Chiral luminescent compounds as a perspective for cholesteric liquid crystal lasers

We present the synthesis and characterization of fluorene based materials for mirror less laser applications. Mirror less lasing is obtained from a cholesteric liquid crystals mixture, that acts as a resonator, doped with a photoluminescent dye, that acts as an active medium. We propose to use fluorene based compounds to combine two necessary properties to achieve laser emission: chirality and luminescence. Two different compounds, a trimer and an oligomer are synthesized. The trimer and the oligomer are both prepared with chiral moieties and, in addition, they are liquid crystalline compatible. More, oligofluorenes are good blue emitters and the emission quantum yield is around 0.8 in the violet–blue range. These fluorene based compounds are used in cholesteric liquid crystals mixtures as luminescent chiral dopants and a fine tuning of the laser emission is obtained. The dependence of lasing efficiency on concentration and the handedness of chiral luminescent dopants are investigated.     

Helix Inversion Controlled by Molecular Motors in Multistate Liquid Crystals

Unravelling the rules of molecular motion is a contemporary challenge that promises to support the development of responsive materials and is likely to enhance the understanding of functional motion. Advances in integrating light-driven molecular motors in soft matter have led to the design and realization of chiral nematic (cholesteric) liquid crystals that can respond to light with modification of their helical pitch, and also with helix inversion. Under illumination, these chiral liquid crystals convert from one helical geometry to another. Here, a series of light-driven molecular motors that feature a rich configurational landscape is presented, specifically which involves three stable chiral states. The succession of chiral structures involved in the motor cycle is transmitted at higher structural levels, as the cholesteric liquid crystals that are formed can interconvert between helices of opposite handedness, reversibly. In these materials, the dynamic features of the motors are thus expressed at the near-macroscopic, functional level, into addressable colors that can be used in advanced materials for tunable optics and photonics.     

Photonics and lasing in liquid crystal materials

Owing to fundamental reasons of symmetry, liquid crystals are soft materials. This softness allows long length-scales, large susceptibilities and the existence of modulated phases, which respond readily to external fields. Liquid crystals with such phases are tunable, self-assembled, photonic band gap materials; they offer exciting opportunities both in basic science and in technology. Since the density of photon states is suppressed in the stop band and is enhanced at the band edges, these materials may be used as switchable filters or as mirrorless lasers. Disordered periodic liquid crystal structures can show random lasing. We highlight recent advances in this rapidly growing area, and discuss future prospects in emerging liquid crystal materials. Liquid crystal elastomers and orientationally ordered nanoparticle assemblies are of particular interest.     

Electro-tunable optical diode based on photonic bandgap liquid-crystal heterojunctions

Manipulation of light is in strong demand in information technologies. Among the wide range of linear and nonlinear optical devices that have been used, growing attention has been paid to photonic crystals that possess a periodic modulation of dielectric function. Among many photonic bandgap (PBG) structures, liquid crystals with periodic structures are very attractive as self-assembled photonic crystals, leading to optical devices such as dye lasers. Here we report a new hetero-PBG structure consisting of an anisotropic nematic layer sandwiched between two cholesteric liquid-crystal layers with different helical pitches. We optically visualized the dispersion relation of this structure, displaying the optical diode performance: that is, the non-reciprocal transmission of circular polarized light at the photonic-bandgap regions. Transmittance spectra with circularly polarized light also reveal the diode performance, which is well simulated in calculations that include an electro-tunable diode effect. Lasing action was also confirmed to show the diode effect with a particular directionality.     

Blue-phase templated fabrication of three-dimensional nanostructures for photonic applications

A promising approach to the fabrication of materials with nanoscale features is the transfer of liquid-crystalline structure to polymers. However, this has not been achieved in systems with full three-dimensional periodicity. Here we demonstrate the fabrication of self-assembled three-dimensional nanostructures by polymer templating blue phase I, a chiral liquid crystal with cubic symmetry. Blue phase I was photopolymerized and the remaining liquid crystal removed to create a porous free-standing cast, which retains the chiral three-dimensional structure of the blue phase, yet contains no chiral additive molecules. The cast may in turn be used as a hard template for the fabrication of new materials. By refilling the cast with an achiral nematic liquid crystal, we created templated blue phases that have unprecedented thermal stability in the range -125 to 125?°C, and that act as both mirrorless lasers and switchable electro-optic devices. Blue-phase templated materials will facilitate advances in device architectures for photonics applications in particular.     

Tunable lasing from a cholesteric liquid crystal film embedded with a liquid crystal nanopore network

Continuous tuning of lasing wavelength is achieved in cholesteric liquid crystal lasers by embedding a network of nanopores with an average size of 10 nm filled with liquid crystals inside a polymerized matrix with helical order. The device possesses both high transparency and a fast response time because the tuning is driven by local reorientation of the liquid crystal molecules in the nanopores.     

