Unpolarized UV Light Research Articles

(Invited) Near Field Photocatalysis for Site-Selective Reactions By Using ZnO Nanoplates

Nanofabrication is a technology for control of the morphology, orientation, and configuration of nanomaterials. When ordinary, propagating light is employed as a processing tool, subwavelength fabrication is difficult due to the diffraction limit. However, if optical near field, which is localized in a subwavelength region is used, nanofabrication beyond the diffraction limit is possible.We have demonstrated that subwavelength nanofabrication is possible by taking advantage of the optical near field. Since hot electron-hole pairs are generated at around the plasmonic resonance sites, the energetic carriers can be used to drive oxidative dissolution of Ag,1,2 oxidative deposition of PbO2,3,4 and reductive deposition of Ag,5 in a site-selective manner. These techniques have been applied to subwavelength photochromic data storage,1,2 fabrication of chiral nanoparticles,4-7 and site-selective modification of a plasmonic photocatalyst with a co-catalyst.8 Generation of optical near field is possible even at non-plasmonic, semiconducting or dielectric nanostructures. Here we employed In-doped ZnO (In:ZnO) as a semiconductor photocatalyst. Hexagonal In:ZnO nanoplates were synthesized and adsorbed onto a glass substrate, and irradiated with linearly polarized UV light in the presence of Ag ions for reductive deposition of Ag. The optical near field generated under polarized UV light gave rise to site-selective Ag deposition. Also, the sample exhibited linear dichroism (LD) signals, indicating that the nanoparticles have optical anisotropy. On the other hand, unpolarized UV light gave no optical anisotropy. Electromagnetic simulations successfully reproduced the LD spectra. We have also performed site-selective oxidation reactions by using the hexagonal In:ZnO nanoplates. Tanabe, I.; Tatsuma, T. Nano Lett. 2012, 12, 5418–5421. Saito, K.; Tanabe, I.; Tatsuma, T. J. Phys. Chem. Lett. 2016, 7, 4363–4368.Nishi, H.; Sakamoto, M.; Tatsuma, T. Chem. Commun. 2018, 54, 11741–11744.Saito, K.; Tatsuma, T. Nano Lett. 2018, 18, 3209–3212.Ishida, T.; Isawa, A.; Kuroki, S.; Kameoka, Y.; Tatsuma, T. Appl. Phys. Lett. 2023, 123, 061111.Morisawa, K.; Ishida, T.; Tatsuma, T. ACS Nano 2020, 14, 3603–3609.Shimomura, K.; Nakane, Y.; Ishida, T.; Tatsuma, T. Appl. Phys. Lett. 2023, 122, 151109.Kim, K.; Nishi, H.; Tatsuma, T. J. Chem. Phys. 2022, 157, 111101.

Polarization-insensitive dielectric metamaterial absorber for near-unity UV-light trapping in monolayer graphene

With the aim of improving UV light trapping capability in monolayer graphene, a nanomesh metamaterial absorber is proposed, which exhibits the polarization-insensitive feature due to the geometrical symmetry. Through the functional combination of magnetic resonance and UV mirror, the absorption of unpolarized UV light in monolayer graphene can reach 99.5% under normal incidence. The absorption enhancement is induced by the magnetic resonance mode between the dielectric silica nanomesh and the calcium fluoride base layer. The effects of geometric parameters on the absorption spectra are systematically investigated. The proposed structure shows insensitive to manufacturing deviations, which can maintain at a high UV absorption rate of more than 99% within the nanomesh width ranging from 50 nm to 90 nm. Furthermore, after delicate optimization of the geometric parameters, two sharp resonances with absorbance more than 90% can be excited simultaneously inside the absorber. Our work provides an important theoretical guide for the design of optoelectronic devices based on two-dimensional materials in the UV range.

