Polarization-Dependent Thin Films with Biaxial Anisotropic Absorption Constructed by a Single Coating and Subsequent Topochemical Polymerization of Chromophores.

For the construction of hierarchical superstructures with biaxial anisotropic absorption, a newly synthesized diacetylene-functionalized bipyridinium is self-assembled to use an electron-accepting host for capturing and arranging guests. The formation of the donor-acceptor complex triggers an intermolecular charge transfer, leading to chromophore activation. Polarization-dependent multichroic thin films are prepared through a sequential process of single-coating, self-assembly, and topochemical polymerization of host-guest chromophores. Molecular packing structures constructed in the single-layer optical thin film possess orthogonal absorption axes for two different wavelengths. By tuning the linear polarization angle, the color of the optical thin film can be intentionally controlled. This single-layered multichroic film provides a new pathway for the development of anticounterfeiting and multiplexing encryptions.

Suppressing Redox Reactions at the Perovskite-Nickel Oxide Interface with Zinc Nitride to Improve the Performance of Perovskite Solar Cells.

For p-i-n perovskite solar cells (PSCs), nickel oxide (NiOx) hole transport layers (HTLs) are the preferred interfacial layer due to their low cost, high mobility, high transmittance, and stability. However, the redox reaction between the Ni≥3+ and hydroxyl groups in the NiOx and perovskite layer leads to oxidized CH3NH3 + and reacts with PbI in the perovskite, resulting in a large number of non-radiative recombination sites. Among various transition metals, an ultra-thin zinc nitride (Zn3N2) layer on the NiOx surface is chosen to prevent these redox reactions and interfacial issues using a simple solution process at low temperatures. The redox reaction and non-radiative recombination at the interface of the perovskite and NiOx reduce chemically by using interface modifier Zn3N2 to reduce hydroxyl group and defects on the surface of NiOx. A thin layer of Zn3N2 at the NiOx/perovskite interface results in a high Ni3+/Ni2+ ratio and a significant work function (WF), which inhibits the redox reaction and provides a highly aligned energy level with perovskite crystal and rigorous trap-passivation ability. Consequently, Zn3N2-modified NiOx-based PSCs achieve a champion PCE of 21.61%, over the NiOx-based PSCs. After Zn3N2 modification, the PSC can improve stability under several conditions.

Self-Assembled and Polymerized Hierarchical Nanostructure Films of Cyanostilbene-Based Reactive AIEgens for Smart Chemosensors.

For the development of acid-responsive advanced fluorescent films with a 2D nanostructure, a pyridyl cyanostilbene-based AIEgen (PCRM) is newly synthesized. The synthesized PCRM exhibits aggregation-induced emission (AIE) and responds reversibly to acid and base stimuli. To fabricate the nanoporous polymer-stabilized film, PCRM and 4-(octyloxy)benzoic acid (8OB) are complexed in a 1:1 ratio through hydrogen bonding. The PCRM-8OB complex with a smectic mesophase is uniaxially oriented at first and photopolymerized with a crosslinker. By subsequently removing 8OB in an alkaline solution, nanopores are generated in the self-assembled and polymerized hierarchical 2D nanostructure film. The prepared nanoporous fluorescent films exhibit not only the reversible response to acid and base stimuli but also mechanical and chemical robustness. Since the nanoporous fluorescent films have different sensitivities to trifluoroacetic acid (TFA) depending on the molecular orientation in the film, advanced acid vapor sensors that can display the risk level according to the concentration of TFA are demonstrated. Reactive AIEgens-based hierarchical nanostructure films with nanopores fabricated by a subsequent process of self-assembly, polymerization, and etching can open a new door for the development of advanced chemosensors.

A Flexible and Transparent Zinc-Nanofiber Network Electrode for Wearable Electrochromic, Rechargeable Zn-Ion Battery.

The flexible electrochromic Zn-ion battery (FE-ZiB), a newly born energy-storage technology having both electrochromic characteristics and energy-storage capability in a single device, will be a promising technology for the future transparent wearable electronics. However, the current technology limits the fabrication of FE-ZIB because the zinc (Zn) anode material is opaque and rigid. The development of a flexible and transparent Zn anode is the key factor to overcoming the current limitation. Here, for the first time, a flexible, transparent zinc-nanofiber network anode electrode (Zn@Ni@AgNFs) is reported for an FE-ZiB device that yields a remarkable electrochemical performance of a high areal capacity of 174.82 mA h m2 at 0.013 mA cm-2 applied current density, high optical contrast (50%), and excellent mechanical flexibility. The fabricated FE-ZiB device also exhibits a high volumetric energy density of 378.8 W h m-3 at a power density of 562.7 W m-3 . Besides, the FE-ZiB demonstrates excellent electrochromic capability with a reversible color transition from a transparent in a discharged state (0.3 V) to a dark bluish-violet in a charged state (1.6 V). These results highlight a new pathway for the development of transparent batteries for smart wearable electronic devices.