Fabrication of a simultaneous red-green-blue reflector using single-pitched cholesteric liquid crystals

A cholesteric liquid crystal (CLC) is a self-assembled photonic crystal formed by rodlike molecules, including chiral molecules, that arrange themselves in a helical fashion. The CLC has a single photonic bandgap and an associated one-colour reflection band for circularly polarized light with the same handedness as the CLC helix (selective reflection). These optical characteristics, particularly the circular polarization of the reflected light, are attractive for applications in reflective colour displays without using a backlight, for use as polarizers or colour filters and for mirrorless lasing. Recently, we showed by numerical simulation that simultaneous multicolour reflection is possible by introducing fibonaccian phase defects. Here, we design and fabricate a CLC system consisting of thin isotropic films and of polymeric CLC films, and demonstrate experimentally simultaneous red, green and blue reflections (multiple photonic bandgaps) using the single-pitched polymeric CLC films. The experimental reflection spectra are well simulated by calculations. The presented system can extend applications of CLCs to a wide-band region and could give rise to new photonic devices, in which white or multicolour light is manipulated.     

Nature-Inspired Emerging Chiral Liquid Crystal Nanostructures: From Molecular Self-Assembly to DNA Mesophase and Nanocolloids

Liquid crystals (LCs) are omnipresent in living matter, whose chirality is an elegant and distinct feature in certain plant tissues, the cuticles of crabs, beetles, arthropods, and beyond. Taking inspiration from nature, researchers have recently devoted extensive efforts toward developing chiral liquid crystalline materials with self-organized nanostructures and exploring their potential applications in diverse fields ranging from dynamic photonics to energy and safety issues. In this review, an account on the state of the art of emerging chiral liquid crystalline nanostructured materials and their technological applications is provided. First, an overview on the significance of chiral liquid crystalline architectures in various living systems is given. Then, the recent significant progress in different chiral liquid crystalline systems including thermotropic LCs (cholesteric LCs, cubic blue phases, achiral bent-core LCs, etc.) and lyotropic LCs (DNA LCs, nanocellulose LCs, and graphene oxide LCs) is showcased. The review concludes with a perspective on the future scope, opportunities, and challenges in these truly advanced functional soft materials and their promising applications.     

Circularly polarized laser emission induced by supramolecular chirality in cholesteric liquid crystals

This paper describes the circularly polarized spectroscopic studies on absorption and emission of an achiral fluorescent dye embedded in cholesteric liquid crystals (CLCs). Optical excitation of the dye-doped CLC cell with a linearly polarized laser brought about the two laser emission peaks at longer and shorter reflection band edges of the CLC host through the internal laser feedback effect of the one-dimensional CLC photonic band-gap. At this stage, the optically excited laser emissions showed circularly polarized characteristic, even though the excitation beam was linearly polarized. The circularly polarized direction of the laser emission was determined by molecular chirality of only few mol% of the enantiomeric chiral dopant in this molecular system.     

Visible‐Light‐Induced Self‐Organized Helical Superstructure in Orientationally Ordered Fluids

Light‐induced phenomena occurring in nature and in synthetic materials are fascinating and have been exploited for technological applications. Here visible‐light‐induced formation of a helical superstructure is reported, i.e., a cholesteric liquid crystal phase, in orientationally ordered fluids, i.e., nematic liquid crystals, enabled by a visible‐light‐driven chiral molecular switch. The cyclic‐azobenzene‐based chiral molecular switch exhibits reversible photoisomerization in response to visible light of different wavelengths due to the band separation of n–π* transitions of its trans‐ and cis‐isomers. Green light (530 nm) drives the trans‐to‐cis photoisomerization whereas the cis‐to‐trans isomerization process of the chiral molecular switch can be caused by blue light (440 nm). It is observed that the helical twisting power of this chiral molecular switch increases upon irradiation with green light, which enables reversible induction of helical superstructure in nematic liquid crystals containing a very small quantity of the molecular switch. The occurrence of the light‐induced helical superstructure enables the formation of diffraction gratings in cholesteric films.     

Polymer-stabilized liquid crystal blue phases

Blue phases are types of liquid crystal phases that appear in a temperature range between a chiral nematic phase and an isotropic liquid phase. Because blue phases have a three-dimensional cubic structure with lattice periods of several hundred nanometres, they exhibit selective Bragg reflections in the range of visible light corresponding to the cubic lattice. From the viewpoint of applications, although blue phases are of interest for fast light modulators or tunable photonic crystals, the very narrow temperature range, usually less than a few kelvin, within which blue phases exist has always been a problem. Here we show the stabilization of blue phases over a temperature range of more than 60 K including room temperature (260-326 K). Furthermore, we demonstrate an electro-optical switching with a response time of the order of 10(-4) s for the stabilized blue phases at room temperature.     

