RESUMEN
Chiral nematic liquid crystals--otherwise referred to as cholesteric liquid crystals (CLCs)--are self-organized helical superstructures that find practical application in, for example, thermography, reflective displays, tuneable colour filters and mirrorless lasing. Dynamic, remote and three-dimensional control over the helical axis of CLCs is desirable, but challenging. For example, the orientation of the helical axis relative to the substrate can be changed from perpendicular to parallel by applying an alternating-current electric field, by changing the anchoring conditions of the substrate, or by altering the topography of the substrate's surface; separately, in-plane rotation of the helical axis parallel to the substrate can be driven by a direct-current field. Here we report three-dimensional manipulation of the helical axis of a CLC, together with inversion of its handedness, achieved solely with a light stimulus. We use this technique to carry out light-activated, wide-area, reversible two-dimensional beam steering--previously accomplished using complex integrated systems and optical phased arrays. During the three-dimensional manipulation by light, the helical axis undergoes, in sequence, a reversible transition from perpendicular to parallel, followed by in-plane rotation on the substrate surface. Such reversible manipulation depends on experimental parameters such as cell thickness, surface anchoring condition, and pitch length. Because there is no thermal relaxation, the system can be driven either forwards or backwards from any light-activated intermediate state. We also describe reversible photocontrol between a two-dimensional diffraction state, a one-dimensional diffraction state and a diffraction 'off' state in a bilayer cell.
RESUMEN
Natural self-assembled three-dimensional photonic crystals such as blue-phase liquid crystals typically assume cubic lattice structures. Nonetheless, blue-phase liquid crystals with distinct crystal symmetries and thus band structures will be advantageous for optical applications. Here we use repetitive electrical pulses to reconfigure blue-phase liquid crystals into stable orthorhombic and tetragonal lattices. This approach, termed repetitively applied field, allows the system to relax between each pulse, gradually transforming the initial cubic lattice into various intermediate metastable states until a stable non-cubic crystal is achieved. We show that this technique is suitable for engineering non-cubic lattices with tailored photonic bandgaps, associated dispersion and band structure across the entire visible spectrum in blue-phase liquid crystals with distinct composition and initial crystal orientation. These field-free blue-phase liquid crystals exhibit large electro-optic responses and can be polymer-stabilized to have a wide operating temperature range and submillisecond response speed, which are promising properties for information display, electro-optics, nonlinear optics, microlasers and biosensing applications.
RESUMEN
Thin-film geo-phase optics have the potential to dramatically reduce size, weight, and power for large-aperture optical components as well as provide nonmechanical functionality. Topics are presented in manner of increasing conceptual and system complexity to convey the different levels and aspects of system performance improvements. An 8'' aperture, lightweight geo-phase lens is presented followed by discussions on both mechanical and nonmechanical beam steering embodiments. Laser damage thresholds for the thin-film geo-phase prisms are reported. Highly efficient and spectrally broadband nonmechanical line-of-sight steering is also demonstrated. Lastly, novel fabrication techniques, to the best of our knowledge, and the associated reduced fabrication cost implications are presented.
RESUMEN
Visible-light-driven molecular switches endowing reversible modulation of the functionalities of self-organized soft materials are currently highly sought after for fundamental scientific studies and technological applications. Reported herein are the design and synthesis of two novel halogen bond donor based chiral molecular switches that exhibit reversible photoisomerization upon exposure to visible light of different wavelengths. These chiral molecular switches induce photoresponsive helical superstructures, that is, cholesteric liquid crystals, when doped into the commercially available room-temperature achiral liquid crystal host 5CB, which also acts as a halogen-bond acceptor. The induced helical superstructure containing the molecular switch with terminal iodo atoms exhibits visible-light-driven reversible unwinding, that is, a cholesteric-nematic phase transition. Interestingly, the molecular switch with terminal bromo atoms confers reversible handedness inversion to the helical superstructure upon irradiation with visible light of different wavelengths. This visible-light-driven, reversible handedness inversion, enabled by a halogen bond donor molecular switch, is unprecedented.
RESUMEN
Development of light-driven functional materials capable of displaying reversible properties is currently a vibrant frontier from both scientific and technological points of view. Here a new visible-light-driven chiral molecular switch is synthesized and characterized. To the best of our knowledge, this is the first example of a chiral molecular switch in which the visible-light-driven azobenzene motif is directly linked to an axially chiral scaffold through a C-C bond. The chiral molecular switch exhibits trans-to- cis photoisomerization upon 530 nm irradiation and cis-to- trans isomerization upon 450 nm irradiation. The switch can thus be photoisomerized in both directions using visible light of different wavelengths, a promising attribute for device applications. It was found that this relatively rigid molecular switch exhibited a high helical twisting power (HTP) in liquid crystal hosts and a large change of HTP value upon photoisomerization. We achieved dynamic reflection tuning across the visible spectrum through incorporation into a self-organized helical superstructure, i.e., a cholesteric liquid crystal. We also demonstrated patterned photodisplays reflecting red, green, and blue circularly polarized light using these cholesteric films. Phototunable color displays were fabricated by selective light irradiation where the information can be reversibly hidden by applying an electric field and restored by applying either a mechanical force or an electric field of higher voltage.
