Cryomilling-assisted high purity ß-chitin extraction from Uroteuthis edulis pens.

We report on the extraction of ß-chitin from pens (or Gladius) of Uroteuthis edulis, a squid species prevalent in the Pacific coastal regions of East Asia. In particular, we employ cryogenic mechanical grinding (or cryomilling) as a pre-treatment process for the raw squid pens. We show that the cryomilling step enables an effective pulverization of the raw materials, which facilitates the removal of protein residues allowing the extraction of high-purity ß-chitin with a high acetylation degree (∼97 %) and crystallinity (∼82 %). We also demonstrate that the Uroteuthis edulis extract ß-chitin affords a free-standing film with excellent optical transmittance and mechanical properties.

Transparent nanocellulose paper-based biodegradable colorimetric nerve agent detectors.

Transparent cellulose nanofiber (t-CNF) films were prepared by succinylation and an aqueous collision counter system treatment, and used for the colorimetric detection of diethyl chlorophosphate (DCP), a nerve agent mimic in the vapor phase. DCP receptor with an oxime residue was anchored on the surface of succinylated CNF films, resulting in the target probe (CNF-Azo films). CNF-Azo films exhibited selective detection behavior toward DCP in the vapor phase. The oxime groups of CNF-Azo film reacted with DCP upon exposure to DCP vapor, which was accompanied by a color change from yellow to purple. Significantly, the film's transparency was preserved throughout the detection process, allowing it to identify objects behind the film during DCP detection. This property could apply to any detection system in which the color change caused by detection does not interfere with the film's transparency. The CNF-based film sensor was biodegradable, allowing it to be disposable after use.

Large-area transparent biocomposite films based on nanocellulose and nanochitin via horizontal centrifugal casting.

In this study, we introduce the horizontal centrifugal casting (HCC) process that enables centrifugal force-assisted, scalable production of large-area (10 in.) polymer composite films based on nanocellulose (CNF) and nanochitin (ChNF). The HCC employs a cylinder mold with its rotation pivot being in a horizontal posture to harness centrifugal force to help flatten the film being cast, from which polymer composite films with excellent uniformity and flatness can be reliably produced in the size of the lateral surface of the cylinder mold. The combination of centrifugal force and horizontal layout of cylinder mold can allow reliable fabrication of large-area self-standing films from both polymeric solution and/or suspension in a scalable and simple fashion, which is a task not readily achieved in common film-forming techniques, such as solvent casting and vacuum filtration. We demonstrate such reliability and versatility of the HCC process by fabricating typical biocomposite films out of both a solution blend of ChNF/silk fibroin and a colloidal suspension of CNF/nanoclay as well as investigating their processing-structure-property relation as an optically transparent composite film targeting for structural component for flexible green optoelectronics and fire-retardant film, respectively.

3D Heterogeneous Device Arrays for Multiplexed Sensing Platforms Using Transfer of Perovskites.

Despite recent substantial advances in perovskite materials, their 3D integration capability for next-generation electronic devices is limited owing to their inherent vulnerability to heat and moisture with degradation of their remarkable optoelectronic properties during fabrication processing. Herein, a facile method to transfer the patterns of perovskites to planar or nonplanar surfaces using a removable polymer is reported. After fabricating perovskite devices on this removable polymer film, the conformal attachment of this film on target surfaces can place the entire devices on various substrates by removing this sacrificial film. This transfer method enables the formation of a perovskite image sensor array on a soft contact lens, and in vivo tests using rabbits demonstrate its wearability. Furthermore, 3D heterogeneous integration of a perovskite photodetector array with an active-matrix array of pressure-sensitive silicon transistors using this transfer method demonstrates the formation of a multiplexed sensing platform detecting distributions of light and tactile pressure simultaneously.

Flexible Transparent Crystalline-ITO/Ag Nanowire Hybrid Electrode with High Stability for Organic Optoelectronics.