Mechanically programmed 2D and 3D liquid crystal elastomers at macro- and microscale via two-step photocrosslinking.

Liquid crystal elastomers (LCEs) are a unique class of active materials with the largest known reversible shape transformation in the solid state. The shape change of LCEs is directed by programming their molecular orientation, and therefore, several strategies to control LC alignment have been developed. Although mechanical alignment coupled with a two-step crosslinking is commonly adopted for uniaxially-aligned monodomain LCE synthesis, the fabrication of 3D-shaped LCEs at the macro- and microscale has been rarely accomplished. Here, we report a facile processing method for fabricating 2D and 3D-shaped LCEs at the macro- and microscales at room temperature by mechanically programming (i.e., stretching, pressing, embossing and UV-imprinting) the polydomain LCE, and subsequent photocrosslinking. The programmed LCEs exhibited a reversible shape change when exposed to thermal and chemical stimuli. Besides the programmed shape changes, the actuation strain can also be preprogrammed by adjusting the extent of elongation of a polydomain LCE. Furthermore, the LCE micropillar arrays prepared by UV-imprinting displayed a substantial change in pillar height in a reversible manner during thermal actuation. Our convenient method for fabricating reversible 2D and 3D-shaped LCEs from commercially available materials may expedite the potential applications of LCEs in actuators, soft robots, smart coatings, tunable optics and medicine.

Programmed Hierarchical Hybrid Nanostructures from Fullerene-Dendrons and Pyrene-Dendrons.

The construction of fullerene (C60 ) hierarchical nanostructures with the help of amphiphilic molecules remains a challenging task in nanoscience and nanotechnology. Utilizing the host-guest complex concept, sub-10 nm layered superstructures are constructed from a monofunctionalized C60 dendron (C60 D, guest) and tweezer-like pyrene dendron (PD, host). Since C60 D and PD are asymmetric shape amphiphiles having liquid crystal (LC) dendrons, both C60 D and PD construct head-to-head bilayer superstructures by themselves. From fluorescence titration experiments, it is realized that the host-guest complex shows 1:1 stoichiometric binding with a binding constant (Ksv = 2.45 × 105 m-1 ). Based on the morphological observations and scattering analyses, it is found that buckle-like asymmetric building blocks (C60 D·PD) are self-assembled by the host-guest complex and construct multilayer hybrid nanostructures. The hierarchical hybrid nanostructures consist of the self-assembled C60 D·PD bilayer with a 2D C60 ·P nanoarray sandwiched between LC dendrons. This advanced strategy is expected to be a practicable and rational guideline for the fabrication of programmed hierarchical hybrid nanostructures.

Asymmetric Fullerene Nanosurfactant: Interface Engineering for Automatic Molecular Alignments.

Since the molecular self-assembly of nanomaterials is sensitive to their surface properties, the molecular packing structure on the surface is essential to build the desired chemical and physical properties of nanomaterials. Here, a new nanosurfactant is proposed for the automatic construction of macroscopic surface alignment layer for liquid crystal (LC) molecules. An asymmetric nanosurfactant (C60 NS) consisted of mesogenic cyanobiphenyl moieties with flexible alkyl chains and a [60]fullerene nanoatom is newly designed and precisely synthesized. The C60 NS directly introduced in the anisotropic LC medium is self-assembled into the monolayered protrusions on the surface because of its amphiphilic nature originated by asymmetrically programmed structural motif of LC-favoring moieties and LC-repelling groups. The monolayered protrusions constructed by the phase-separation and self-assembly of asymmetric C60 NS nanosurfactant in the anisotropic LC media amplify and transfer the molecular orientational order from surface to bulk, and finally create the automatic vertical molecular alignment on the macroscopic length scale. The asymmetric C60 NS nanosurfactant and its self-assembly described herein can offer the direct guideline of interface engineering for the automatic molecular alignments.

Conversion of retardation dispersion in self-organized smectic reactive mesogen compound and its dependence on the UV polymerization temperature and the molecular orientation.