RESUMEN
Owing to their dynamic attributes, non-covalent supramolecular interactions have enabled a new paradigm in the design and fabrication of multifunctional material systems with programmable properties, performances, and reconfigurable traits. Recently, the "halogen bond" has become an enticing supramolecular synthetic tool that displays a plethora of promising and advantageous characteristics. Consequently, this versatile and dynamic non-covalent interaction has been extensively harnessed in various fields such as crystal engineering, self-assembly, materials science, polymer chemistry, biochemistry, medicinal chemistry and nanotechnology. In recent years, halogen bonding has emerged as a tunable supramolecular synthetic tool in the design of functional liquid-crystalline materials with adjustable phases and properties. In this Concept article, the use of halogen bond in the field of stimuli-responsive smart soft materials, that is, liquid crystals is discussed. The design, synthesis and characterization of molecular and macromolecular liquid crystalline materials are described and the modulation of their properties has been emphasized. The power of halogen bonding in offering a large variety of functional liquid crystalline materials from readily accessible mesomorphic and non-mesomorphic complementary building blocks is highlighted. The article concludes with a perspective on the challenges and opportunities in this emerging endeavor towards the realization of enabling and elegant dynamic functional materials.
RESUMEN
Electrical control of the pitch has been reported in a variant of the cholesteric liquid crystal phase composed of chiral dopants and liquid crystal dimers with a bent conformation, such as CB7CB. For a finite range of applied electric field, the dimeric mesogens assume an oblique helicoidal structure, in which the helical axis is aligned along the electric field and the local director is tilted towards the helical axis (rather than being perpendicular to it). An electric field can directly regulate the periodicity (pitch), allowing reconfiguration of the optical response from a scattering or transparent state to a reflective state. Here, we employ po stabilization to retain the oblique helicoidal state absent an applied field. The polymer stabilized oblique helicoidal structures were investigated under various conditions and material compositions. With polymer stabilization, the magnitude of the selective reflection is found to be dependent on the strength of the applied field. Comparison of the electro-optical response of samples with and without a polymer network elucidates the relative role of boundary conditions, anchoring strength, and elastic energy on the stability of the oblique helicoidal state.
RESUMEN
Liquid crystals are traditionally classified as thermotropic, lyotropic or polymeric, based on the stimulus that governs the organization and order of the molecular system. The most widely known and applied class of liquid crystals are a subset of thermotropic liquid crystals known as calamitic, in which adding heat can result in phase transitions from or into the nematic, cholesteric and smectic mesophases. Photoresponsive liquid-crystal materials and mixtures can undergo isothermal phase transitions if light affects the order parameter of the system within a mesophase sufficiently. In nearly all previous examinations, light exposure of photoresponsive liquid-crystal materials and mixtures resulted in order-decreasing photo-induced isothermal phase transitions. Under specialized conditions, an increase in order with light exposure has been reported, despite the tendency of the photoresponsive liquid-crystal system to reduce order in the exposed state. A direct, photo-induced transition from the isotropic to the nematic phase has been observed in a mixture of spiropyran molecules and a nematic liquid crystal. Here we report a class of naphthopyran-based materials that exhibit photo-induced conformational changes in molecular structure capable of yielding order-increasing phase transitions. Appropriate functionalization of the naphthopyran molecules leads to an exceedingly large order parameter in the open form, which results in a clear to strongly absorbing dichroic state. The increase in order with light exposure has profound implications in optics, photonics, lasing and displays and will merit further consideration for applications in solar energy harvesting. The large, photo-induced dichroism exhibited by the material system has been long sought in ophthalmic applications such as photochromic and polarized variable transmission sunglasses.
RESUMEN
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.
RESUMEN
The formation and characterization of a switchable volume reflective element fabricated from a polymer liquid crystal (LC) polymer slice (POLICRYPS) structure by holographic photopolymerization at high temperature (65 °C) using a photosensitive/nematic liquid crystal prepolymer mixture is reported. The submicron Bragg structure formed consists of periodic continuous polymeric walls separated by periodic LC channels. The phase separated NLC self-aligns in a homeotropic alignment between the polymer walls as indicated by polarizing optical microscopy analysis (Maltese cross). The resulting periodic grating structure results in a Bragg reflection notch upon illumination with white light due to the periodic variation in refractive index. Electro-optical experiments realized through in-plane electrodes and temperature experiments confirm that the multilayer structure acts as a Bragg mirror whose reflection efficiency can be controlled by either a small (~3V/µm) electric field or temperature.
