Thermoresponsive mobility of liquid crystals and reactive mesogens during photopolymerization-induced phase separation.

Molecular interactions between liquid crystals (LCs) and reactive mesogens (RMs) at temperatures across the phase transition regions were comprehensively studied during photopolymerization-induced phase separation (PPIPS) beginning with raw mixtures until the formation of polymer network liquid crystals (PNLCs). Then, the molecules were found to be nonuniformly more and less mobile in response to temperature as PPIPS progressed. Optical birefringence and infrared absorption were carefully measured throughout PPIPS, using 4-cyano-4'-hexylbiphenyl (6CB) and 1,4bis-[4-(3-acryloyloxypropyloxy) benzoyloxy]-2-methylbenzene (RM257) as typical LCs and RMs. Microscopic views of thermoresponsive changes in the molecular orientation order of both LCs and RMs were obtained: LCs and RMs in raw mixtures interacted with one another but uniformly transformed their molecular orientation. Such interactions continuously change to become nonuniform with progress in PPIPS. At the incipient stages of PPIPS, RMs, which are polymerized but not completely networked, inhibit LCs from changing their molecular orientation and vice versa. As PPIPS progresses, some LCs become more mobile and some less mobile owing to RM constraints. The domain configuration of the submicrometer phase separation affects the thermoresponsive mobility of LCs and RMs, that is, LCs become more mobile in LC-richer areas. The quantitative knowledge here provides comprehensive insight that LCs and RMs are mutually constrained and that such interactive behavior varies nonuniformly as PPIPS progresses.

Thermally responsive polymer-dispersed liquid crystal diffusers fabricated using laser speckle pattern irradiation.

This study examined the thermal response of polymer-dispersed liquid crystal (PDLC) diffusers, patterned using a two-lens imaging system. Optical modulation was achieved by modifying the PDLC transmittance using temperature-induced changes to liquid crystal (LC) orientation. PDLCs with controllable scattering properties were obtained by irradiating LC-polymer composites with laser speckle patterns. The variation of the scattering characteristics of the PDLCs with temperature, average speckle size, and LC orientation order was analyzed to determine the most suitable parameters for a diffuser for smart window solar-ray control applications. The findings of these experiments demonstrate that using speckle patterns, a one-time laser exposure process, can provide a simple fabrication method of novel optical devices.

Thermoresponsive Reflective Scattering of Meso-Scale Phase Separation Structures of Uniaxially Orientation-Ordered Liquid Crystals and Reactive Mesogens.

Polymer network liquid crystals (PNLCs) capable of thermoresponsive change in reflective scattering were fabricated using a self-organization technique called photopolymerization-induced phase separation. These PNLCs exhibit nonscattering states at temperatures τ below the nematic-to-isotropic (NI) phase transition temperature τNI but reflective scattering states at τ values above τNI. The magnitude of change of optical clarity is 80% and of solar transmittance is 20% in PNLCs with a thickness of 50 µm. The microscopic structures consist of wavelength- or meso-scale phase separation domains of liquid crystals (LCs) and polymerized reactive mesogens (RMs) in which cyanobiphenyl (CB) groups are thermoresponsively transformed between uniaxially orientation-co-ordered and disordered states. Such thermoresponsive structures were fabricated by employing the CB groups as mesogenic bodies, which were expected to mutually associate due to their physicochemical structures. Cross-linkers stabilized the meso-scale domains and made the PNLCs durable through repeated temperature changes. Polarizing optical microscopy (POM) and scanning electron microscopy showed meso-scale composites that reflectively scatter visible and near-infrared light. POM and Fourier-transform infrared spectroscopy at different temperatures suggest that the orientation order of the CB groups changes in the LC phase in response to temperature but remains ordered in the RM phase. Such a thermoresponsive change in the orientation order produces the switchability in meso-scale nonuniformity and consequently in reflective light scattering. The thermoresponsive PNLCs are not only effective as energy-saving smart windows but also advantageous at stages of manufacture, installation, and operation.

Normal- and Reverse-Mode Thermoresponsive Controllability in Optical Attenuation of Polymer Network Liquid Crystals.

A simple nonuniform irradiation method for photopolymerization-induced phase separation (PPIPS) was developed to produce unconventional mesoscale domain structures composed of liquid crystal (LC) and reactive mesogen (RM) phases. The LC/RM phase formations and their molecular orientation ordering through PPIPS were comprehensively investigated as a function of LC/RM molar ratio, curing temperature, and the use of uniform or nonuniform irradiation. Then, two different optical-anisotropic structures that can cause normal- or reverse-mode thermoresponsive light attenuation were formed by nonuniform irradiation at different curing temperatures at the same molar ratios. These two structures consist of mesoscale domains organized with multiaxially orientation-ordered LCs and orientation-disordered RMs for normal-mode thermoresponse and uniaxially orientation-ordered LCs and RMs for reverse-mode thermoresponse. Phase-separation nuclei were generated by nonuniform irradiation at the incipient stage during the PPIPS process under nonuniform irradiation and subsequently coalesced to form mesoscale polymer networks while maintaining their molecular orientation order. This is a promising method to overcome the restraint of structural controllability due to intrinsic material properties and thus to provide unconventional optical and photonic devices, such as thermoresponsive smart windows and thermometric sheets.