Metal nanowires (NWs) are promising transparent conducting electrode (TCE) materials because of their excellent optoelectrical performance, intrinsic mechanical flexibility, and large-scale processability. However, the surface roughness, thermal/chemical instability, and limited electrical conductivity associated with empty spaces between metal NWs are problems that are yet to be solved. Here, we report a highly reliable and robust composite TCE/substrate all-in-one platform that consists of crystalline indium tin oxide (c-ITO) top layer and surface-embedded metal NW (c-ITO/AgNW-GFRH) films for flexible optoelectronics. The c-ITO top layer (thickness: 10-30 nm) greatly improves the electrical performance of a AgNW-based electrode, retaining its transparency even after a high-temperature annealing process at 250 °C because of its thermally stable basal substrate (i.e., AgNW-GFRH). By introducing c-ITO thin film, we achieve an extremely smooth surface (Rrms < 1 nm), excellent optoelectrical performance, superior thermal (> 250 °C)/chemical stability (in sulfur-contained solution), and outstanding mechanical flexibility (bending radius = 1 mm). As a demonstration, we fabricate flexible organic devices (organic photovoltaic and organic light-emitting diode) on c-ITO/AgNW-GFRH films that show device performance comparable to that of references ITO/glass substrates and superior mechanical flexibility. With excellent stability and demonstrations, we expect that the c-ITO/AgNW-GFRHs can be used as flexible TCE/substrate films for future thin-film optoelectronics.

Transparent, water-stable, cellulose nanofiber-based packaging film with a low oxygen permeability.

Herein, we report on a transparent, water-stable, high oxygen barrier packaging film made from a combination of cellulose nanofiber (CNF) and a fluoropolymer (FP) coating. Nanofibrillation of the hardwood kraft pulp was carried out using succinic anhydride pretreatment and aqueous counter collision (ACC) technique to obtain ultrafine (5-7 nm) succinylated cellulose nanofibers (SCNF), which was readily fabricated into a thin coating (on PET film) as well as a self-standing film. Introducing the FP topcoat on SCNF enabled a synergistic enhancement of both oxygen barrier performance and stability against water-swelling.

Tailored Poly(vinylidene fluoride-co-trifluoroethylene) Crystal Orientation for a Triboelectric Nanogenerator through Epitaxial Growth on a Chitin Nanofiber Film.

Tailoring the crystal orientation of poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) has attracted widespread interest because of its effects on the ferroelectric properties required for various electronic devices. In this study, we investigated the epitaxial growth of PVDF-TrFE on a chitin film for developing triboelectric nanogenerators (TENGs). The crystallographic match between the chitin and PVDF-TrFE enables the development of the intended crystal orientation, with the PVDF-TrFE polarization axis aligned perpendicular to the substrate. In addition, the epitaxially grown PVDF-TrFE on chitin not only enhances the performance of the TENG but also increases the stability of the hygroscopic chitin film against water. The corresponding TENG exhibits a significantly higher output current compared to that of a nonepitaxial PVDF-TrFE/chitin film. Furthermore, the triboelectric sensors based on epitaxial PVDF-TrFE/chitin films allow the monitoring of subtle pressures, suggesting that tailoring the crystal orientation of PVDF-TrFE is a promising approach for developing high-performance TENGs.

Optically Transparent Multiscale Composite Films for Flexible and Wearable Electronics.

One of the key breakthroughs enabling flexible electronics with novel form factors is the deployment of flexible polymer films in place of brittle glass, which is one of the major structural materials for conventional electronic devices. Flexible electronics requires polymer films with the core properties of glass (i.e., dimensional stability and transparency) while retaining the pliability of the polymer, which, however, is fundamentally intractable due to the mutually exclusive nature of these characteristics. An overview of a transparent fiber-reinforced polymer, which is suggested as a potentially viable structural material for emerging flexible/wearable electronics, is provided. This includes material concept and fabrication and a brief review of recent research progress on its applications over the past decade.

Bioinspired Transparent Laminated Composite Film for Flexible Green Optoelectronics.