Higher–Order Bragg Reflection Colors in Polymer–Stabilized Cholesteric Liquid Crystals

The dynamic electro‐optic (EO) response of polymer‐stabilized cholesteric liquid crystals prepared using unpolarized UV light (U–PSCLC), such as reflection bandwidth broadening and either red or blue tuning of the reflection peak, has been previously reported. Herein, recent efforts to use a polarized single argon‐ion laser beam to create PSCLCs (L–PSCLCs) with higher‐order reflections are described. The L–PSCLCs exhibit a primary reflection peak in the near‐infrared (NIR) regime and a second‐order reflection band with a narrow bandwidth in the visible regime that results from a deformed in‐plane CLC helical structure. The initial positions of the reflection bands are adjusted by the chiral dopant concentrations of the CLC mixture, and red, green, and blue reflection colors from the second‐order Bragg reflection are demonstrated. The primary and the second‐order reflection bands can be shifted to longer wavelengths by application of a DC electric field. The reflection efficiency of the higher‐order reflection notch increases with polymer concentration, which affects the degree of in‐plane deformation and fixation of the CLC helix. Modeling is used to further explain the formation of the higher‐order reflection bands of PSCLCs observed experimentally.

Manipulation of liquid crystal alignment through interfacial modification of photoresponsive polyimides remotely actuated by dual wavelength linearly polarized light

High-quality alignment of liquid crystals (LCs) for large area display has been highly demanding for display market. To achieve a uniform and stable LC alignment, a photoresponsive azo-polyimide with two different substitution ratio of azo-dye moiety in the side chain of the polyimide has been successfully synthesized and characterized. Depending on the ratio of azo-dye substitutions, the solubility and coating nature of polyimides vary greatly and initially show random planar or homeotropic alignment of LCs. In situ photoalignment process has been performed to achieve a homogeneous planar alignment of LCs from the initial random planar state and a uniform pretilt state from the initial homeotropic cells using linearly polarized visible light (LPVL) irradiation in the isotropic phase of LCs. Furthermore, obtained alignment states have been stabilized using unpolarized UV light for RM polymerization in the nematic phase of LCs. Hence, the dual wavelength photoalignment approach has been successfully implemented to obtain the different stable alignments of LCs. Also, the results conclude that the tilt angle varies by dose of LPVL irradiation and gets significantly altered due to change in reactive mesogen (RM) concentrations. The surface investigations reveal a contrasting nature for the planar and vertically aligned substrates before and after RM stabilization.

Highly enantioselective photo-polymerization enhanced by chiral nanoparticles and in situ photopatterning of chirality

Chiral noble metal nanoparticles has recently gained great interest due to their potential applications including ultrasensitive chiral recognition and asymmetric synthesis. We anticipate that they could be utilized to induce asymmetric photo-polymerization reactions with high enantioselectivity and reactivity. Here, we report such a system. By employing silver nanoparticles modified with cysteine as the chiral inducer, polydiacetylene (PDA) with high chiral asymmetry was obtained from achiral diacetylene monomers triggered with unpolarized UV light. Furthermore, the helical sense of chirality can be controlled by varying the wavelength of UV irradiation. This enables a feasible and economical method to fabricate programmable 2D patterns of chiral PDA with tailored chirality distributions, such as smooth gradients in chirality and micropatterns with tailorable circularly polarized luminescence. Our finding not only opens a pathway for producing programmable chiroptical micropatterns, but also is highly valuable for deeper understanding of symmetry breaking in enantioselective photochemical reactions.

Direct Visualization of Optical Activity in Chiral Substances Using a Helical Nanofilament (B4) Liquid Crystal Phase

AbstractDetecting the chirality of material is very important in material science, chemistry, pharmacology, and biomaterial science because it is useful for identifying and discarding unintended side effects. Here, directly visualized is the optical activity of chiral samples using an orientation‐controlled helical nanofilament (HNF, B4) liquid crystal (LC) phase made of achiral bent‐shaped molecules. The vertical orientation of the HNFs is induced by shining unpolarized UV light. Right‐ or left‐handed domains of the HNFs are formed because of the lack of molecular chirality, each single‐handed domain is large enough to be seen with the naked eye, up to ≈several mm2. The periodic arrays of aligned HNFs reflect a specific color, here green, due to the Bragg reflection. Such a reflector enables an easy detection of optical activity of a sample placed on it. The device is tested with naturally chiral substances, like fructose and glucose, which exhibit opposite sense of optical activity, as well as with structurally chiral nematic LC phase and reveals high sensitivity of a detection.

