Voxel resolution in the directed self-assembly of liquid crystal polymer networks and elastomers.

Monomeric mixtures formulated to prepare a liquid crystal polymer network (LCN) or elastomer (LCE) can be "programmed" by surface alignment to retain complex and arbitrary spatial distributions of the director orientation upon polymerization. The localized control of orientation in a given volume (voxel) within these materials is the subject of intense research, currently motivated by the prospect of distinctive mechanical responses (both active and passive). Here, we report on a rapid and scalable photopatterning method to prepare alignment surfaces with a throughput of 10 mm2 s-1, using a commercial spatial light modulator and projection optics. Enabled by this method, we detail that the resolution limit of the inscribed director profile is not dictated by the optical system but is determined by the elastic-mediated orientational relaxation of the liquid crystalline materials. A simple model is experimentally validated and the implications for device design are discussed.

Blue-shifting tuning of the selective reflection of polymer stabilized cholesteric liquid crystals.

We report on electrically-induced, large magnitude (>300 nm), and reversible tuning of the selective reflection in polymer stabilized cholesteric liquid crystals (PSCLCs) prepared from negative dielectric anisotropy nematic liquid crystal hosts. The electrically-induced blue shift in the selective reflection of the PSCLCs is distinguished from our prior reports of bandwidth broadening and red-shifting tuning of the selective reflection in PSCLCs. The dominant factor in delineating the electro-optic response of the PSCLCs detailed here are the preparation conditions. Specifically, long exposure to UV intensity exceeding 250 mW cm-2. Other factors are shown to contribute to the response, including the type and concentration of photoinitiator.

Photosensitivity of reflection notch tuning and broadening in polymer stabilized cholesteric liquid crystals.

The position or bandwidth of the selective reflection of polymer stabilized cholesteric liquid crystals (PSCLCs) prepared from negative dielectric anisotropy ("-Δε") liquid crystalline hosts can be shifted by applying a DC voltage. The underlying mechanism of the tuning or broadening of the reflection of PSCLCs detailed in these recent efforts is ion-facilitated, electromechanical deformation of the structurally chiral, polymer stabilizing network in the presence of a DC bias. Here, we show that these electro-optic responses can also be photosensitive. The photosensitivity is most directly related to the presence of photoinitiator, which is a known ionic contaminant to liquid crystal devices. Measurement of the ion density of a series of control compositions before, during, and after irradiation with UV light confirms that the ion density in compositions that exhibit photosensitivity is increased by irradiation and correlates to not only the concentration of the photoinitiator but also the type. Thus, the magnitude of the electrically tuned or broadened reflection of PSCLC of certain compositions when subjected to DC field is further increased in the presence of UV light. While interesting and potentially useful in applications such as architectural windows, the effect may be deleterious to some device implementations. Accordingly, compositions in which photosensitivity is not observed are identified.

Dynamic, infrared bandpass filters prepared from polymer-stabilized cholesteric liquid crystals.

We report on the formulation and electrical control of the position and bandwidth of reflective bandpass filters prepared from cholesteric liquid crystal (CLC) in the infrared (3-5 µm). These filters are prepared from alignment cells employing infrared transparent electrodes and substrates. The optical nature of the electrodes is shown to strongly influence the resulting transmission of the bandpass filters outside of the spectral reflection.

Contactless, photoinitiated snap-through in azobenzene-functionalized polymers.