RESUMEN
Constructing and tuning self-organized three-dimensional (3D) superstructures with tailored functionality is crucial in the nanofabrication of smart molecular devices. Herein we fabricate a self-organized, phototunable 3D photonic superstructure from monodisperse droplets of one-dimensional cholesteric liquid crystal (CLC) containing a photosensitive chiral molecular switch with high helical twisting power. The droplets are obtained by a glass capillary microfluidic technique by dispersing into PVA solution that facilitates planar anchoring of the liquid-crystal molecules at the droplet surface, as confirmed by the observation of normal incidence selective circular polarized reflection in all directions from the core of individual droplet. Photoirradiation of the droplets furnishes dynamic reflection colors without thermal relaxation, whose wavelength can be tuned reversibly by variation of the irradiation time. The results provided clear evidence on the phototunable reflection in all directions.
RESUMEN
We studied the appearance of second- and third-order Bragg reflections in cholesteric liquid crystals (CLCs) in cells where the electric field was perpendicular to the helical axis. Second-order reflections with reflectance values as large as 80% of the first-order one were observed in the gap regions of alignment cells with interdigitated electrodes for CLC mixtures with pitches in the range 0.5-1.0 µm upon application of a field. The characterization was enabled by local probing of the CLC using a microspectrophotometer. LC cells that are transparent in the visible spectrum in the off-state and become colored upon application of a field due the second- or third-order reflection band appearance were demonstrated. The spectral position of the higher-order Bragg reflections can also be tuned by adjusting the magnitude of the electric field.
RESUMEN
A microspectrophotometer was used to elucidate the local optical properties of cholesteric liquid crystals (CLCs) in cells with interdigitated electrodes as a function of applied voltage. The spectra collected from a spatially selective and micron-sized sampling area allow for new insights into the spectral properties of CLCs in the gaps between patterned electrodes. The microscopic electro-optic response is shown to be highly dependent on the cell thickness and the electrode periodicity. Specifically, the helix unwinding of the CLC superstructure does not always occur uniformly in the sample, as a result of field gradients through the cell thickness: for cells with relatively narrow gaps and electrodes, the redshift occurs initially only in the CLC layers closest to the substrate with the electrodes, leading to broad reflection spectra and different reflection colors depending on which side of the cell is illuminated. Theoretical estimates of the expected shift in the reflection band gap based on the critical field for a given CLC material and the spatial variation of electric field in the cell are found to be in good agreement with the complex behavior observed experimentally. In contrast, in thin cells with wider gaps, the pitch increase affects the whole CLC layer uniformly, because the electric field gradient is small.
RESUMEN
In this study, we utilize plasma-enhanced chemical vapor deposition (PECVD) for the deposition of nanostructures composed of diphenylalanine. PECVD is a solvent-free approach and allows sublimation of the peptide to form dense, uniform arrays of peptide nanostructures on a variety of substrates. The PECVD deposited d-diphenylalanine nanostructures have a range of chemical and physical properties depending on the specific discharge parameters used during the deposition process.
Asunto(s)
Nanoestructuras/química , Péptidos/química , Fenilalanina/análogos & derivados , Gases em Plasma/química , Dipéptidos , Tamaño de la Partícula , Péptidos/síntesis química , Fenilalanina/química , Propiedades de SuperficieRESUMEN
Soft-matter-based photonic crystals like blue-phase liquid crystals (BPLC) have potential applications in wide-ranging photonic and bio-chemical systems. To date, however, there are limitations in the fabrication of large monocrystalline BPLCs. Traditional crystal-growth process involves the transition from a high-temperature disordered phase to an ordered (blue) phase and is generally slow (takes hours) with limited achievable lattice structures, and efforts to improve molecular alignment through post-crystallization field application typically prove ineffective. Here we report a systematic study on the molecular self-assembly dynamics of BPLC starting from a highly ordered phase in which all molecules are unidirectionally aligned by a strong electric field. We have discovered that, near the high-temperature end of the blue phase, if the applied field strength is then switched to an intermediate level or simply turned off, large-area monocrystalline BPLCs of various symmetries (tetragonal, orthorhombic, cubic) can be formed in minutes. Subsequent temperature tuning of the single crystal at a fixed applied field allows access to different lattice parameters and the formation of never-before-seen monoclinic structures. The formed crystals remain stable upon field removal. The diversity of stable monocrystalline BPLCs with widely tunable crystalline symmetries, band structures, and optical dispersions will significantly improve and expand their application potentials.