Tolerance of holographic polymer-dispersed liquid crystal memory for gamma-ray irradiation.

The radiation-hardened characteristics of holographic polymer-dispersed liquid crystal (HPDLC) memory are discussed in the application for an optically reconfigurable gate array. The radiation experiments are conducted using a cobalt 60 gamma radiation source to examine the tolerance of a 100 Mrad total ionizing dose for the HPDLC memory. The optical properties are compared in the conditions before and after gamma-ray irradiation for the fabricated HPDLC gratings. The effects of gamma-ray irradiation on the internal grating structure are also investigated by polarization optical microscopy and scanning electron microscopy observations. The HPDLC memory irradiated by a 100 Mrad total ionizing dose demonstrates the implementation of the optical reconfiguration in a gate-array VLSI.

Multiple Bragg Diffractions with Different Wavelengths and Polarizations Composed of Liquid Crystal/Polymer Periodic Phases.

We first fabricated holographic polymer-dispersed liquid crystals (HPDLCs) that produce multiple Bragg diffractions with different polarization states for every angle of incidence, through a photopolymerization-induced phase separation by one-time interferential exposure. The polarizations of the Bragg diffractions were well-controlled at individual wavelengths in the fabrication process by the compositional ratio of LCs to monomers. The raw mixtures of extremely low-functionality monomers having very different viscosities were used to reduce the domain size in phase separation and subsequently to form elaborate periodic structures of the LC and polymer phases. A cross-linker (1-vinyl-2-pyrrolidione) and a prepolymer with urethane groups were employed to strengthen the polymer network. Note that the diffractions of our HPDLCs are regarded as not purely but mostly Bragg type, according to the evaluation with the established criteria. The devices, which are monolithic but versatile in diffractive behaviors, have advantages of simple manufacturing and handling.

Formation of holographic polymer-dispersed liquid crystal memory by angle-multiplexing recording for optically reconfigurable gate arrays.

Formation of holographic polymer-dispersed liquid crystal (HPDLC) memory for an optically reconfigurable gate array is discussed for angle-multiplexing recording by controlling the laser interference exposure in LC composites. The successive laser illumination system to record the various configuration contexts at the specified region and angle in HPDLC memory is constructed by using the combination of a half-mirror and a photomask placed on the motorized stages under the control of a personal computer. The effect of laser exposure energy on the formation of holographic memory is investigated by measuring diffraction intensity as a function of exposure energy during the grating formation process and observing the internal grating structure by scanning electron microscopy. The optical reconfiguration in the gate-array VLSI is executed for configuration contexts of OR and NOR operations shown as logical operators that are reconstructed by laser irradiation at different incident angles for a specified region in the HPDLC memory.

Temperature dependence of anisotropic diffraction in holographic polymer-dispersed liquid crystal memory.

Grating devices using photosensitive organic materials play an important role in the development of optical and optoelectronic systems. High diffraction efficiency and polarization dependence achieved in a holographic polymer-dispersed liquid crystal (HPDLC) grating are expected to provide polarization-controllable optical devices, such as a holographic memory for optically reconfigurable gate arrays (ORGAs). However, the optical property is affected by the thermal modulation around the transition temperature (T(ni)) where the liquid crystal (LC) changes from nematic to isotropic phases. The temperature dependence of the diffraction efficiency in HPDLC grating is investigated using four types of LC composites comprised of LCs and monomers having different physical properties such as T(ni) and anisotropic refractive indices. The holographic memory formed by the LC with low anisotropic refractive index and LC diacrylate monomer implements optical reconfiguration for ORGAs at a high temperature beyond T(ni) of LC.

Formation of temperature dependable holographic memory using holographic polymer-dispersed liquid crystal.

Grating devices using photosensitive organic materials play an important role in the development of optical and optoelectronic systems. High diffraction efficiency and polarization dependence achieved in a holographic polymer-dispersed liquid crystal (HPDLC) grating are expected to provide polarization controllable optical devices, such as the holographic memory for optically reconfigurable gate arrays (ORGAs). However, the optical property is affected by the thermal modulation around the transition temperature (T(ni)) that the liquid crystal (LC) changes from nematic to isotropic phases. The temperature dependence of the diffraction efficiency in HPDLC grating is discussed with two types of LC composites comprised of isotropic and LC diacrylate monomers. The holographic memory formed by the LC and LC diacrylate monomer performs precise reconstruction of the context information for ORGAs at high temperatures more than 150°C.

Optical reconfiguration by anisotropic diffraction in holographic polymer-dispersed liquid crystal memory.

Holographic polymer dispersed liquid crystal (HPDLC) memory is fabricated by a photoinduced phase separation comprised of polymer and liquid crystal (LC) phases using laser light interference exposures. The anisotropic diffraction induced by the alignment of LC in the periodic structure of the HPDLC memory is applied to reconstruct the configuration contexts for the optically reconfigurable gate arrays. Optical reconfiguration for various circuits under parallel programmability is implemented by switching the polarization state of incident light on the HPDLC memory using a spatial light modulator.

