Extending the capabilities of vectorial ptychography to circular-polarizing materials such as cholesteric liquid crystals.

The problem of imaging materials with circular-polarization properties is discussed within the framework of vectorial ptychography. We demonstrate, both theoretically and numerically, that using linear polarizations to investigate such materials compromises the unicity of the solution provided by this computational method. To overcome this limitation, an improved measurement approach is proposed, which involves specific combinations of elliptical polarizations. The effectiveness of this strategy is demonstrated by numerical simulations and experimental measurements on cholesteric liquid crystal films, which possess unique polarization properties. With the help of Pauli matrices algebra, our results highlight the technique's ability to discern between the different types of circular polarizers, uniform vs. non-uniform, and determine their handedness.

Bioinspired, Cholesteric Liquid-Crystal Reflectors with Time-Controlled Coexisting Chiral and Achiral Structures.

The twisted structures of the chitin-based cuticle of beetles confer specific optical characteristics on them. Intrigued by the observation of Bragg gratings with a depth-dependent periodicity in the cuticle of Chrysina beetles, we determine the experimental conditions leading to their transcription into cholesteric liquid-crystal oligomers. We correlate the optical properties of reflectors thus produced with their internal morphology, as observed by transmission electron microscopy. With the use of a single parameter, thermal annealing time, the reflection color is made time-tunable. Different spectral bands and reflection colors from golden yellow to NIR are available, and the irreversibility of the final color is reached at the end. On the basis of the design concept and these properties, these hybrid chiral-achiral materials inspire the fabrication of smart reflective labels. When encapsulated in the package of a product to be kept under cold conditions, the label records the history of the product conservation. Two kinds of information based on color changes are recorded as follows: qualitative information reporting that the product was kept outside of the specified storage temperature and quantitative information giving an indication of the time elapsed since the temperature exceeded the storage temperature of the product.

Biomimetic design of iridescent insect cuticles with tailored, self-organized cholesteric patterns.

Replicating biological patterns is promising for designing materials with multifaceted properties. Twisted cholesteric liquid crystal patterns are found in the iridescent tessellated cuticles of many insects and a few fruits. Their accurate replication is extremely difficult since discontinuous patterns and colors must coexist in a single layer without discontinuity of the structures. Here, a solution is demonstrated by addressing striped insect cuticles with a complex twisted organization. Geometric constraints are met by controlling the thermal diffusion in a cholesteric oligomer bilayer subjected to local changes in the molecular anchoring conditions. A multicriterion comparison reveals a very high level of biomimicry. Proof-of-concept prototypes of anti-counterfeiting tags are presented. The present design involves an economy of resources and a high versatility of chiral patterns unreached by the current manufacturing techniques such as metallic layer vacuum deposition, template embossing and various forms of lithography which are limited and often prohibitively expensive.

Biomimicry of iridescent, patterned insect cuticles: comparison of biological and synthetic, cholesteric microcells using hyperspectral imaging.

Biological systems inspire the design of multifunctional materials and devices. However, current synthetic replicas rarely capture the range of structural complexity observed in natural materials. Prior to the definition of a biomimetic design, a dual investigation with a common set of criteria for comparing the biological material and the replica is required. Here, we deal with this issue by addressing the non-trivial case of insect cuticles tessellated with polygonal microcells with iridescent colours due to the twisted cholesteric organization of chitin fibres. By using hyperspectral imaging within a common methodology, we compare, at several length scales, the textural, structural and spectral properties of the microcells found in the two-band cuticle of the scarab beetle Chrysina gloriosa with those of the polygonal texture formed in flat films of cholesteric liquid crystal oligomers. The hyperspectral imaging technique offers a unique opportunity to reveal the common features and differences in the spectral-spatial signatures of biological and synthetic samples at a 6-nm spectral resolution over 400 nm-1000 nm and a spatial resolution of 150 nm. The biomimetic design of chiral tessellations is relevant to the field of non-specular properties such as deflection and lensing in geometric phase planar optics.