RESUMEN
Cholesteric liquid crystals (CLCs) are selectively reflective optical materials, the color of which can be tuned via electrical, thermal, mechanical, or optical stimuli. In this work, we show that self-regulation of the transmission of a circularly polarized incident beam can occur upon phototuning of the selective reflection peak of a photosensitive CLC mixture towards the pump wavelength. The autonomous behavior occurs as the red-shifting selective reflection peak approaches the wavelength of the incident laser light. Once the red-edge of the CLC bandgap and incident laser wavelength overlap, the rate of tuning dramatically slows. The dwell time (i.e., duration of the overlap of stimulus wavelength with CLC bandgap) is shown to depend on the radiation wavelength, polarization, and intensity. Necessary conditions for substantial dwell time of the CLC reflection peak at the pump beam wavelength include irradiation with low intensity light (~1mW/cm²) and the utilization of circularly polarized light of the same handedness as the helical structure within the CLC. Monitoring the optical properties in both reflection and transmission geometries elucidates differences associated with attenuation of the light through the thickness of the CLC film.
Asunto(s)
Rayos Láser , Cristales Líquidos/química , Cristales Líquidos/efectos de la radiación , Refractometría/instrumentación , Diseño de Equipo , Análisis de Falla de Equipo , Retroalimentación , LuzRESUMEN
The thermal bimorph is a very popular thermal sensing mechanism used in various applications from meat thermometers to uncooled infrared cameras. While thermal bimorphs have remained promising for scanning thermal microscopy, unfortunately the bending of the bimorph directly interferes with the bending associated with topographical information. We circumvent this issue by creating bimorphs that twist instead of bending and demonstrate the superior properties of this approach as compared to conventional scanning thermal microscopy.
Asunto(s)
Aleaciones/química , Aumento de la Imagen/instrumentación , Microscopía/instrumentación , Nanoestructuras/química , Nanotecnología/instrumentación , Termografía/instrumentación , Termómetros , Diseño de Equipo , Análisis de Falla de Equipo , Aumento de la Imagen/métodos , Microscopía/métodos , Nanoestructuras/ultraestructura , Nanotecnología/métodos , Termografía/métodos , TransductoresRESUMEN
Polymer electrolyte membranes (PEMs) with high and controlled ionic conductivity are important for energy-related applications, such as solid-state batteries and fuel cells. Herein we disclose a new strategy to fabricate long-range ordered PEMs with tunable ion conducting pathways using a holographic polymerization (HP) method. By incorporating polymer electrolyte into the carefully selected HP system, electrolyte layers/channels with length scales of a few tens of nanometers to micrometers can be formed with controlled orientation and anisotropy; ionic conductivity anisotropy as high as 37 has been achieved.
Asunto(s)
Holografía/métodos , Membranas Artificiales , Impresión Molecular/métodos , Nanoestructuras/química , Nanoestructuras/ultraestructura , Polímeros/química , Cristalización/métodos , Conductividad Eléctrica , Iones , Ensayo de Materiales , Tamaño de la PartículaRESUMEN
Pairs of cycloidal diffractive waveplates can be used to doubly diffract or collinearly propagate laser radiation of the appropriate wavelength. The use of a dynamic phase retarder placed in between the pair can be utilized to switch between the two optical states. We present results from the implementation of an azo-based retarder whose optical properties can be modulated using light itself. We show fast and efficient switching between the two states for both CW and single nanosecond laser pulses of green radiation. Contrasts greater than 100:1 were achieved. The temporal response as a function of light intensity is presented and the optical switching is shown to be polarization independent.
Asunto(s)
Dispositivos Ópticos , Refractometría/instrumentación , Procesamiento de Señales Asistido por Computador/instrumentación , Diseño de Equipo , Análisis de Falla de EquipoRESUMEN
In this paper we report the use of plasma-enhanced chemical vapor deposition (PECVD) for the simultaneous deposition and copolymerization of an amino acid with other organic and inorganic monomers. We investigate the fundamental effects of plasma-enhanced copolymerization on different material chemistries in stable ultrathin coatings of mixed composition with an amino acid component. This study serves to determine the feasibility of a direct, facile method for integrating biocompatible/active materials into robust polymerized coatings with the ability to plasma copolymerize a biological molecule (L-tyrosine) with different synthetic materials in a dry, one-step process to form ultrathin coatings of mixed composition. This process may lead to a method of interfacing biologic systems with synthetic materials as a way to enhance the biomaterial-tissue interface and preserve biological activity within composite films.