Optical diffractometry of highly anisotropic holographic gratings formed by liquid crystal and polymer phase separation.

Optical diffractometry is proposed as a practical method of quantitatively analyzing the microscopic structural origins of a wide range of highly efficient and linearly polarized optical diffraction grating produced from holographic polymer-dispersed liquid crystal. The structure is organized by a spatially periodical distribution of submicrometer-scale liquid crystal (LC) droplets in a polymer matrix. Six independent Bragg diffraction spectra were obtained at two orthogonal polarization states at temperatures below, at, and above the nematic-to-isotropic phase transition point. These spectra were simultaneously analyzed by employing anisotropic diffraction theory under the restraint of a simple and widely useful structural model constructed on the basis of the previously reported microscopic observations. The refractive indices of spatially periodic LC- and polymer-rich phases were analyzed using Cauchy's equation as a function of optical wavelength. The present diffractometry was demonstrated for a variety of holographic structures, and the structural parameters were discussed such as the filling ratio of LC droplets to polymer matrix, the orientational order in the droplets, and the thermo-optic properties in the LC droplets. Furthermore, the higher order Bragg diffractions were measured and discussed. The proposed method was examined in consistency by comparisons with polarizing optical microscopy and scanning electron microscopy.

Holographic polymer-dispersed liquid crystal memory for optically reconfigurable gate array using subwavelength grating mask.

Holographic polymer-dispersed liquid crystal (HPDLC) memory formed by a subwavelength grating (SWG) mask is presented for new optical information processing. The SWG structure in a photomask is formed on the SiO(2) plate using the anisotropic reactive ion etching technique. The configuration contexts for optically reconfigurable gate arrays (ORGAs) are stored in the HPDLC memory by polarization modulation property based on the form birefringence of the SWG plate. The configuration context pattern in the HPDLC memory is reconstructed to write it for the ORGAs under parallel programmability.

Effects of anisotropic diffractions on holographic polymer-dispersed liquid-crystal gratings.

Volume gratings fabricated by interferometric exposure using composite materials composed of nematic liquid crystals (LC) and LC diacrylate monomers are discussed in the effects of diffraction properties on different grating formations, such as varying LC content ratios, film thicknesses, and the surface conditions composed of alignment layers and rubbing directions. Diffraction properties are experimentally investigated in the viewpoints of anisotropic diffraction and LC orientation. The polarization-azimuth dependence of diffraction efficiencies as functions of the incident polarization states shows the controllability of anisotropic diffractions based on the effects of different surface conditions.

Effects of thermal modulation on diffraction in liquid crystal composite gratings.

A microperiodic structure composed of polymer and liquid crystal (LC) phases, called holographic polymer dispersed LC, is fabricated by a photo-induced phase separation technique using LC composites with different physical properties, such as refractive indices and clearing points. Effects of thermal modulation on diffraction properties of LC composite gratings are experimentally investigated in the viewpoints of polarization and temperature dependences. The diffractions based on the change of refractive index induced by the nematic-isotropic transition of LCs with the increase of temperature are applied for a holographic image reconstruction.

Formation of holographic memory for defect tolerance in optically reconfigurable gate arrays.

Holographic polymer-dispersed liquid-crystal (HPDLC) memory using liquid-crystal composites is proposed for new optical information processing. Formation of HPDLC memory using a photomask is discussed for parallel programmability to realize fast reconfiguration of optically reconfigurable gate arrays (ORGAs). The defect tolerance of HPDLC memory is investigated to clarify the defect limitation of holographic configurations using ORGAs. Experimental results show that the noise ratio less than 15% applied to HPDLC memory rarely affects its diffraction pattern or a reconfiguration context.

Control of anisotropic diffraction in liquid-crystal composite volume gratings.

Orientation-controlled anisotropic diffraction gratings are realized by interferometric exposure using composite materials of nematic liquid crystals (LCs) and LC diacrylate monomers. The anisotropic diffraction properties in volume gratings, which dominantly diffract p- or s-polarized light, are shown to be controlled by the rubbed directions of the alignment layers under the control of the photopolymerization temperature. Images of the fringe patterns observed by polarization microscopy show the effects of the alignment layers on the LC orientation during grating formation.

Formation of anisotropic diffraction gratings in a polymer-dispersed liquid crystal by polarization modulation using a spatial light modulator.

Anisotropic diffraction gratings based on a holographic polymer-dispersed liquid crystal (HPDLC) are realized by interferometric exposure using a spatial light modulator (SLM). The SLM is used in the HPDLC grating formation for anisotropic holographic recordings of two-dimensional polarization states for an incident light beam. The diffraction efficiency for P-polarization and the distinctive ratio of diffraction efficiency in P-polarization to that in S-polarization increases with the signal level applied to the SLM. The resulting volume gratings exhibit diffraction efficiency of more than 60% and a distinctive ratio of diffraction over 100. The microscopic origin of the anisotropic property is investigated by an optical polarizing microscope. The novel characteristics of the anisotropic diffraction properties of HPDLC are applied to an image reconstruction technique.