Dispersion of 20 fs pulses through band edges of cholesteric liquid crystals.

We demonstrate the ability to manipulate ultrashort pulses in cholesteric liquid crystals in the linear regime. We present an extensive analysis of the spectral changes undergone by 20fs pulses when propagating through band edges of cholesteric liquid crystals. The accurate quantification of the introduced optical dispersion opens the way to controlled stretching and compression of ultrashort pulses. The behaviors of cholesteric liquid crystal films with different thickness, bandgap and structural parameters (monotonic pitch versus pitch-gradient films) are compared. A statistical approach is disclosed to fidelize and deepen the set of experimental investigations.

Nanoscale hyperspectral imaging of tilted cholesteric liquid crystal structures.

Ongoing research on chiral liquid crystals takes advantage of the peculiar behavior of twisted structures subject to curvature. We demonstrate the fine tunability of the characteristics of the bandgap of a cholesteric structure in which the orientation of the helix axis spatially changes. To date, the spectral resolution of the order of 6 nm, herein reached by hyperspectral imaging, has not been solved in tilted helices. A correlation between spectral shifts and spatial twists is thus made possible.

Observation of an anisotropic texture inside the wax layer of insect cuticle.

The outermost part of insect cuticles is very often covered with wax, which prevents desiccation and serves for chemical communication in many species. Earlier studies on cuticular waxes have mainly focused on their chemical composition revealing complex mixtures of lipids. In the absence of information on their physical organization, cuticular waxes have been considered isotropic. Here we report the presence of parallel stripes in the wax layer of the carapace of the scarab beetle, Chrysina gloriosa, with a textural periodicity of ca. 28 nm, as revealed by electron microscopy of transverse sections. Observations at oblique incidence argue for a layered organization of the wax, which might be related to a layer-by-layer deposition of excreted wax. Our findings may lay the foundation for further studies on the internal structure of cuticular waxes for other insects.

Cholesteric liquid crystals in living matter.

Liquid crystals play an important role in biology because the combination of order and mobility is a basic requirement for self-organisation and structure formation in living systems. Cholesteric liquid crystals are omnipresent in living matter under both in vivo and in vitro conditions and address the major types of molecules essential to life. In the animal and plant kingdoms, the cholesteric structure is a recurring design, suggesting a convergent evolution to an optimised left-handed helix. Herein, we review the recent advances in the cholesteric organisation of DNA, chromatin, chitin, cellulose, collagen, viruses, silk and cholesterol ester deposition in atherosclerosis. Cholesteric structures can be found in bacteriophages, archaea, eukaryotes, bacterial nucleoids, chromosomes of unicellular algae, sperm nuclei of many vertebrates, cuticles of crustaceans and insects, bone, tendon, cornea, fish scales and scutes, cuttlebone and squid pens, plant cell walls, virus suspensions, silk produced by spiders and silkworms, and arterial wall lesions. This article specifically aims at describing the consequences of the cholesteric geometry in living matter, which are far from being fully defined and understood, and discusses various perspectives. The roles and functions of biological cholesteric liquid crystals include maximisation of packing efficiency, morphogenesis, mechanical stability, optical information, radiation protection and evolution pressure.

Multiwavelength micromirrors in the cuticle of scarab beetle Chrysina gloriosa.