We investigated the dependence of the dispersion of retardation on the UV-polymerization temperature and the molecular orientation in a self-organized smectic host-guest reactive mesogen (RM) compound. The positive dispersion of retardation was converted to the negative dispersion of retardation with decreasing the UV-polymerization temperature. From the Fourier-transform infrared (FT-IR) dichroism measurement, it was found that more fractions of the guest molecules were aligned parallel to the smectic layer plane with decreasing the UV-polymerization temperature. The guest molecules located in the inter-layer space absorb a longer wavelength of UV light compared to the host and induce the negative dispersion of retardation.

Kinetically Controlled Polymorphic Superstructures of Pyrene-Based Asymmetric Liquid Crystal Dendron: Relationship Between Hierarchical Superstructures and Photophysical Properties.

To understand the relationship between kinetically controlled hierarchical superstructures and photophysical properties, pyrene-based asymmetric liquid crystal (LC) dendrons (abbreviated as PD) were newly synthesized by covalently attaching a pyrene moiety (P) at a biphenyl-based LC dendritic group (D). The phase transition behavior of PD has been systematically studied with a combined technique of thermal analysis, microscopy, spectroscopy, and scattering analysis. PD formed two different crystalline structures depending on the cooling rate: a stable crystalline phase (Ks , slow cooling) and a metastable crystalline phase (Kms , quenching). The kinetically controlled molecular packing structures of PD depend on the competition and cooperation of intermolecular physical interactions with nanophase separation. Upon slow cooling, the PD dimer formed by intermoelcular H-bonding constructed a layered hierarchical structure with the help of nanophase separation. Owing to the strong π-π stacking (J-aggregation) with weak H-bondings, the PD dimer in the layer was slightly tilted to give a monoclinic layered structure with a periodic layer d-spacing of 6.6 nm. In contrast, the metastable Kms phase formed by the quenching process showed a significant tilt of the PD dimer in the layer (d-spacing=4.4 nm) due to the weak π-π stacking (H-aggregation) and the strong H-bondings.

Formation of spherical-shaped GaN and InN quantum dots on curved SiN/Si surface.

This paper reports the formation of GaN and InN quantum dots (QDs) with symmetric spherical shapes, grown on SiN/Si(111). Spherical QDs are grown by modulating initial growth behavior via gallium and indium droplets functioning as nucleation sites for QDs. Field-emission scanning electron microscope (FE-SEM) images show that GaN and InN QDs are formed on curved SiN/Si(111) instead of on a flat surface similar to balls on a latex mattress. This is considerably different from the structural properties of In(Ga)As QDs grown on GaAs or InP. In addition, considering the shape of the other III-V semiconductor QDs, the QDs in this study are very close to the ideal shape of zero-dimensional nanostructures. Transmission-electron microscope images show the formation of symmetric GaN and InN QDs with a round shape, agreeing well with the FE-SEM results. Compared to other III-V semiconductor QDs, the unique structural properties of Si-based GaN and InN QDs are strongly related to the modulation in the initial nucleation characteristics due to the presence of droplets, the degree of lattice mismatch between GaN or InN and SiN/Si(111), and the melt-back etching phenomenon.

Yellow-red light-emitting diodes using periodic Ga-flow interruption during deposition of InGaN well.

We report a possible way to extend the emission wavelength of InyGa1-yN/InxGa1-xN quantum-well (QW) light-emitting diodes (LEDs) to the yellow-red spectral range with little degradation of the radiative efficiency. The InyGa1-yN well with high indium (In) content (HI-InyGa1-yN) was realized by periodic Ga-flow interruption (Ga-FI). The In contents of the HI-InyGa1-yN well and the InxGa1-xN barrier were changed to manipulate the emission wavelength of the LEDs. An In0.34Ga0.66N/In0.1Ga0.9N-QW LED, grown by continuous growth mode (C-LED), was prepared as a reference. The photoluminescence (PL) wavelengths of the HI-InyGa1-yN/InxGa1-xN QW LEDs were changed from 556 to 597 nm. The PL intensity of the HI-InyGa1-yN/InxGa1-xN LED with a peak wavelength of 563 nm was 2.7 times stronger than that of the C-LED (λ = 565 nm). The luminescence intensity for the HI-InyGa1-yN/InxGa1-xN QW LED emitting at 597 nm was stronger than those of the other LED samples with shorter wavelengths. Considering the previous works on degradation in crystal quality and increase in the quantum-confined Stark effect with increasing In content in InGaN, the approach in this work is very promising for yellow-red InGaN LEDs.

Nanosegregated Chiral Materials with Self-Assembled Hierarchical Mesophases: Effect of Thermotropic and Photoinduced Polymorphism in Rodlike Molecules.

