Enhanced Energy Storage Performance and Efficiency in Bi0.5(Na0.8K0.2)0.5TiO3-Bi0.2Sr0.7TiO3 Relaxor Ferroelectric Ceramics via Domain Engineering.

Dielectric materials are highly desired for pulsed power capacitors due to their ultra-fast charge-discharge rate and excellent fatigue behavior. Nevertheless, the low energy storage density caused by the low breakdown strength has been the main challenge for practical applications. Herein, we report the electric energy storage properties of (1 - x) Bi0.5(Na0.8K0.2)0.5TiO3-xBi0.2Sr0.7TiO3 (BNKT-BST; x = 0.15-0.50) relaxor ferroelectric ceramics that are enhanced via a domain engineering method. A rhombohedral-tetragonal phase, the formation of highly dynamic PNRs, and a dense microstructure are confirmed from XRD, Raman vibrational spectra, and microscopic investigations. The relative dielectric permittivity (2664 at 1 kHz) and loss factor (0.058) were gradually improved with BST (x = 0.45). The incorporation of BST into BNKT can disturb the long-range ferroelectric order, lowering the dielectric maximum temperature Tm and inducing the formation of highly dynamic polar nano-regions. In addition, the Tm shifts toward a high temperature with frequency and a diffuse phase transition, indicating relaxor ferroelectric characteristics of BNKT-BST ceramics, which is confirmed by the modified Curie-Weiss law. The rhombohedral-tetragonal phase, fine grain size, and lowered Tm with relaxor properties synergistically contribute to a high Pmax and low Pr, improving the breakdown strength with BST and resulting in a high recoverable energy density Wrec of 0.81 J/cm3 and a high energy efficiency η of 86.95% at 90 kV/cm for x = 0.45.

Preparation and Characterization of Poly(Acrylic Acid)-Based Self-Healing Hydrogel for 3D Shape Fabrication via Extrusion-Based 3D Printing.

The three-dimensional (3D) printing of hydrogel is an issue of interest in various applications to build optimized 3D structured devices beyond 2D-shaped conventional structures such as film or mesh. The materials design for the hydrogel, as well as the resulting rheological properties, largely affect its applicability in extrusion-based 3D printing. Here, we prepared a new poly(acrylic acid)-based self-healing hydrogel by controlling the hydrogel design factors based on a defined material design window in terms of rheological properties for application in extrusion-based 3D printing. The hydrogel is designed with a poly(acrylic acid) main chain with a 1.0 mol% covalent crosslinker and 2.0 mol% dynamic crosslinker, and is successfully prepared based on radical polymerization utilizing ammonium persulfate as a thermal initiator. With the prepared poly(acrylic acid)-based hydrogel, self-healing characteristics, rheological characteristics, and 3D printing applicability are deeply investigated. The hydrogel spontaneously heals mechanical damage within 30 min and exhibits appropriate rheological characteristics, including G'~1075 Pa and tan δ~0.12, for extrusion-based 3D printing. Upon application in 3D printing, various 3D structures of hydrogel were successfully fabricated without showing structural deformation during the 3D printing process. Furthermore, the 3D-printed hydrogel structures exhibited excellent dimensional accuracy of the printed shape compared to the designed 3D structure.

Synthesis of Yttria-Stabilized Zirconia Nanospheres from Zirconium-Based Metal-Organic Frameworks and the Dielectric Properties.

Yttria-stabilized zirconia (YSZ) nanospheres were synthesized by calcination at 900 °C after the adsorption of Y3+ ions into the pores of a zirconium-based metal-organic framework (MOF). The synthesized 3YSZ (zirconia doped with 3 mol% Y2O3), 8YSZ (8 mol% Y2O3), and 30YSZ (30 mol% Y2O3) nanospheres were found to exhibit uniform sizes and shapes. Complex permittivity and complex permeability were carried out in K-band (i.e., 18-26.5 GHz) to determine their suitability for use as low-k materials in 5G communications. The real and imaginary parts of the permittivity of the sintered 3YSZ were determined to be 21.24 and 0.12, respectively, while those of 8YSZ were 22.80 and 0.16, and those of 30YSZ were 7.16 and 0.38. Control of the real part of the permittivity in the sintered YSZ was facilitated by modifying the Y2O3 content, thereby rendering this material an electronic ceramic with potential for use in high-frequency 5G communications due to its excellent mechanical properties, high chemical resistance, and good thermal stability. In particular, it could be employed as an exterior material for electronic communication products requiring the minimization of information loss.

