed in terms of Jones matrices, and intensity-based polarization manipulation has been realized experimentally. The proposed tunable polarization holographic grating is recorded on an azobenzene liquid-crystalline film by a pair of coherent light beams with orthogonal polarization states and asymmetrically controlled intensities. It is found that the diffracted light can be actively manipulated from linearly to circularly polarized based on the light intensity of the recording holographic field when the polarization state of incident light keeps constant. Our work could enrich the field of light manipulation and holography.

Color-tunable circularly polarized luminescence from liquid crystalline polymer networks

Chiroptical materials with circularly polarized luminescence (CPL) activities have attracted increasing interest because of their promising applications in optoelectronics, biosensing and imaging. Nevertheless, the construction of CPL-active materials with large luminescence dissymmetry (glum) factors and high emission efficiency is still challenging. Herein, a series of liquid crystalline polymer network films have been prepared by photopolymerization of cholesteric liquid-crystalline mixtures doped with aggregation-induced emission-active luminogens, TPE-TA and BDABFN. Through adjustment of the mass ratio of the two luminogens, the resultant films exhibit multicolour CPL from blue to red to white with absolute glum values up to 0.71 and fluorescence quantum yields up to 44 %. This work provides a strategy for fabricating polymeric film materials with color-tunable CPL properties and high fluorescence efficiency.

Efficient multicolour and white circularly polarized luminescence from liquid crystalline polymer networks.

Twelve liquid crystalline polymer network films were fabricated through photopolymerization of cholesteric liquid-crystalline mixtures containing two aggregation-induced emissive-active luminogens. The films exhibit multicolour and white circularly polarized luminescence with dissymmetry factors up to 0.85 and fluorescence quantum yields up to 90%.

Unrestricted Chiral Patterning by Laser Writing in Liquid Crystalline and Plasmonic Nanocomposite Thin Films.

Obtaining hierarchical structures with arbitrarily controlled chirality remains a challenge. Here, thin films featuring chiroptically bipolar patterns are produced by a device utilizing microscale photothermal re-melting of materials exhibiting chirality synchronization. This device operates autonomously, guided by an algorithm that facilitates the homochiral growth of supramolecular organic helices through controlling their re-melting. The chirality synchronization phenomena of constitutionally achiral molecules grants availability of both handednesses of the helices, enabling unrestricted chiral writing in the film. The collective chiroptical response of assembled molecules is utilised to guide the patterning process, creating a foundation for optically secured information. The established methodology enables achieving dissymmetry factor values for circular dichroism (CD) a magnitude higher than previously reported, as confirmed with state-of-the-art, synchrotron-based Mueller matrix polarimetry (MMP). Moreover, the developed method is extended to nanocomposites comprising gold nanoparticles, providing the opportunity to tune the CD toward the plasmonic region. This strategic application of photothermal processing, specifically laser-directed melting, uncovers the potential to broaden the selection of nanostructured materials with precisely designed functionalities for photonic applications.

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.

Multi-channel generation of vortex beams with controllable polarization states and orbital angular momentum

Optical vortices with tunable polarization states and topological charges are widely investigated in various physical systems and practical devices for high-capacity optical communication. However, this kind of structured light beams is usually generated using several polarization and spatial phase devices, which decreases the configurability of optical systems. Here, we have designed a kind of polarized optical multi-vortices generator based on the Stokes–Mueller formalism and cross-phase modulation. In our scheme, multi-channel generation of polarized vortex beams can be realized through a single optical element and a single-input Gaussian beam. The polarization states and orbital angular momentum of the generated light beams are all-optically controllable. Furthermore, the proposed polarized optical multi-vortices generator has also been demonstrated experimentally through one-step holographic recording in an azobenzene liquid-crystalline film and the experimental results agree with theoretical analysis.

Spin-orbit optical Hall effect in π-vector fields.

Given the tremendous increase of data in digital era, vector vortex light with strongly coupled spin and orbital angular momenta of photons have attracted great attention for high-capacity optical applications. To fully utilize such rich degrees of freedom of light, it is highly anticipated to separate the coupled angular momentum with a simple but powerful method, and the optical Hall effect becomes a promising scheme. Recently, the spin-orbit optical Hall effect has been proposed in terms of general vector vortex light using two anisotropic crystals. However, angular momentum separation for π-vector vortex modes, another important part in vector optical fields, have not been explored and it remains challenging to realize broadband response. Here, the wavelength-independent spin-orbit optical Hall effect in π-vector fields has been analyzed based on Jones matrices and verified experimentally using a single-layer liquid-crystalline film with designed holographic structures. Every π-vector vortex mode can be decoupled into spin and orbital components with equal magnitude but opposite signs. Our work could enrich the fields of high-dimensional optics.