Photomechanical effects in polymeric materials and composites transduce light into mechanical work. The ability to control the intensity, polarization, placement, and duration of light irradiation is a distinctive and potentially useful tool to tailor the location, magnitude, and directionality of photogenerated mechanical work. Unfortunately, the work generated from photoresponsive materials is often slow and yields very small power densities, which diminish their potential use in applications. Here, we investigate photoinitiated snap-through in bistable arches formed from samples composed of azobenzene-functionalized polymers (both amorphous polyimides and liquid crystal polymer networks) and report orders-of-magnitude enhancement in actuation rates (approaching 10(2) mm/s) and powers (as much as 1 kW/m(3)). The contactless, ultra-fast actuation is observed at irradiation intensities <<100 mW/cm(2). Due to the bistability and symmetry of the snap-through, reversible and bidirectional actuation is demonstrated. A model is developed to elucidate the underlying mechanics of the snap-through, specifically focusing on isolating the role of sample geometry, mechanical properties of the materials, and photomechanical strain. Using light to trigger contactless, ultrafast actuation in an otherwise passive structure is a potentially versatile tool to use in mechanical design at the micro-, meso-, and millimeter scales as actuators, as well as switches that can be triggered from large standoff distances, impulse generators for microvehicles, microfluidic valves and mixers in laboratory-on-chip devices, and adaptive optical elements.

Mechanism of electrically induced photonic band gap broadening in polymer stabilized cholesteric liquid crystals with negative dielectric anisotropies.

We experimentally observed that the photonic band gap (reflection band) of polymer stabilized cholesteric liquid crystals with negative dielectric anisotropies can be greatly broadened under DC electric fields. We explored the underlying mechanism. We found that the dispersed polymer network moved when DC voltages were applied across the liquid crystal cell. The motion of the polymer network stretched the helical pitch of the liquid crystal on one side of the cell and compressed the helical pitch on the other side of the cell. We proposed a phenomenological theory to explain the motion of the polymer network and the effect of the polymer network on the helical pitch, and this theoretical prediction agreed well with the experimental results.

Non-uniform helix unwinding of cholesteric liquid crystals in cells with interdigitated electrodes.

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.

Photopiezoelectric composites of azobenzene-functionalized polyimides and polyvinylidene fluoride.

Light is a readily available and sustainable energy source. Transduction of light into mechanical work or electricity in functional materials, composites, or systems has other potential advantages derived from the ability to remotely, spatially, and temporally control triggering by light. Toward this end, this work examines photoinduced piezoelectric (photopiezoelectric) effects in laminate composites prepared from photoresponsive polymeric materials and the piezoelectric polymer polyvinylidene fluoride (PVDF). In the geometry studied here, photopiezoelectric conversion is shown to strongly depend on the photomechanical properties inherent to the azobenzene-functionalized polyimides. Based on prior examinations of photomechanical effects in azobenzene-functionalized polyimides, this investigation focuses on amorphous materials and systematically varies the concentration of azobenzene in the copolymers. The baseline photomechanical response of the set of polyimides is characterized in cantilever deflection experiments. To improve the photomechanical response of the materials and enhance the electrical conversion, the polyimides are drawn to increase the magnitude of the deflection as well as photogenerated stress. In laminate composites, the photomechanical response of the materials in sequenced light exposure is shown to transduce light energy into electrical energy. The frequency of the photopiezoelectric response of the composite can match the frequency of the sequenced light exposing the films.

Photostimulated control of laser transmission through photoresponsive cholesteric liquid crystals.

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.

Tuning ion conducting pathways using holographic polymerization.

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.

Electrically switchable, photoaddressable cholesteric liquid crystal reflectors.

We report on the development of photoaddressable cholesteric liquid crystal (CLC) mixtures capable of large range color tuning as well as direct on-off electrical switching. The continuously photoaddressable CLC mixtures are based on a high HTP azo-containing chiral material mixed with an off-the-shelf nematic liquid crystal (QL9/E44). By polymer stabilizing the QL9/E44 mixture, it is demonstrated that the photoaddressable reflection of the notch can be switched on and off with an AC voltage. The novel combination of these effects has potential utility in lasing, dynamic notch filters, and spatial light modulators.

Electrically Reconfigurable Liquid Crystalline Mirrors.