Process Design and Fabrication of Sample for Non-contact Liquid Crystal Alignment with High Yield

In this study, we report the results of an experiment for aligning liquid crystals (LCs) by irradiating ultraviolet rays that are not polarized to an alignment layer, and a simulation result on the alignment principle. In the case of irradiating un-polarized ultraviolet rays to the substrate coated with the alignment film, there have been many experimental reports on the alignment mechanism of the LC due to the anisotropy generated in the substrate, but the theoretical approach is somewhat lacking. As a result of the experiment, the best orientation was observed at around 45°. As a result of the simulation, it was found that the maximum difference between the p-polarization and the s-polarization was within the range of similar angles there was. The theoretical approach to the alignment mechanism of LC was possible. And we have experimentally confirmed that the mechanism of liquid crystal alignment by conventional Groove theory is possible by irradiation of unpolarized UV light. The AFM analysis confirmed that the surface anisotropy that causes this orientation principle actually occurs in the unpolarized UV light. It is expected that this non-contact orientation method can realize higher production yield than the conventional contact type rubbing method, and the result of this study could contribute to the improvement of the yield.

Polyimide-Free Planar Alignment of Nematic Liquid Crystals: Sequential Interfacial Modifications through Dual-Wavelength in Situ Photoalignment.

High-quality alignment control of liquid crystals (LCs) for ultrahigh-definition large-sized display is a challenging task. A conventional rubbing method has obvious limitations for fabricating large-sized displays with a small pixel size and an uneven inner surface. To comply with the current trend, we propose a simple and reliable polyimide-less in situ photoalignment. It was achieved using a visible-light-sensitive azo-dye and a mesogenic acrylate, both doped to host LCs. Without using a pretreated alignment layer, mono- and multidomain uniaxial alignments of LC molecules were induced by linearly polarized visible light (LPVL) and subsequently stabilized by unpolarized UV-light irradiation. The stepwise process was monitored by adopting a fluorescent indicator. By loading the mixture into a confined cell, azo-dyes were spontaneously adsorbed at inner surfaces of the cell, whereas reactive mesogens (RMs) were homogeneously dissolved in an LC host. The molecular orientational anisotropy of dyes at the surface, induced by LPVL, aligned the LC director perpendicular to the polarization direction. Upon the second step, UV-irradiation, the RMs in an LC host were photopolymerized into thin interfacial layers, stabilizing the aligned LC director. The overlaid cross-linked RM layers secured a thermal and a radiative stability of LC alignment. The RM layers completely screened the effect of azo-dyes, which can be easily randomized by heat and irradiation. The interfacial RM layer functioned as a permanently stable alignment layer. It provided sufficient azimuthal anchoring strength together with heat and light stabilities, which are essential for practical applications. Such sequential interfacial modifications through dual-wavelength processes can completely avoid interference between forming alignment and stabilization layers, inevitable if the same wavelength light is used. The proposed method provides a simple fabrication process and reliable alignment characteristics by employing effective in situ photoalignment and without using a traditional alignment layer. Therefore, it meets a current trend in the display market toward ultrahigh-resolution and large-area displays.