3D Antidrying Antifreezing Artificial Skin Device with Self-Healing and Touch Sensing Capability.

Hydrogels are attractive, active materials for various e-skin devices based on their unique functionalities such as flexibility and biocompatibility. Still, e-skin devices are generally limited to simple structures, and the realization of optimal-shaped 3D e-skin devices for target applications is an intriguing issue of interest. Furthermore, hydrogels intrinsically suffer from drying and freezing issues in operational capability for practical applications. Herein, 3D artificial skin devices are demonstrated with highly improved device stability. The devices are fabricated in a target-oriented 3D structure by extrusion-based 3D printing, spontaneously heal mechanical damage, and enable stable device operation over time and under freezing conditions. Based on the material design to improve drying and freezing resistance, an organohydrogel, prepared by solvent displacement of hydrogel with ethylene glycol for 3 h, exhibits excellent drying resistance over 1000 h and improved freezing resistance by showing no phase transition down to -60 °C while maintaining its self-healing functionality. Based on the improved drying and freezing resistance, artificial skin devices in target-oriented optimal 3D structures are presented, which enable accurate positioning of touchpoints even on a complicated 3D structure stably over time and excellent operation at temperatures below 0 °C without losing their flexibility.

Three-Dimensional Self-Healable Touch Sensing Artificial Skin Device.

Human skin is a unique functional material that perfectly covers body parts having various complicated shapes, spontaneously heals mechanical damage, and senses a touch. E-skin devices have been actively researched, focusing on the sensing functionality of skin. However, most e-skin devices still have limitations in their shapes, and it is a challenging issue of interest to realize multiple functionalities in one device as human skin does. Here, new artificial skin devices are demonstrated in application-oriented three-dimensional (3D) shapes, which can sense exact touch location and heal mechanical damage spontaneously. Beyond the conventional film-type e-skin devices, the artificial skin devices are fabricated in optimal three-dimensional structures, via systematic material design and characterization of ion-conductive self-healing hydrogel system and its extrusion-based 3D printing. The ring-shaped and fingertip-shaped artificial skin devices are successfully fabricated to fit perfectly on finger models, and shows large electronic signal contrast, ∼5.4 times increase in current, upon a human finger contact. Furthermore, like human skin, the device provides the exact positional information of an arbitrary touch location on a three-dimensional artificial skin device without complicated device fabrication or data processing.

Alignment of Lyotropic Liquid Crystalline Conjugated Polymers in Floating Films.

Directed alignment of polymer chains plays an indispensable role in charge transport properties. We focus not only on a specific method to induce the alignment but also on the design of a liquid crystalline (LC) conjugated polymer to take advantage of an intrinsic self-assembly characteristic. We synthesized a lyotropic LC conjugated polymer, CP1-P, having o-nitrobenzyl (ONB) esters as photocleavable side chains and adopted a floating film transfer method to induce the polymer chain alignment through a lyotropic LC phase transition. An optimum amount of a high boiling point solvent (1,2-dichlorobenzene) in chloroform turned out to be an important factor to maximize the polymer chain alignment. The hole transport mobility along the polymer chain alignment direction was 13-14 times higher than that in the direction perpendicular to the alignment. In addition, the removal of side chains resulted in the solvent resistivity while maintaining the alignment feature in organic thin-film transistors.

Room-Temperature-Phosphorescence-Based Dissolved Oxygen Detection by Core-Shell Polymer Nanoparticles Containing Metal-Free Organic Phosphors.

The highly sensitive optical detection of oxygen including dissolved oxygen (DO) is of great interest in various applications. We devised a novel room-temperature-phosphorescence (RTP)-based oxygen detection platform by constructing core-shell nanoparticles with water-soluble polymethyloxazoline shells and oxygen-permeable polystyrene cores crosslinked with metal-free purely organic phosphors. The resulting nanoparticles show a very high sensitivity for DO with a limit of detection (LOD) of 60 nm and can be readily used for oxygen quantification in aqueous environments as well as the gaseous phase.

A Novel Mechanism for Chemical Sensing Based on Solvent-Fluorophore-Substrate Interaction: Highly Selective Alcohol and Water Sensor with Large Fluorescence Signal Contrast.