Beetles from the genus Chrysina show vivid reflections from bright green to metallic silver-gold as a consequence of the cholesteric liquid crystal organization of chitin molecules. Particularly, the cuticle of Chrysina gloriosa exhibits green and silver stripes. By combining confocal microscopy and spectrophotometry, scanning electron microscopy and numerical simulations, the relationship between the reflectance and the structural parameters for both stripes at the micro- and nanoscales are established. Over the visible and near IR spectra, polygonal cells in tessellated green stripes behave as multiwavelength selective micro-mirrors and the silver stripes as specular broadband mirrors. Thermoregulation, conspecifics or intra-species communication, or camouflage against predators are discussed as possible functions. As a prerequisite to bio-inspired artificial replicas, the physical characteristics of the polygonal texture in Chrysina gloriosa cuticle are compared to their equivalents in synthetic cholesteric oligomers and their fundamental differences are ascertained. It is shown that the cuticle has concave cells whereas the artificial films have convex cells, contrary to expectation and assumption in the literature. The present results may provide inspiration for fabricating multiwavelength selective micromirrors or spatial wavelength-specific light modulators. STATEMENT OF SIGNIFICANCE: Many insects own a tessellated carapace with bumps, pits or indentations. Little is known on the physical properties of these geometric variations and biological functions are unknown or still debated. We show that the polygonal cells in scarab beetle Chrysina gloriosa behave as multiwavelength selective micromirrors over the visible and infrared spectra, with a variety of spatial patterns. In the context of biomimetic materials, we demonstrate that the carapace has concave cells whereas the artificial films have convex cells, contrary to expectation in the literature. Thermoregulation, communication or camouflage are discussed as advanced functions. Results may provide inspiration for fabricating spatial wavelength-specific light modulators and optical packet switching in routing technologies.

Size-effect of oligomeric cholesteric liquid-crystal microlenses on the optical specifications.

In cholesteric liquid-crystalline microlenses, we have studied the role of the microlens size on the focused light intensity and the focal length. We have found that the intensity is maximized by aiming a specific range for the diameter and the thickness of microlenses and that the focal length is adjusted by controlling the diameter and the annealing time of the optical film. Cholesteric microlenses may be used as wavelength-tunable directional light sources in organic soft-matter circuits.

Smectic layer instabilities in liquid crystals.

Scientists aspire to understand the underlying physics behind the formation of instabilities in soft matter and how to manipulate them for diverse investigations, while engineers aim to design materials that inhibit or impede the nucleation and growth of these instabilities in critical applications. The present paper reviews the field-induced rotational instabilities which may occur in chiral smectic liquid-crystalline layers when subjected to an asymmetric electric field. Such instabilities destroy the so-named bookshelf geometry (in which the smectic layers are normal to the cell surfaces) and have a detrimental effect on all applications of ferroelectric liquid crystals as optical materials. The transformation of the bookshelf geometry into horizontal chevron structures (in which each layer is in a V-shaped structure), and the reorientation dynamics of these chevrons, are discussed in details with respect to the electric field conditions, the material properties and the boundary conditions. Particular attention is given to the polymer-stabilisation of smectic phases as a way to forbid the occurrence of instabilities and the decline of related electro-optical performances. It is also shown which benefit may be gained from layer instabilities to enhance the alignment of the liquid-crystalline geometry in practical devices, such as optical recording by ferroelectric liquid crystals. Finally, the theoretical background of layer instabilities is given and discussed in relation to the experimental data.

Cholesteric liquid crystal gels with a graded mechanical stress.

In cholesteric liquid-crystalline gels, the mechanical role of the polymer network over the structure of the whole gel has been ignored. We show that it is the stress gradient exerted by the network over the helical structure that drives the broadening of the optical band gap, as evidenced by the absence of a gradient in chiral species. Model calculations and finite-difference time-domain simulations show that the network acts as a spring with a stiffness gradient. The present results indicate a revision to the common understanding of the physical properties of liquid-crystalline gels is necessary when a concentration gradient in a polymer network is present.

Wavelength-tunable light shaping with cholesteric liquid crystal microlenses.

The ability to guide light on the mesoscopic scale is important both scientifically and technologically. Especially relevant is the development of wavelength-tunable light-shaping microdevices. Here we demonstrate the use of cholesteric liquid crystal polygonal textures organized as an array of microlenses for this purpose. The beam shaping is controlled by tuning the wavelength of the incident light in the visible spectrum. By taking advantage of the self-organization property of liquid crystals, the structure of the lens and its optical response are tailored by changing the annealing time of the single layer material during a completely integrated one-step process. The intrinsic helical organization of the layer is the cause of the light shaping and not the shape of the surface as for conventional lenses. A new concept of light manipulation using the structure chirality of liquid crystals is demonstrated, which concerns soft matter photonic circuits to mould the light.