Supramolecular chirality in a binary mixture of achiral bent-core (BC) and achiral rodlike mesogens was observed. Three different nanosegregated mesophases were determined in the binary system, and meaningful changes in circular dichroism (CD) were detected near the phase-transition temperatures of the rodlike mesogens. The highest CD intensity in the binary system was noted in the nanosegregated mesophase, in which the BC mesogens were in the helical nanofilament (HNF) phase and the rodlike mesogens were in the smectic A phase. The supramolecular chirality in the binary mixture was attributed to the self-assembled hierarchical chiral superstructures. Based on the experimental results, plausible scenarios for the chiral superstructures of the rodlike molecules embedded in the HNF networks are suggested. In addition, a system comprising BC and rodlike molecules doped with a photoresponsive compound exhibited remarkable photoswitching of CD intensity. According to the isothermal photoinduced phase transition of the embedded molecules in BC molecular HNFs, the observed CD intensities can be dynamically and reversibly modulated. Such a material with easily controllable functionality is of considerable interest in the field of materials science.

Topochemical polymerization of dumbbell-shaped diacetylene monomers: relationship between chemical structure, molecular packing structure, and gelation property.

Herein, we have synthesized novel photopolymerizable dumbbell-shaped diacetylene liquid crystal (LC) monomers by locating a diacetylene dicarboxylic acid group at the center and chemically connecting swallow-tails, such as hydrophobic alkyl chains (abbreviated as AT3DI) and amphiphilic biphenyl mesogens (abbreviated as BP3DI), with bisamide groups. Major phase transitions of dumbbell-shaped diacetylene monomers were identified using differential scanning calorimetry (DSC), polarized optical microscopy (POM), and Fourier transform infrared spectroscopy (FT IR). Molecular packing structures were studied based on structure-sensitive wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) analyses. Mainly, due to nanophase separations and strong intermolecular hydrogen bonding, AT3DI formed a low-ordered lamellar LC phase at room temperature. BP3DI self-assembled into highly-ordered crystal phases (K1 and K2) at lower temperatures below a low-ordered lamellar LC phase, in which BP3DI were intercalated with each other to compensate the mutual volume differences. From the photopolymerization of AT3DI and BP3DI, it was realized that the topochemical reactions of dumbbell-shaped diacetylene monomers were closely related to their chemical structures as well as molecular packing structures.

Single layer retarder with negative dispersion of birefringence and wide field-of-view.

A single layer retarder possessing negative dispersion (ND) of birefringence as well as wide field-of-view (FOV) was long-term objective in optical science. We synthesized new guest reactive monomers with x-shape and mixed them with the host smectic reactive mesogen. The host-guest molecules formed two dimensionally self-organized nanostructure and showed both the ND of birefringence and wide FOV properties. We simulated the antireflection property of a circular polarizer using the optical properties of the retarder. The average reflectance of the retarder was 0.52% which was much smaller than that of the commercial single layer ND retarder 1.83%.

Optical characteristics of InGaN/GaN light-emitting diodes depending on wafer bowing controlled by laser-treated grid patterns.

We evaluated the effects of grid patterns (GPs) realized on 2-inch sapphire substrates by simple laser treatment on the device characteristics of InGaN/GaN light-emitting diodes (LEDs). The degrees of wafer bowing for the LEDs with distances between the GPs of 1 (GP1-LED), 2 (GP2-LED), and 3 mm (GP3-LED) were 100.05, 100.43, and 101.59 µm, respectively, which are significantly improved compared to that (108.06 µm) of a conventional LED (C-LED) without GPs. Consequently, a blue-shift of the emission wavelength for the GP-LEDs was observed compared to the C-LED via alleviation of the quantum-confined stark effect. A comparative study of the fluorescence microscopy images of the C-LED and GP2-LED samples showed a significant reduction of threading dislocations as a result of the GPs. In the electroluminescence mapping results for the entire 2-inch region, the standard deviations of the emission wavelengths were 1.64, 1.49, and 2.55 nm for the GP1-LED, GP2-LED, and GP3-LED samples, respectively, which are smaller than that of the C-LED (2.66 nm). In addition, the average output power of the GP2-LED was 8.5% higher than that of the C-LED.

Field-symmetrization to solve luminance deviation between frames in a low-frequency-driven fringe-field switching liquid crystal cell.