Liquid-crystalline elastomer photoactuator with photorearrangeable network structures

ABSTRACTCrosslinked liquid-crystalline polymers (CLCPs) containing azobenzene moieties show reversible macroscopic deformation upon irradiation with light. The deformation of CLCPs strongly depends on alignment of mesogens. Therefore, it is desirable that the alignment of mesogens in CLCPs can be freely controlled even after crosslinking. We successfully realigned the mesogens in CLCPs with the aid of dynamic covalent bonds to accomplish this challenge. In this study, we prepared CLCP films containing dynamic covalent bonds and photoalignable azobenzene moieties. Photoalignment of the films was performed by irradiation with linearly polarized UV light at 120°C. The films after photoalignment showed bending behavior along the direction in which the mesogens had been realigned by photoalignment when irradiated with unpolarized UV light. This result indicates that alignment of mesogens in the films changes before and after photoalignment even after crosslinking.

Anisotropic Diffusion of Microbeads Surrounded by an Anisotropically Elongated Supramolecular Diarylethene Architecture under Linearly Polarized Light

AbstractUpon irradiation of an amphiphilic diarylethene derivative (which shows a photoinduced morphological transformation in water between sphere and fiber states) with linearly polarized light, elongation of the fiber in the direction of polarization was observed in TEM images. The diffusive motion was suppressed in the direction perpendicular to that of the generated fiber, as revealed by means of trajectory tracking of added polystyrene (PS) beads. When unpolarized UV light was used, the TEM image showed no anisotropic features and the diffusion of PS beads was isotropic. These results provide a means for anisotropic photocontrol of the morphology of supramolecular architectures.

Photo-Induced Bending Behavior of Post-Crosslinked Liquid Crystalline Polymer/Polyurethane Blend Films.

Photoresponsive blend films with post-crosslinked liquid crystalline polymer (CLCP) as a photosensitive component and flexible polyurethane (PU) as the matrix are successfully fabricated. After being uniaxially stretched, even at low concentration, the azobenzene-containing CLCP effectively transfers its photoresponsiveness to the photoinert PU matrix, resulting in the fast photo-induced bending behavior of whole blend film thanks to the effective dispersion of CLCP. Specifically, the blend film shows photo-induced deformations upon exposure to unpolarized UV light at ambient temperature. The film unbends after thermal treatment, and the randomly orientated mesogens in the film can be realigned by the mechanical stretching, which endows the film with a reversible deformation behavior. The photosensitive blend film possesses favorable mechanical property and good processability at low cost, and it is a promising candidate for a new generation of actuators.

Integration of celestial compass cues in the central complex of the locust brain.

Many insects rely on celestial compass cues such as the polarization pattern of the sky for spatial orientation. In the desert locust, the central complex (CX) houses multiple sets of neurons, sensitive to the oscillation plane of polarized light and thus probably acts as an internal polarization compass. We investigated whether other sky compass cues like direct sunlight or the chromatic gradient of the sky might contribute to this compass. We recorded from polarization-sensitive CX neurons while an unpolarized green or ultraviolet light spot was moved around the head of the animal. All types of neuron that were sensitive to the plane of polarization (E-vector) above the animal also responded to the unpolarized light spots in an azimuth-dependent way. The tuning to the unpolarized light spots was independent of wavelength, suggesting that the neurons encode solar azimuth based on direct sunlight and not on the sky chromatic gradient. Two cell types represented the natural 90 deg relationship between solar azimuth and zenithal E-vector orientation, providing evidence to suggest that solar azimuth information supports the internal polarization compass. Most neurons showed advances in their tuning to the E-vector and the unpolarized light spots dependent on rotation direction, consistent with anticipatory signaling. The amplitude of responses and its variability were dependent on the level of background firing, possibly indicating different internal states. The integration of polarization and solar azimuth information strongly suggests that besides the polarization pattern of the sky, direct sunlight might be an important cue for sky compass navigation in the locust.