Liquid-crystal science from 1888 to 1922: building a revolution.

The saga of liquid crystals started with their discovery in 1888 by the botanist Friedrich Reinitzer, who unexpectedly observed "two melting points" for crystals extracted from the root of a carrot. At the end of the nineteenth century, most scientists did not believe in the existence of "liquid crystals" as promoted by the crystallographer Otto Lehmann. The controversies were very vivid; to the point that the recognition of mesomorphic states of matter by the scientific community required more than two decades. In the end, liquid crystals have changed our vision of matter by shattering the three-state paradigm. Since the mid-1970s, liquid crystals have revolutionized the worldwide information-display industry and now play a host of key roles in various technologies.

Cholesteric liquid crystals with a broad light reflection band.

The cholesteric-liquid-crystalline structure, which concerns the organization of chromatin, collagen, chitin, or cellulose, is omnipresent in living matter. In technology, it is found in temperature and pressure sensors, supertwisted nematic liquid crystal displays, optical filters, reflective devices, or cosmetics. A cholesteric liquid crystal reflects light because of its helical structure. The reflection is selective - the bandwidth is limited to a few tens of nanometers and the reflectance is equal to at most 50% for unpolarized incident light, which is a consequence of the polarization-selectivity rule. These limits must be exceeded for innovative applications like polarizer-free reflective displays, broadband polarizers, optical data storage media, polarization-independent devices, stealth technologies, or smart switchable reflective windows to control solar light and heat. Novel cholesteric-liquid-crystalline architectures with the related fabrication procedures must therefore be developed. This article reviews solutions found in living matter and laboratories to broaden the bandwidth around a central reflection wavelength, do without the polarization-selectivity rule and go beyond the reflectance limit.

Cholesteric liquid crystalline materials with a dual circularly polarized light reflection band fixed at room temperature.

An unpolarized normal-incidence light beam reflected by a cholesteric liquid crystal is left- or right-circularly polarized, in the cholesteric temperature range. In this article, we present a novel approach for fabricating a cholesteric liquid crystalline material that exhibits reflection bands with both senses of polarization at room temperature. A cholesteric liquid crystal that presents a twist inversion at a critical temperature T(c) is blended with a small quantity of photopolymerizable monomers. Upon ultraviolet irradiation above T(c), the liquid crystal becomes a polymer-stabilized liquid crystal. Below T(c), the material reflects a dual circularly polarized band in the infrared. By quenching the experimental cell at a temperature below the blend's melting point, the optical properties of the material in an undercooled state are conserved for months at room temperature, which is critical to potential applications such as heat-repelling windows and polarization-independent photonic devices.

Theoretical and experimental optical studies of cholesteric liquid crystal films with thermally induced pitch gradients.

The reflection properties of cholesteric films with thermally induced pitch gradients are theoretically and experimentally studied. It is shown that the optical behavior of such films corresponds to the averaged contribution of a number of stochastic pitch variation profiles, due to the transversal and longitudinal nonuniformities that develop in the helical structure of such samples. Depending on the annealing time, both narrow-band and broadband behavior can be selectively achieved. The influence of the pitch profile gradient on the broadband reflection performance of cholesteric samples is theoretically analyzed, and a multi-slab structure for achieving optimum efficiency is proposed.

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.

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.

Performances of a polymer-cholesteric-liquidcrystal output-coupler in Nd-doped fiber lasers.

The performances and characteristics of a polymer-cholestericliquid-crystal reflector, used as an output coupler in a Nd-doped fiber laser, are presented. We show that a judicious combination of a linear polarizer and a quarter wave plate with the cholesteric coupler allows for a continuous scanning of the output-intensity from zero to a maximum value following the well-known Malus law. The results are shown to be contained in a simple Jones Matrix formalism. The LP-QW-PCLC combination is characterized by a reflection coefficient that can be freely adjusted from 0 to 1 by a simple rotation of the quarter-wave plate.