The development of low-frequency-driven liquid crystal displays (LCDs) has recently received intense attention to open up low-power consumption display devices, such as portable displays, advertising panels and price tags. In fringe-field switching (FFS) LCD mode, a unidirectional electric field gives rise to head-tail symmetry breaking in liquid crystals, so that the flexoelectric effect, a coupling between the elastic distortion and the electric polarization, becomes enormously significant. The effect is thus linked to an unusual optical effect, which badly damages the quality of images by image-flickering, and this image-flickering is mainly caused by transmittance difference between the applied signal frames. Here, we intensively investigate the mechanism of the transmittance deviation, and propose an essential and promising approach to solve the poor image-quality, that is, symmetrization of electric fields between the frames. The result of our work clearly demonstrates that the field-symmetry is crucial to reduce the image-flickering, and it can be obtained by optimization of the thickness of an insulation layer with respect to the ratio of the space between electrodes to the electrode width.

Influences of Si-doped graded short-period superlattice on green InGaN/GaN light-emitting diodes.

We report significant improvement in optical and electrical properties of green InGaN/GaN light-emitting diodes (LEDs) by using Si-doped graded short-period InGaN/GaN superlattice (SiGSL) formed by so called indium-conversion technique. For comparison, a conventional LED without the superlattice (C-LED) and a LED with undoped graded superlattice (unGSL-LED) were prepared, respectively. The photoluminescence (PL) intensity of the SiGSL-LED was increased more than 3 times at room temperature (RT) as compared to C-LED. The PL intensity ratios of RT to 10K for the C-LED, unGSL-LED, and SiGSL-LED were measured to be 25, 40.9, and 47.5%, respectively. The difference in carrier lifetimes between 10K and RT for the SiGSL-LED is relatively small compared to that of the C-LED, which is consistent with the variation in PL intensity. The output power of a transistor-outline type SiGSL-LED was increased more than 2 times higher than that of the C-LED.

Dual photo-functionalized amphiphile for photo-reversible liquid crystal alignments.

Without the conventional polymer-based liquid crystal (LC) alignment process, a newly synthesized dual photo-functionalized amphiphile (abbreviated as ADMA1 ) was successfully applied as a robust photo-reversible LC alignment layer by self-assembly and photo-polymerization. The LC alignment layer constructed by directly adding dual photo-functionalized amphiphiles into LC media significantly cuts the manufacturing cost as well as opens new doors for the fabrication of novel electro-optical devices.

Multi-responsible chameleon molecule with chiral naphthyl and azobenzene moieties.

A photochromic chiral molecule with azobenzene mesogens and a (R)-configuration naphthyl moiety (abbreviated as NCA2M) was specifically designed and synthesized for the demonstration of chameleon-like color changes responding to multitudinous external stimuli, such as temperature, light and electric field. The basic phase transition behaviors of NCA2M were first studied by the combination of differential scanning calorimetry (DSC) and polarized optical microscopy (POM). Based on the structure-sensitive X-ray diffraction results obtained at different temperatures, it was comprehended that the NCA2M molecule exhibited the tilted version of highly ordered smectic crystal phase with 5.45 nm layer thickness. Chiral nematic (N*) liquid crystals (LC) with helical superstructures were formed by doping the NCA2M photochromic chiral molecule in an achiral nematic (N) LC medium. By controlling the helical pitch length of N*-LC with respect to temperature, light and electric field, the wavelength of selectively reflected light from the N* photonic crystal was finely tuned. The light-induced color change of N*-LC film was the most efficient method for covering the whole visible region from blue to green and to red, which allowed us to fabricate remote-controllable photo-responsive devices.

Optically isotropic liquid crystal media formulated by doping star-shaped cyclic oligosiloxane liquid crystal surfactants in twin nematic liquid crystals.

The formation of optically isotropic liquid crystal (LC) media has been investigated by doping the star-shaped LC molecular surfactants (SiLC) into the rod-shaped twin LC host molecules (DiLC). The experimental phase diagram was constructed on the basis of differential scanning calorimetry (DSC) and then a theoretical calculation was conducted through a combined Flory-Huggins (FH)/Maier-Saupe-McMillan (MSM)/phase field (PF) model to account for the experimental results. The phase diagram of the SiLC/DiLC mixtures revealed the broad coexistence regions such as smectic A + crystal (SmA1 + Cr2), liquid + crystal (L1 + Cr2), and liquid + nematic (L1 + N2) at the intermediate composition along with the narrow single phase crystal (Cr2), smectic (SmA1), and nematic (N2) regions. The morphologies and structures of these coexistence regions were further confirmed by polarized optical microscopy (POM) and wide-angle X-ray diffraction (WAXD). At the 80/20 SiLC/DiLC composition, the optical anisotropy was induced under an alternating current (AC) electric field above its isotropization temperature. The formation of an optically isotropic LC medium in mixtures of the SiLC molecular surfactants and nematic LC host may allow us to develop new electro-optical devices.