Research on the Morphology, Electro-Optical Properties and Mechanical Properties of Electrochromic Polymer-Dispersed Liquid Crystalline Films Doped with Anthraquinone Dyes

In this paper, dye-doped polymer-dispersed liquid crystalline (DDPDLC) films were prepared with high mechanical properties and low driving voltage by doping different dichroic anthraquinone dyes. The effects of various dye and doping concentrations on microscopic morphology, electro-optical characteristics, and mechanical characteristics were investigated. The optimal doping concentrations of different dyes were also explored. The results show that the addition of all dyes decreased the contrast ratio (CR) and the transmittance and mechanical properties of the polymer-dispersed liquid crystalline (PDLC) films. Similar mechanisms underlie the effects of solvent red 111 and solvent blue 104, which lower the driving voltages of the PDLC films. With the increasing concentration of the dye, the haze of the films first decreased and then increased after the content of the dye reached a certain level. For PDLC films doped with solvent green 28, the driving voltage and haze increased with the increasing content of the dye. According to different influencing factors, the dye content corresponding to the best performance of solvent red 111, solvent green 28 and solvent blue 104 is 0.8 wt%, 2.0 wt% and 0.3 wt%. Electrochromic PDLC films have been prepared based on the research results of dye content. The mechanical properties, electro-optical properties and microstructures of the films have been studied. The results show that the DDPDLC films could change color by tuning the applied voltages. The research provides a theoretical basis for obtaining PDLC films with a wider color gamut and supports the practical application of visible light camouflage technology in the military.

Preparation of High-quality Vapor-deposited Crystalline Organic Thin Films through Crystallization from Their Liquid Crystal Phase

High-quality crystalline organic thin films with large crystalline domain size were fabricated by vacuum deposition, followed by a post-annealing and cooling crystallization from their respective smectic A (SmA) liquid crystal precursor states. Crystallinity, surface smoothness and air exposure stability of ionic liquid crystalline thin films were much improved by this process, and the electric double layer action was for the first time observed at the SmA phase. Moreover, a seeded temperature gradient cooling process from the SmA phase was proposed and its capability was demonstrated in the fabrication of benzothienobenzothiophene derivative thin films, achieving their directional lateral crystal growth with high precision controllability.

Liquid Crystalline Mixtures with Induced Polymorphic Smectic Phases Targeted for Energy Investigations

In this study, 4-Biphenyle-4′-alkyloxybenzenamines were synthesized as a homologous series of liquid crystals based on the biphenyl moiety. Their mesomorphic and optical properties were examined for both pure and mixed components. Elemental analysis, NMR, and FT-IR spectroscopy were used to determine the molecular structures of the developed materials. Using differential scanning calorimetry (DSC), the mesophase transitions were studied, and polarized optical microscopy was used to identify the textures of the mesophases (POM). The obtained results showed that all compounds are dimorphic and only have smectic B (SmB) and smectic A (SmA) phases for all terminal side chains, which are enantiotropic. With variably proportionated terminal side chains and a focus on the mesomorphic temperature range, binary phase diagrams were constructed and an induced smectic C phase was achieved (SmC). It was found that terminal chain length affects both conformation and steric impact in the mixed states. The absorption and fluorescence emission spectra of pure as well as their binary mixtures liquid crystalline films were recorded to investigate the optical and photophysical properties. It was noted that, with the increase in alkyl chain length, the energy bandgap increases from 3.24 eV (for C6H13) to 3.37 eV (for C16H33) and charge carrier lifetime decreases, ascribing to the increase in stearic hindrance causing, consequently, the faster decay of charge carriers.

Non-volatile optical memory based on cooperative orientation switching: improvement of recording speed and contrast by utilizing out-of-plane orientation mode.

Herein, we report a novel strategy toward non-volatile optical memory with high-contrast, high-speed recording, and non-destructive readout capability based on the cooperative out-of-plane orientation of a fluorescent dye doped into azobenzene liquid crystalline polymer film. By employing the out-of-plane orientation switching upon irradiation with UV light and thermal heating, high-contrast turn-on fluorescence switching was successfully achieved and the optical recording was demonstrated with non-destructive fluorescence readout capability. Furthermore, the recording speed and the fluorescence on/off contrast in the present system were dramatically improved compared to the previous in-plane orientation mode.