Reconfigurable optical materials are critical to realizing light control in eyewear or architectural windows. Here, we report on the electrical reconfiguration of the selective reflection of cholesteric liquid crystals (LCs). The distinctive responses detailed here are enabled by the preparation of a structurally chiral polymer stabilizing network that enforces anchoring of a low-molar-mass liquid crystalline media with positive dielectric anisotropy. The pitch of the reflective optical elements is directly regulated by a dc field, resulting in red or blue reflection wavelength tuning or broadening. The use of the positive dielectric LC host in concert with optimization of the material preparation conditions allows for reorientation of the LC molecules to achieve an optically clear state (homeotropic orientation) by the application of an ac field. In this way, the selective reflection of the optical elements can be moved, widened, and turned on and off. The electro-optic characteristics of these materials are another step forward to enabling the use of these materials in optics and photonics.

Electrical Control of Shape in Voxelated Liquid Crystalline Polymer Nanocomposites.

Liquid crystal elastomers (LCEs) exhibit anisotropic mechanical, thermal, and optical properties. The director orientation within an LCE can be spatially localized into voxels [three-dimensional (3-D) volume elements] via photoalignment surfaces. Here, we prepare nanocomposites in which both the orientation of the LCE and single-walled carbon nanotube (SWNT) are locally and arbitrarily oriented in discrete voxels. The addition of SWNTs increases the stiffness of the LCE in the orientation direction, yielding a material with a 5:1 directional modulus contrast. The inclusion of SWNT modifies the thermomechanical response and, most notably, is shown to enable distinctive electromechanical deformation of the nanocomposite. Specifically, the incorporation of SWNTs sensitizes the LCE to a dc field, enabling uniaxial electrostriction along the orientation direction. We demonstrate that localized orientation of the LCE and SWNT allows complex 3-D shape transformations to be electrically triggered. Initial experiments indicate that the SWNT-polymer interfaces play a crucial role in enabling the electrostriction reported herein.

3D Printing of Regenerated Silk Fibroin and Antibody-Containing Microstructures via Multiphoton Lithography.

Regenerated silk fibroin, a biopolymer derived from silkworm cocoons, is a versatile material that has been widely explored for a number of applications (e.g., drug delivery, tissue repair, biocompatible electronics substrates, and optics) due to its attractive biochemical properties and processability. Here, we report on the free-form printing of silk-based, 3D microstructures through multiphoton lithography. Utilizing multiphoton lithography in conjunction with specific photoinitiator chemistry and postprint cross-linking, a number of microarchitectures were achieved including self-supporting fibroin arches. Further, the straightforward production of high fidelity and biofunctional protein architectures was enabled through the printing of aqueous fibroin/immunoglobulin solutions.

Initiatorless Photopolymerization of Liquid Crystal Monomers.

Liquid crystal monomers are widely employed in industry to prepare optical compensating films as well as extend or enhance the properties of certain display modes. Because of the thermotropic nature of liquid crystalline materials, polymerization of liquid crystalline monomers (sometimes referred to as reactive mesogens) is often initiated by radical photoinitiation (photopolymerization) of (meth)acrylate functional groups. Here, we report on the initiatorless photopolymerization of commercially available liquid crystalline monomers upon exposure to 365 nm UV light. Initiatorless polymerization is employed to prepare thin films as well as polymer stabilizing networks in mixtures with low-molar-mass liquid crystals. EPR and FTIR confirm radical generation upon exposure to 365 nm light and conversion of the acrylate functional groups. A potential mechanism is proposed, informed by control experiments that indicate that the monomers undergo a type II Norrish mechanism. The initiatorless polymerization of the liquid crystalline monomers yield liquid crystalline polymer networks with mechanical properties that can be equal to those prepared with conventional radical photoinitiators. We demonstrate that initiatorless polymerization of display modes significantly increases the voltage holding ratio, which could result in a reduction in drive voltages in flat-panel televisions and hand-held devices, extending battery life and reducing power consumption.

Polymer crystallization/melting induced thermal switching in a series of holographically patterned Bragg reflectors.