Herein, we report a new version of a bioinspired chitin nanofiber (ChNF) transparent laminated composite film (HCLaminate) made of siloxane hybrid materials (hybrimers) reinforced with ChNFs, which mimics the nanofiber-matrix structure of hierarchical biocomposites. Our HCLaminate is produced via vacuum bag compressing and subsequent UV-curing of the matrix resin-impregnated ChNF transparent paper (ChNF paper). It is worthwhile to note that this new type of ChNF-based transparent substrate film retains the strengths of the original ChNF paper and compensates for ChNF paper's drawbacks as a flexible transparent substrate. As a result, compared with high-performance synthetic plastic films, such as poly(ethylene terephthalate), poly(ether sulfone), poly(ethylene naphthalate), and polyimide, our HCLaminate is characterized to exhibit extremely smooth surface topography, outstanding optical clarity, high elastic modulus, high dimensional stability, etc. To prove our HCLaminate as a substrate film, we use it to fabricate flexible perovskite solar cells and a touch-screen panel. As far as we know, this work is the first to demonstrate flexible optoelectronics, such as flexible perovskite solar cells and a touch-screen panel, actually fabricated on a composite film made of ChNF. Given its desirable macroscopic properties, we envision our HCLaminate being utilized as a transparent substrate film for flexible green optoelectronics.

Hierarchical Chitin Fibers with Aligned Nanofibrillar Architectures: A Nonwoven-Mat Separator for Lithium Metal Batteries.

Here, we introduce regenerated fibers of chitin (Chiber), the second most abundant biopolymer after cellulose, and propose its utility as a nonwoven fiber separator for lithium metal batteries (LMBs) that exhibits an excellent electrolyte-uptaking capability and Li-dendrite-mitigating performance. Chiber is produced by a centrifugal jet-spinning technique, which allows a simple and fast production of Chibers consisting of hierarchically aligned self-assembled chitin nanofibers. Following the scrutinization on the Chiber-Li-ion interaction via computational methods, we demonstrate the potential of Chiber as a nonwoven mat-type separator by monitoring it in Li-O2 and Na-O2 cells.

Flexible Hard Coating: Glass-Like Wear Resistant, Yet Plastic-Like Compliant, Transparent Protective Coating for Foldable Displays.

A flexible hard coating for foldable displays is realized by the highly cross-linked siloxane hybrid using structure-property relationships in organic-inorganic hybridization. Glass-like wear resistance, plastic-like flexibility, and highly elastic resilience are demonstrated together with outstanding optical transparency. It provides a framework for the application of siloxane hybrids in protective hard coatings with high scratch resistance and flexibility for foldable displays.

A Flexible and Robust Transparent Conducting Electrode Platform Using an Electroplated Silver Grid/Surface-Embedded Silver Nanowire Hybrid Structure.

In this paper, we report flexible transparent conducting electrode (TCE) film using a silver grid (Ag grid)/silver nanowire (AgNW) hybrid structure (AG/NW-GFRHybrimer). The AG/NW-GFRHybrimer consists of an AgNW-embedded glass-fabric reinforced plastic film (AgNW-GFRHybrimer) and an electroplated Ag grid. The AgNW-GFRHybrimer is used as a flexible transparent substrate and a seed layer for electroplating. The Ag grid is fabricated via an all-solution-process; the grid pattern is formed using conventional photolithography, and Ag is deposited through electroplating. The AG/NW-GFRHybrimer exhibits excellent opto-electrical properties (transparency = 87%, sheet resistance = 13 Ω/□), superior thermal stability (250 °C for 720 min and 85 °C/85% RH for 100 h), and outstanding mechanical flexibility (bending radius = 1 mm for 2000 cycles). Finally, a touch-screen panel (four-wire resistive type) was fabricated using the AG/NW-GFRHybrimer to demonstrate its potential for use in actual optoelectronic applications.

Chitin Nanofiber Transparent Paper for Flexible Green Electronics.

A transparent paper made of chitin nanofibers (ChNF) is introduced and its utilization as a substrate for flexible organic light-emitting diodes is demonstrated. Given its promising macroscopic properties, biofriendly characteristics, and availability of the raw material, the utilization of the ChNF transparent paper as a structural platform for flexible green electronics is envisaged.

A high-performance, flexible and robust metal nanotrough-embedded transparent conducting film for wearable touch screen panels.

We report a high-performance, flexible and robust metal nanotrough-embedded transparent conducting hybrid film (metal nanotrough-GFRHybrimer). Using an electro-spun polymer nanofiber web as a template and vacuum-deposited gold as a conductor, a junction resistance-free continuous metal nanotrough network is formed. Subsequently, the metal nanotrough is embedded on the surface of a glass-fabric reinforced composite substrate (GFRHybrimer). The monolithic composite structure of our transparent conducting film allows simultaneously high thermal stability (24 h at 250 °C in air), a smooth surface topography (Rrms < 1 nm) and excellent opto-electrical properties. A flexible touch screen panel (TSP) is fabricated using the transparent conducting films. The flexible TSP device stably operates on the back of a human hand and on a wristband.