Orientation of Azobenzene Mesogens in Side-Chain Liquid Crystalline Polymers: Interplay between Effects of Mechanical Stretching, Photoisomerization and Thermal Annealing

The interplay of the mechanically and optically induced orientation of azobenzene mesogens as well as the effect of thermal annealing was investigated for both a side-chain liquid crystalline polymer (SCLCP) and a diblock copolymer comprising two SCLCPs bearing azobenzene and biphenyl mesogens, respectively. Typically, the polymer film was first subjected to stretching in either nematic or smectic phase to yield orientation of azobenzene mesogens either parallel or perpendicular to the strain direction, then exposed to unpolarized UV light to erase the mechanically induced orientation upon the trans–cis isomerization, followed by linearly polarized visible light for photoinduced reorientation as a result of the cis–trans backisomerization, and finally heated to different liquid crystalline phases for thermal annealing. The change in orientation was monitored by means of infrared dichroism. The results have unveiled complex and different orientational behaviors for the homopolymer of poly{6-[4-(4-methoxyph...

Optically driven translational and rotational motions of microrod particles in a nematic liquid crystal

A small amount of azo-dendrimer molecules dissolved in a liquid crystal enables translational and rotational motions of microrods in a liquid crystal matrix under unpolarized UV light irradiation. This motion is initiated by a light-induced trans-to-cis conformational change of the dendrimer adsorbed at the rod surface and the associated director reorientation. The bending direction of the cis conformers is not random but is selectively chosen due to the curved local director field in the vicinity of the dendrimer-coated surface. Different types of director distortions occur around the rods, depending on their orientations with respect to the nematic director field. This leads to different types of motions driven by the torques exerted on the particles by the director reorientations.

A Distinct Layer of the Medulla Integrates Sky Compass Signals in the Brain of an Insect

Mass migration of desert locusts is a common phenomenon in North Africa and the Middle East but how these insects navigate is still poorly understood. Laboratory studies suggest that locusts are able to exploit the sky polarization pattern as a navigational cue. Like other insects locusts detect polarized light through a specialized dorsal rim area (DRA) of the eye. Polarization signals are transmitted through the optic lobe to the anterior optic tubercle (AOTu) and, finally, to the central complex in the brain. Whereas neurons of the AOTu integrate sky polarization and chromatic cues in a daytime dependent manner, the central complex holds a topographic representation of azimuthal directions suggesting a role as an internal sky compass. To understand further the integration of sky compass cues we studied polarization-sensitive (POL) neurons in the medulla that may be intercalated between DRA photoreceptors and AOTu neurons. Five types of POL-neuron were characterized and four of these in multiple recordings. All neurons had wide arborizations in medulla layer 4 and most, additionally, in the dorsal rim area of the medulla and in the accessory medulla, the presumed circadian clock. The neurons showed type-specific orientational tuning to zenithal polarized light and azimuth tuning to unpolarized green and UV light spots. In contrast to neurons of the AOTu, we found no evidence for color opponency and daytime dependent adjustment of sky compass signals. Therefore, medulla layer 4 is a distinct stage in the integration of sky compass signals that precedes the time-compensated integration of celestial cues in the AOTu.

광반응성 작용기를 주사슬에 갖는 폴리아미드의 합성과 특성 분석 및 액정분자의 배향 특성

고분자의 주사슬에 광반응을 할 수 있는 phenyldiacryloyl 그룹을 가지고, 곁사슬에 액정분자와 비슷한 메조겐인 biphenyl을 에테르 결합을 통해서 도입된 가용성 광반응성 폴리아미드를 합성하였다. 합성된 폴리아미드 고분자는 0.65 dL/g의 대수점도를 가지며, 일반적인 코팅 방법으로 여러 기질의 표면에 잘 도포되는 성질을 보였다. 광반응성 폴리아미드 고분자의 화학 구조는 1H NMR과 Fourier transform infrared(FTIR) spectroscopy를 이용해서 확인하였다. 합성된 고분자의 유리전이온도는 150 ℃까지 관측되지 않았으며, 열분해 온도는 280 ℃로 관측되어, 열안정성이 높음을 확인하였다. 합성된 폴리아미드 고분자 박막을 비편광된 자외선을 노광시켜 노광하는 에너지에 따른 변화를 조사했을 때, 좋은 광반응성을 보였다. 광반응성 폴리아미드를 이용하여 선편광된 자외선을 노광하여 제작한 액정 셀 내에서, 액정분자들은 노광된 선편광 자외선의 electric vector 방향의 수직으로 배향되는 것이 관측되었으며, 이러한 현상은 선편광 자외선의 노광량에는 무관함을 보였다. 액정 셀 내에서 액정분자들의 pretilt angle은 선편광된 자외선의 노광량에 따라 약간의 차이를 보이며 0.2°에서 0.5° 사이의 값을 보였다.