Optically pumped surface-emitting lasing using self-assembled block-copolymer-distributed Bragg reflectors

A thin-film organic laser cavity using a block-copolymer-based one-dimensional (1D) photonic crystal was fabricated. Polymeric distributed Bragg reflectors (DBRs) were prepared through the self-assembly of a lamellar-forming poly(styrene-b-isoprene) (PS-b-PI) diblock copolymer having a 1D photonic stop band overlapping with the fluorescence spectrum of a gain medium. Optically pumped surface-emitting lasing was obtained using poly(methyl methacrylate) (PMMA) doped with 1,4-di-(2-methylstyryl)benzene (Bis-MSB) as an organic gain medium and the polymeric self-assembled DBR as a spectral-band selective feedback element.     

Long-range structuring of nanoparticles by mimicry of a cholesteric liquid crystal

Patterning nano-objects is an exciting interdisciplinary research area in current materials science, arising from new optical and optoelectronic properties and the need to miniaturize electronic components. Many techniques have been developed for assembling nanoparticles into two- and three-dimensional arrays. Most studies involving liquid crystals as templates have dealt with colloidal particles and nematic and smectic phases. Here, we demonstrate the long-range ordering of nanoparticle assemblies that adopt the helical configuration of the cholesteric liquid crystalline phase. Because we used glass-forming cholesterics, the nanostructures could be examined by transmission electron microscopy. The platinum nanoparticles form periodic ribbons that mimic the well-known 'fingerprint' cholesteric texture. Surprisingly, the nanoparticles do not decorate the original cholesteric texture but create a novel helical structure with a larger helical pitch. By varying the molar fraction of cholesterol-containing mesogen in the liquid crystal host, we show that the distance between the ribbons is directly correlated to the pitch. Therefore this inherent lengthscale becomes a simple control parameter to tune the structuring of nanoparticles. These results demonstrate how such an assembly process could be modulated, providing a versatile route to new materials systems.     

Dynamic Spirals of Nanoparticles in Light‐Responsive Polygonal Fields

Nanoparticles tend to aggregate once integrated into soft matter and consequently, self‐assembling nanoparticles into large‐scale, regular, well‐defined, and ultimately chiral patterns remains an ongoing challenge toward the design and realization of organized superstructures of nanoparticles. The patterns of nanoparticles that are reported in liquid crystals so far are all static, and this lack of responsiveness extends to assemblies of nanoparticles formed in topological singularities and other localized structures of anisotropic matter. Here, it is shown that gold nanoparticles form spiral superstructures in polygonal fields of cholesteric liquid crystals. Moreover, when the cholesteric liquid crystals incorporate molecular photoswitches in their composition, the pitch of the nanoparticulate spirals follows the light‐induced reorganization of the cholesteric liquid crystals. These experimental findings indicate that chiral liquid crystals can be used as chiral and dynamic templates for soft photonic nanomaterials. Controlling the geometry of these spirals of nanoparticles will ultimately allow modulating the plasmonic signature of hybrid and chiral systems.     

Optically Rewritable Transparent Liquid Crystal Displays Enabled by Light‐Driven Chiral Fluorescent Molecular Switches

Functional soft materials exhibiting distinct functionalities in response to a specific stimulus are highly desirable towards the fabrication of advanced devices with superior dynamic performances. Herein, two novel light‐driven chiral fluorescent molecular switches have been designed and synthesized that are able to exhibit unprecedented reversible Z/E photoisomerization behavior along with tunable fluorescence intensity in both isotropic and anisotropic media. Cholesteric liquid crystals fabricated using these new fluorescent molecular switches as chiral dopants exhibit reversible reflection color tuning spanning the visible and infrared region of the spectrum. Transparent display devices have been fabricated using both low chirality and high chirality cholesteric films that operate either exclusively in fluorescent mode or in both fluorescent and reflection mode, respectively. The dual mode display device employing short pitch cholesteric film is able to function on demand under all ambient light conditions including daylight and darkness with fast response and high resolution. Moreover, the proof‐of‐concept for a “remote‐writing board” using cholesteric films containing one of the light‐driven chiral fluorescent molecular switches with ease of fabrication and operation is disclosed herein. Such optically rewritable transparent display devices enabled by light‐driven chiral fluorescent molecular switches pave a new way for developing novel display technology under different lighting conditions.     