Holographic photopolymerization (H-P) is a simple, fast and attractive means to fabricate one-, two- and three-dimensional complex structures. Liquid crystals, nanoparticles and silicate nano-plates have been patterned into submicron periodical structures. In this article, we report fabrication of a one-dimensional reflection grating structure by patterning a semicrystalline polymer, polyethylene glycol (PEG), in Norland resin (thiol-ene based UV curable resin) matrix using the H-P technique. Sharp notches observed in the reflection grating of this Norland/PEG system indicate a finite Δ present in the system due to spatial segregation of the PEG and Norland resin. The notch position red shifts upon heating and the diffraction efficiency (ratio between diffraction and incident light intensity, DE) increases from ∼20% to 60% for the Norland 65/PEG 4600 grating. This dynamic behavior of the reflection grating is also fully reversible. The unique thermal switching behavior is attributed to the melting/formation of PEG crystals during heating/cooling. By employing different molecular weight PEGs which have different melting temperatures, a series of switching temperatures have been achieved. Since PEG can be easily coupled with a variety of functional groups, this research might shed light on fabricating multifunctional Bragg gratings using the H-P technique.

Actuating materials. Voxelated liquid crystal elastomers.

Dynamic control of shape can bring multifunctionality to devices. Soft materials capable of programmable shape change require localized control of the magnitude and directionality of a mechanical response. We report the preparation of soft, ordered materials referred to as liquid crystal elastomers. The direction of molecular order, known as the director, is written within local volume elements (voxels) as small as 0.0005 cubic millimeters. Locally, the director controls the inherent mechanical response (55% strain) within the material. In monoliths with spatially patterned director, thermal or chemical stimuli transform flat sheets into three-dimensional objects through controlled bending and stretching. The programmable mechanical response of these materials could yield monolithic multifunctional devices or serve as reconfigurable substrates for flexible devices in aerospace, medicine, or consumer goods.

Topography from topology: photoinduced surface features generated in liquid crystal polymer networks.

Films subsumed with topological defects are transformed into complex, topographical surface features with light irradiation of azobenzene-functionalized liquid crystal polymer networks (azo-LCNs). Using a specially designed optical setup and photoalignment materials, azo-LCN films containing either singular or multiple defects with strengths ranging from |½| to as much as |10| are examined. The local order of an azo-LCN material for a given defect strength dictates a complex, mechanical response observed as topographical surface features.

Photoinduced hyper-reflective cholesteric liquid crystals enabled via surface initiated photopolymerization.

A structured polymer was synthesized by surface initiated photopolymerization in the presence of a cholesteric liquid crystal (CLC). The templated helical polymer (traversing 2/3 the cell thickness) was backfilled with an opposite handedness, photoresponsive CLC mixture yielding a photo-induced, large contrast, hyper-reflective (R > 99%) CLC film.

Holographically directed assembly of polymer nanocomposites.

Layered polymer/nanoparticle composites have been created through the one-step two-beam interference lithographic exposure of a dispersion of 25 and 50 nm silica particles within a photopolymerizable mixture at a wavelength of 532 nm. The polymerizable mixture is composed of pentaerythritol triacrylate (monomer), 1-vinyl-2-pyrrolidinone (monomer), and photoinitiator. In the areas of constructive interference, the monomer begins to polymerize via a free-radical process and concurrently the nanoparticles move into the regions of destructive interference. The effects of exposure time, power density, nanoparticle size, and periodicity on the final nanocomposite structure were measured with transmission electron microscopy to determine the mechanism for particle segregation. Diffraction from the sample was monitored as well, though its magnitude was not a good predictor of nanostructure in this relatively low index contrast system. Exposure time did not have a strong effect on the final structure. The best nanoparticle sequestration was observed at reduced laser power density, smaller interferogram periodicity, and decreased nanoparticle size, indicating that particle segregation is dominated by diffusion-limited nanoparticle transport directed by a matrix containing a gradient of polymerization kinetics.