Dual liquid crystal alignment configuration based on nanoparticle-doped polymer films

This paper proposes an approach for producing dual liquid crystal (LC) alignment configuration based on nanoparticle-doped polymer films. Experimental results indicate that illuminating a nanoparticle-doped pre-polymer film, coated onto a substrate with a homogeneous alignment layer, with unpolarized UV light through a photomask causes the polymerization of pre-polymer, ultimately generating homogeneous and vertical alignment layers in unpolymerized and polymerized regions, respectively. The dual LC alignment configuration of the homogeneous (vertical) and hybrid alignments can be achieved by combining the treated substrate with another substrate that has a homogeneous (vertical) alignment layer. Additionally, the applications of the dual LC alignment layer in phase gratings and transflective LC displays are demonstrated.

Liquid crystal alignment on patterned-alignment films

To come up with a bistable liquid crystal (LC) device using unpolarized UV light, single-step laser patterning on a photoalignment layer using a photomask was proposed to achieve an equilibrium configuration of LC molecules in contact with a periodically patterned substrate. The patterns were formed by stripes of alternating random planar and homeotropic anchoring on a submicrometer scale in the order of 0.5 μm. Two possible configurations of bistable LC cells that can be obtained by combining a micropatterned surface formed with alternating random-planar- and homeotropic-alignment with planar- or homeotropic-alignment surfaces were proposed. The alignment properties of the two proposed models were investigated, along with the microscopic switching behavior of micropatterned nematic LC cells.

Bistable Characteristics of Liquid Crystal Devices with Patterned Alignment Films

The photoalignment technology for the alignment of liquid crystal molecules has lately gathered much attention because its advantages over the conventional rubbing of polyimide coating and several different approaches for the realization of photoalignment have been presented. Due to its non-contact nature, a photoalignment eliminates generation of dust and electrostatic charges as well as mechanical damage to the surface. Up to now, the study of the photoalignment effect has been focused mostly on uniform substrates through linearly polarized light. With the aim to achieve such a bistable liquid crystal device by means of unpolarized UV light, we have proposed a single-step laser patterning on a photoalignment layer using a photomask to achieve an equilibrium configuration of LC molecules in contact with a periodically patterned substrate. The patterns were formed by stripes of alternating random planar and homeotropic anchoring in a sub-micron scale on the order of 0.5 micron. We proposed two possible configurations of bistable LC cells that can be obtained by combination of micro-patterned surface formed with alternating random planar alignment with either planar alignment or homeotropic alignment surfaces. In this study, we have investigated the alignment properties and switching behaviours of both proposed models.

Controlling pitch length of chiral monomer-doped nematic/cholesteric liquid crystals using photopolymerization

This work presents a simple approach to control the pitch length of chiral monomer-doped nematic/cholesteric liquid crystals (CM-NLCs/CM-CLCs) using photopolymerization. Illuminating CM-NLCs/CM-CLCs with unpolarized UV light causes the diffusion and polymerization of CM, and then increases/decreases the pitch length by reducing the concentration of the CM in the bulk. It should be noted that the pitch length change is irreversible in either red- or blue-shift. The key to control the pitch length of CM-NLCs/CM-CLCs is the competition between the right- and left-hand chiral dopants in the sample. CM-NLCs and CM-CLCs are used to study the red- and blue-shifts, respectively. The properties of cobweb-like polymer layers are also discussed.