Stimuli‐Driven Control of the Helical Axis of Self‐Organized Soft Helical Superstructures

Supramolecular and macromolecular functional helical superstructures are ubiquitous in nature and display an impressive catalog of intriguing and elegant properties and performances. In materials science, self‐organized soft helical superstructures, i.e., cholesteric liquid crystals (CLCs), serve as model systems toward the understanding of morphology‐ and orientation‐dependent properties of supramolecular dynamic helical architectures and their potential for technological applications. Moreover, most of the fascinating device applications of CLCs are primarily determined by different orientations of the helical axis. Here, the control of the helical axis orientation of CLCs and its dynamic switching in two and three dimensions using different external stimuli are summarized. Electric‐field‐, magnetic‐field‐, and light‐irradiation‐driven orientation control and reorientation of the helical axis of CLCs are described and highlighted. Different techniques and strategies developed to achieve a uniform lying helix structure are explored. Helical axis control in recently developed heliconical cholesteric systems is examined. The control of the helical axis orientation in spherical geometries such as microdroplets and microshells fabricated from these enticing photonic fluids is also explored. Future challenges and opportunities in this exciting area involving anisotropic chiral liquids are then discussed.     

Biodegradable Laser Arrays Self-Assembled from Plant Resources

The transition toward future sustainable societies largely depends on disruptive innovations in biobased materials to substitute nonsustainable advanced functional materials. In the field of optics, advanced devices (e.g., lasers or metamaterial devices) are typically manufactured using top-down engineering and synthetic materials. This work breaks with such concepts and switchable lasers self-assembled from plant-based cellulose nanocrystals and fluorescent polymers at room temperature and from water are shown. Controlled structure formation allows laser-grade cholesteric photonic bandgap materials, in which the photonic bandgap is matched to the fluorescence emission to function as an efficient resonator for low threshold multimode lasing. The lasers can be switched on and off using humidity, and can be printed into pixelated arrays. Additionally, the materials exhibit stiffness above typical thermoplastic polymers and biodegradability in soil. The concept showcases that highly advanced functions can be encoded into biobased materials, and opens the design space for future sustainable optical devices of unprecedented function.     

1.55 $mu$m InAs/InAlGaAs Quantum Dot DFB Lasers

For the fabrication of quantum dot (QD) distributed feedback (DFB) lasers, self-assembled InAs/InAlGaAs QDs were grown on the InP/InGaAs grating structures by a molecular beam epitaxy. Ridge-waveguide QD DFB lasers with a stripe width of 3 mum were fabricated. Single-mode lasing operation around the wavelength of 1.56 mum was successfully achieved under the pulsed and continuous-wave (CW) modes at room temperature. The lasing operation was also observed up to 70 degC under pulsed mode, which is the first observation on the single-mode lasing around 1.55 mum. The characteristic temperatures calculated from the temperature dependence of the threshold current density were 121.8 K from room temperature to 45 degC, which was reduced to 74.2 K from 45 degC to 70 degC.     

Optical multi-stability of bimesogenic cholesteric liquid crystal

In this paper, we present a multi-stable property in a bimesogenic cholesteric liquid crystal material with a proper chiral additive and check its potential as an energy saving transmissive type liquid crystal display (LCD) through its electro-optic characteristics. Experimental results show that the multi-stable characteristics in the fabricated cholesteric LC cell are very stable. Such multi-stable properties depend on the driving frequency, voltage, and field direction. The contrast ratio in the fabricated transmissive type cholesteric LC cell was 15:1, which is a result produced by voltage and frequency control.     

Going beyond the reflectance limit of cholesteric liquid crystals

Cholesteric liquid-crystalline states of matter are abundant in nature: atherosclerosis, arthropod cuticles, condensed phases of DNA, plant cell walls, human compact bone osteon, and chiral biopolymers. The self-organized helical structure produces unique optical properties. Light is reflected when the wavelength matches the pitch (twice periodicity); cholesteric liquid crystals are not only coloured filters, but also reflectors and polarizers. But, in theory, the reflectance is limited to 50% of the ambient (unpolarized) light because circularly polarized light of the same handedness as the helix is reflected. Here we give details of a cholesteric medium for which the reflectance limit is exceeded. Photopolymerizable monomers are introduced into a cholesteric medium exhibiting a thermally induced helicity inversion, and the blend is then cured with ultraviolet light when the helix is right-handed. Because of memory effects attributable to the polymer network, the reflectance exceeds 50% when measured at the temperature assigned for a cholesteric helix with the same pitch but a left-handed sense before the reaction. As cholesteric materials are used as tunable bandpass filters, reflectors or polarizers and temperature or pressure sensors, novel opportunities to modulate the reflection over the whole light flux range, instead of only 50%, are offered.