Non-equilibrium ordering of liquid crystalline (LC) films driven by external gradients in surfactant concentration

HypothesisGradients in the concentration of amphiphiles play an important role in many non-equilibrium processes involving complex fluids. Here we explore if non-equilibrium interfacial behaviors of thermotropic (oily) liquid crystals (LCs) can amplify microscopic gradients in surfactant concentration into macroscopic optical signals. ExperimentsWe use a milli-fluidic system to generate gradients in aqueous sodium dodecyl sulfate (SDS) concentration and optically quantify the dynamic ordering of micrometer-thick nematic LC films that contact the gradients. FindingsWe find that the reordering of the LCs is dominated by interfacial shearing by Marangoni flows, thus providing simple methods for rapid mapping of interfacial velocities from a single optical image and investigating the effects of confinement of surfactant-driven interfacial flows. Additionally, we establish that surface advection and surfactant desorption are the two key processes that regulate the interfacial flows, revealing that the dynamic response of the LC can provide rapid and potentially high throughput approaches to measurement of non-equilibrium interfacial properties of amphiphiles. We also observe flow-induced assemblies of microparticles to form at the LC interface, hinting at new non-equilibrium approaches to microparticle assembly. We conclude that dynamic states adopted by LCs in the presence of surfactant concentration gradients provide new opportunities for engineering complex fluids beyond equilibrium.

Spatial manipulation of topological defects in nematic shells.

It is well known that positions of topological defects (TDs) in liquid crystals can be manipulated experimentally by locally distorting the liquid crystalline (LC) order, as for example by melting induced by optical tweezers. In this work, we study numerically the nematic ordering profiles and the corresponding topological defect configurations in thin nematic liquid crystalline shells controlled by imposed local distortion of LC order. We demonstrate that within curved LC films such manipulations could be strongly affected by local Gaussian curvature if it exhibits strong spatial variations. We use mesoscopic approach in which the shell geometry and LC orientational order are described by curvature of the surface and nematic order parameter tensor. For illustration purposes, we consider LC shells exhibiting spherical topology. We show that on increasing prolateness of shells, which imposes spatially inhomogeneous Gaussian curvature, TDs are relatively strongly "glued" to a local Gaussian curvature.

Hydrogen‐Bonded Cholesteric Liquid Crystals—A Modular Approach Toward Responsive Photonic Materials

A supramolecular approach for photonic materials based on hydrogen‐bonded cholesteric liquid crystals is presented. The modular toolbox of low‐molecular‐weight hydrogen‐bond donors and acceptors provides a simple route toward liquid crystalline materials with tailor‐made thermal and photonic properties. Initial studies reveal broad application potential of the liquid crystalline thin films for chemo‐ and thermosensing. The chemosensing performance is based on the interruption of the intermolecular forces between the donor and acceptor moieties by interference with halogen‐bond donors. Future studies will expand the scope of analytes and sensing in aqueous media. In addition, the implementation of the reported materials in additive manufacturing and printed photonic devices is planned.

All-Optical Polarization Manipulation Through Orbital Polarization Holography

Spin-orbital optical phenomena are closely related with light-matter interactions and have been of great interest in the last few years. Here, the effect of optical orbital angular momentum (OAM) on polarized waves carrying spin angular momentum (SAM) has been investigated experimentally by means of orbital polarization holography and analyzed with Jones matrices theoretically. We report that all-optical OAM-to-polarization manipulation can be realized with a controllable holographic grating recorded through the interference of orthogonally polarized beams in various helical modes in a kind of photo-alignment supermolecular liquid-crystalline films. The polarization states of diffraction beams can be controlled through adjusting the spatial degree of freedom of the recording light field. The OAM-controlled polarization manipulation is discussed in terms of Jones matrices and photoinduced birefringence. Because of the realization of OAM-to-SAM conversion, this work may find applications in a variety of devices.

Photoindeuced bending behavior of uniaxial aligned crosslinked NBA liquid crystalline polymer films

Crosslinked liquid crystal polymers (CLCPs) have recently attracted much attention because they exhibit unique properties in stimuli responsiveness. We have recently focused on the photoinduced deformation behavior of CLCP containing N-benzylideneaniline (NBA) as a photoresponsive moiety. We prepared two types uniaxially aligned NBA-containing crosslinked liquid crystalline polymer film, homogeneous and homeotropic, and evaluated its photomechanical properties. The initial alignment of photoactive mesogens significantly affects the bending behavior of the CLCP films: the homogeneous films bent toward the irradiation direction of the actinic UV light, while the homeotropic films bent away from the light source.

High intrinsic thermally conductivity side-chain liquid crystalline polysiloxane films grafted with pendent difunctional mesogenic groups

Herein, the microscopic ordered aggregation morphologies of SCLCP films are investigated, and molecular structures with regular arrangement can increase heat transfer via suppressing the scattering of phonons, thus greatly improving the λ of SCLCPs.