Differentiation of solvents having similar physicochemical properties, such as ethanol and methanol, is an important issue of interest. However, without performing chemical analyses, discrimination between methanol and ethanol is highly challenging due to their similarity in chemical structure as well as properties. Here, we present a novel type of alcohol and water sensor based on the subtle differences in interaction among solvent analytes, fluorescent organic molecules, and a mesoporous silica gel substrate. A gradual change in the chemical structure of the fluorescent diketopyrrolopyrrole (DPP) derivatives alters their interaction with the substrate and solvent analyte, which creates a distinct intermolecular aggregation of the DPP derivatives on the silica gel substrate depending on the solvent environment and produces a change in the fluorescence color and intensity as a sensory signal. The devised sensor device, which is fabricated with simple drop-casting of the DPP derivative solutions onto a silica gel substrate, exhibited a completely reversible fluorescence signal change with large fluorescence signal contrast, which allows selective solvent detection by simple optical observation with the naked eye under UV light. Superior selectivity of the alcohol and water sensor system, which can clearly distinguish among ethanol, methanol, ethylene glycol, and water, is demonstrated.

Multi-luminescent switching of metal-free organic phosphors for luminometric detection of organic solvents.

Metal-free organic phosphors can be an attractive smart optical sensing materials since, in such compounds, intersystem crossing (ISC) and the phosphorescence process are placed in subtle competition with fluorescence, internal conversion (IC), and non-radiative decay pathways. Here, we report a unique environment-dependent multi-luminescence switching behavior of metal-free organic phosphorescent materials. Through combined photophysical measurements and computational electronic structure analysis, we systematically investigated how physicochemical properties of organic solvents affect the photophysical pathways of the metal-free organic phosphors. By rationally adapting the finding into phosphor-doped electrospun polymer fibers, we developed a new luminometric sensory platform and achieved selective detection of eight different common organic solvents. The presented finding provides new possibilities for metal-free organic phosphors to be a novel class of smart optical sensory materials.

Suppressing molecular motions for enhanced room-temperature phosphorescence of metal-free organic materials.

Metal-free organic phosphorescent materials are attractive alternatives to the predominantly used organometallic phosphors but are generally dimmer and are relatively rare, as, without heavy-metal atoms, spin-orbit coupling is less efficient and phosphorescence usually cannot compete with radiationless relaxation processes. Here we present a general design rule and a method to effectively reduce radiationless transitions and hence greatly enhance phosphorescence efficiency of metal-free organic materials in a variety of amorphous polymer matrices, based on the restriction of molecular motions in the proximity of embedded phosphors. Covalent cross-linking between phosphors and polymer matrices via Diels-Alder click chemistry is devised as a method. A sharp increase in phosphorescence quantum efficiency is observed in a variety of polymer matrices with this method, which is ca. two to five times higher than that of phosphor-doped polymer systems having no such covalent linkage.

High-Performing Thin-Film Transistors in Large Spherulites of Conjugated Polymer Formed by Epitaxial Growth on Removable Organic Crystalline Templates.

Diketopyrrolopyrrole (DPP)-based conjugated polymer PDTDPPQT was synthesized and was used to perform epitaxial polymer crystal growth on removable 1,3,5-trichlorobenzene crystallite templates. A thin-film transistor (TFT) was successfully fabricated in well-grown large spherulites of PDTDPPQT. The charge carrier mobility along the radial direction of the spherulites was measured to be 5.46-12.04 cm(2) V(-1) s(-1), which is significantly higher than that in the direction perpendicular to the radial direction. The dynamic response of charge transport was also investigated by applying a pulsed bias to TFTs loaded with a resistor (∼20 MΩ). The charge-transport behaviors along the radial direction and perpendicular to the radial direction were investigated by static and dynamic experiments through a resistor-loaded (RL) inverter. The RL inverter made of PDTDPPQT-based TFT operates well, maintaining a fairly high switching voltage ratio (Vout(ON)/Vout(OFF)) at a relatively high frequency when the source-drain electrodes are aligned parallel to the radial direction.

Elongation of fibers from highly viscous dextran solutions enables fabrication of rapidly dissolving drug carrying fabrics.

A simple method is presented for forming thread-like fibers from highly viscous dextran solutions. Based on the cohesive and adhesive forces between a dextran solution and the substrate to which it is applied, multiple fibers of approximately 10 µm in diameter can be elongated simultaneously. These fibers can be woven into multiple layers to produce fabrics of varying fiber orientations and mechanical properties. Various bioactive agents can be incorporated into the dextran solution prior to fiber formation, including hemostatic and antibiotic agents. Fabrics containing thrombin are capable of coagulating human platelet poor plasma in vitro. Fabrics containing antibiotics are capable of suppressing bacterial growth in a disk diffusion assay. These data suggest that this new material composed entirely of dextran has promise as a drug delivery component in wound dressings.