Squid beak inspired water processable chitosan composites with tunable mechanical properties.

Natural biological composites often couple light weight with tunable and spatially controlled mechanical properties including stiffness, toughness, and hardness. Examples include the toughness of seashells, the hardness of the chiton tooth, and the stiffness gradient of the squid beak. While seashells and the chiton tooth have a mineralized inorganic component, the squid beak is entirely organic. The squid beak is known as one of the hardest fully organic materials. The hydrated squid beak has a large stiffness gradient from soft, at the interface with the squid mouth, to hard at the tip. This gradient occurs from the spatially controlled cross-linking of chitin nanofibers with a protein matrix aided by catecholamines. Here, we introduce a water processable deacetylated chitin composite with tunable mechanical properties from spatially controlled cross-linking assisted by catecholamines. Given the natural abundance of chitin and the ease of water processing, this composite can find applications for bridging mechanically mismatched materials.

Ultraviolet light stable and transparent sol-gel methyl siloxane hybrid material for UV light-emitting diode (UV LED) encapsulant.

An ultraviolet (UV) transparent and stable methyl-siloxane hybrid material was prepared by a facile sol-gel method. The transparency and stability of a UV-LED encapsulant is an important issue because it affects UV light extraction efficiency and long-term reliability. We introduced a novel concept for UV-LED encapsulation using a thermally curable oligosiloxane resin. The encapsulant was fabricated by a hydrosilylation of hydrogen-methyl oligosiloxane resin and vinyl-methyl siloxane resin, and showed a comparable transmittance to polydimethylsiloxane (PDMS) in the UVB (∼300 nm) region. Most remarkably, the methyl-siloxane hybrid materials exhibited long-term UV stability under light soaking in UVB (∼300 nm) for 1000 h.

Flexible transparent conducting hybrid film using a surface-embedded copper nanowire network: a highly oxidation-resistant copper nanowire electrode for flexible optoelectronics.

We report a flexible high-performance conducting film using an embedded copper nanowire transparent conducting electrode; this material can be used as a transparent electrode platform for typical flexible optoelectronic devices. The monolithic composite structure of our transparent conducting film enables simultaneously an outstanding oxidation stability of the copper nanowire network (14 d at 80 °C), an exceptionally smooth surface topography (R(rms) < 2 nm), and an excellent opto-electrical performances (Rsh = 25 Ω sq(-1) and T = 82%). A flexible organic light emitting diode device is fabricated on the transparent conducting film to demonstrate its potential as a flexible copper nanowire electrode platform.

Sol-gel derived transparent zirconium-phenyl siloxane hybrid for robust high refractive index LED encapsulant.

We report a zirconium-phenyl siloxane hybrid material (ZPH) that can be used as a robust LED encapsulant. The ZPH encapsulant was fabricated via hydrosilylation-curing of sol-gel derived multifunctional (vinyl- and hydride-functions) siloxane resins containing phenyl-groups and Zr-O-Si heterometallic phase for achieving a high refractive index (n ≈ 1.58). In thermal aging, the ZPH LED encapsulant exhibited superior performances with a high optical transparency (∼88% at 450 nm) and exhibited high thermal stability (no yellowing at 180 °C for 1008 h), compared to a commercial LED encapsulant (OE-6630, Dow Corning Corporation). This suggests potential for ZPH to be a robust LED encapsulant.

Flexible transparent conducting composite films using a monolithically embedded AgNW electrode with robust performance stability.

We report on the performance of an all-in-one flexible hybrid conducting film employing a monolithically embedded AgNW transparent electrode and a high-performance glass-fabric reinforced composite substrate (AgNW-GFRHybrimer film). Specifically, we perform in-depth investigations on the stability of the AgNW-GFRHybrimer film against heat, thermal oxidation, and wet chemicals to demonstrate the potential of the hybrid conducting film as a robust electrode platform for thin-film optoelectronic devices. With the ease of large-area processability, smooth surface topography, and robust performance stability, the AgNW-GFRHybrimer film can be a promising platform for high-performance optoelectronic devices.