Designing interchain and intrachain properties of conjugated polymers for latent optical information encoding.

Building molecular-design insights for controlling both the intrachain and the interchain properties of conjugated polymers (CPs) is essential to determine their characteristics and to optimize their performance in applications. However, most CP designs have focused on the conjugated main chain to control the intrachain properties, while the design of side chains is usually used to render CPs soluble, even though the side chains critically affect the interchain packing. Here, we present a straightforward and effective design strategy for modifying the optical and electrochemical properties of diketopyrrolopyrrole-based CPs by controlling both the intrachain and interchain properties in a single system. The synthesized polymers, P1, P2 and P3, show almost identical optical absorption spectra in solution, manifesting essentially the same intrachain properties of the three CPs having restricted effective conjugation along the main chain. However, the absorption spectra of CP films are gradually tuned by controlling the interchain packing through the side-chain design. Based on the tailored optical properties, we demonstrate the encoding of latent optical information utilizing the CPs as security inks on a silica substrate, which reveals and conceals hidden information upon the reversible aggregation/deaggregation of CPs.

Shear-Triggered Crystallization and Light Emission of a Thermally Stable Organic Supercooled Liquid.

Thermodynamics drive crystalline organic molecules to be crystallized at temperatures below their melting point. Even though molecules can form supercooled liquids by rapid cooling, crystalline organic materials readily undergo a phase transformation to an energetically favorable crystalline phase upon subsequent heat treatment. Opposite to this general observation, here, we report molecular design of thermally stable supercooled liquid of diketopyrrolopyrrole (DPP) derivatives and their intriguing shear-triggered crystallization with dramatic optical property changes. Molten DPP8, one of the DPP derivatives, remains as stable supercooled liquid without crystallization through subsequent thermal cycles. More interestingly, under shear conditions, this supercooled liquid DPP8 transforms to its crystal phase accompanied by a 25-fold increase in photoluminescence (PL) quantum efficiency and a color change. By systematic investigation on supercooled liquid formation of crystalline DPP derivatives and their correlation with chemical structures, we reveal that the origin of this thermally stable supercooled liquid is a subtle force balance between aromatic interactions among the core units and van der Waals interactions among the aliphatic side chains acting in opposite directions. Moreover, by applying shear force to a supercooled liquid DPP8 film at different temperatures, we demonstrated direct writing of fluorescent patterns and propagating fluorescence amplification, respectively. Shear-triggered crystallization of DPP8 is further achieved even by living cell attachment and spreading, demonstrating the high sensitivity of the shear-triggered crystallization which is about 6 orders of magnitude more sensitive than typical mechanochromism observed in organic materials.

Molecular design principle of all-organic dyes for dye-sensitized solar cells.

All-organic dyes have shown promising potential as an effective sensitizer in dye-sensitized solar cells (DSSCs). The design concept of all-organic dyes to improve light-to-electric-energy conversion is discussed based on the absorption, electron injection, dye regeneration, and recombination. How the electron-donor-acceptor-type framework can provide better light harvesting through bandgap-tuning and why proper arrangement of acceptor/anchoring groups within a conjugated dye frame is important in suppressing improper charge recombination in DSSCs are discussed. Separating the electron acceptor from the anchoring unit in the donor-acceptor-type organic dye would be a promising strategy to reduce recombination and improve photocurrent generation.

A white-light-emitting molecule: frustrated energy transfer between constituent emitting centers.

White-light-emitting single molecules are promising materials for use in a new generation of displays and light sources because they offer the possibility of simple fabrication with perfect color reproducibility and stability. To realize white-light emission at the molecular scale, thereby eliminating the detrimental concentration- or environment-dependent energy transfer problem in conventional fluorescent or phosphorescent systems, energy transfer between a larger band-gap donor and a smaller band-gap acceptor must be fundamentally blocked. Here, we present the first example of a concentration-independent ultimate white-light-emitting molecule based on excited-state intramolecular proton transfer materials. Our molecule is composed of covalently linked blue- and orange-light-emitting moieties between which energy transfer is entirely frustrated, leading to the production of reproducible, stable white photo- and electroluminescence.