Siloxane Hybrid Material-Encapsulated Highly Robust Flexible µLEDs for Biocompatible Lighting Applications.

Flexible micro-light-emitting diodes (f-µLEDs) have been regarded as an attractive light source for the next-generation human-machine interfaces, thanks to their noticeable optoelectronic performances. However, when it comes to their practical utilizations fulfilling industrial standards, there have been unsolved reliability and durability issues of the f-µLEDs, despite previous developments in the high-performance f-µLEDs for various applications. Herein, highly robust flexible µLEDs (f-HµLEDs) with 20 × 20 arrays, which are realized by a siloxane-based organic-inorganic hybrid material (SHM), are reported. The f-HµLEDs are created by combining the f-µLED fabrication process with SHM synthesis procedures (i.e., sol-gel reaction and successive photocuring). The outstanding mechanical, thermal, and environmental stabilities of our f-HµLEDs are confirmed by a host of experimental and theoretical examinations, including a bending fatigue test (105 bending/unbending cycles), a lifetime accelerated stress test (85 °C and 85% relative humidity), and finite element method simulations. Eventually, to demonstrate the potential of our f-HµLEDs for practical applications of flexible displays and/or biomedical devices, their white light emission due to quantum dot-based color conversion of blue light emitted by GaN-based f-HµLEDs is demonstrated, and the biocompatibility of our f-HµLEDs is confirmed via cytotoxicity and cell proliferation tests with muscle, bone, and neuron cell lines. As far as we can tell, this work is the first demonstration of the flexible µLED encapsulation platform based on the SHM, which proved its mechanical, thermal, and environmental stabilities and biocompatibility, enabling us to envisage biomedical and/or flexible display applications using our f-HµLEDs.

Photopatternable Poly(dimethylsiloxane) (PDMS) for an Intrinsically Stretchable Organic Electrochemical Transistor.

Patterning elastomers is an essential process for the application of elastomers to stretchable bioelectric devices. In general, replication of a mold and laser ablation are used for patterning elastomers. However, these methods are inefficient and time consuming due to complex patterning procedures and a heat-induced curing mechanism. In this work, we developed a photopatternable elastomer called thiol-ene cross-linked poly(dimethylsiloxane) (TC-PDMS). TC-PDMS showed high-resolution patternability (∼100 µm) through a direct patterning process. It also had high stretchability (∼140%) and low Young's modulus (∼2.9 MPa) similar to conventional PDMS. To demonstrate its practicability in stretchable bioelectric devices, TC-PDMS was applied to a passivation layer of an intrinsically stretchable organic electrochemical transistor (OECT), which showed a low leakage current (∼20 µA) and a high transconductance (0.432 mS) at high strain (60%). The stretchable OECT was able to record electrocardiographic (ECG) signals from human skin, and the measured ECG signals exhibited a high signal-to-noise ratio of 12.2 dB.

Stretchable Printed Circuit Board Based on Leak-Free Liquid Metal Interconnection and Local Strain Control.

In order to realize a transition from conventional to stretchable electronics, it is necessary to make a universal stretchable circuit board in which passive/active components can be robustly integrated. We developed a stretchable printed circuit board (s-PCB) platform that enables easy and reliable integration of various electronic components by utilizing a modulus-gradient polymeric substrate, liquid metal amalgam (LMA) circuit traces, and Ag nanowire (AgNW) contact pads. Due to the LMA-AgNW biphasic structure of interconnection, the LMA is hermetically sealed by a homogeneous interface, realizing complete leak-free characteristics. Furthermore, integration reliability is successfully achieved by local strain control of the stretchable substrate with a selective glass fiber reinforcement (GFR). A strain localization derived by GFR makes almost 50,000% of strain difference within the board, and the amount of deformation applied to the constituent elements can be engineered. We finally demonstrated that the proposed integrated platform can be utilized as a universal s-PCB capable of integrating rigid/conventional electronic components and soft material-based functional elements with negligible signal distortion under various mechanical deformations.

Conformable microneedle pH sensors via the integration of two different siloxane polymers for mapping peripheral artery disease.

Flexible microneedles are important tools that allow access to the inside of biological tissue from the outside without surgery. However, it had been hard to realize microneedle sensor arrays on flexible substrates because of the difficulty of attaining a needle with a high Young's modulus for a selected area on a thin or soft substrate. In this work, we developed a microneedle sensor on a hybrid substrate based on high Young's modulus epoxy siloxane for the microneedles and low Young's modulus polydimethylsiloxane for the conformable substrate. Polyaniline was deposited on the microneedle for pH sensing. The mechanical durability of the device was assessed by insertion into pig skin 1000 times. Last, the flexible microneedle pH sensors showed their utility for monitoring pH distribution in rats in a peripheral artery diseases model.

Low-Temperature and High-Quality Growth of Bi2O2Se Layered Semiconductors via Cracking Metal-Organic Chemical Vapor Deposition.

Ternary metal-oxy-chalcogenides are emerging as next-generation layered semiconductors beyond binary metal-chalcogenides (i.e., MoS2). Among ternary metal-oxy-chalcogenides, especially Bi2O2Se has been demonstrated in field-effect transistors and photodetectors, exhibiting ultrahigh performance with robust air stability. The growth method for Bi2O2Se that has been reported so far is a powder sublimation based chemical vapor deposition. The first step for pursuing the practical application of Bi2O2Se as a semiconductor material is developing a gas-phase growth process. Here, we report a cracking metal-organic chemical vapor deposition (c-MOCVD) for the gas-phase growth of Bi2O2Se. The resulting Bi2O2Se films at very low growth temperature (∼300 °C) show single-crystalline quality. By taking advantage of the gas-phase growth, the precise phase control was demonstrated by modulating the partial pressure of each precursor. In addition, c-MOCVD-grown Bi2O2Se exhibits outstanding electrical and optoelectronic performance at room temperature without passivation, including maximum electron mobility of 127 cm2/(V·s) and photoresponsivity of 45134 A/W.

Extremely Stable Luminescent Crosslinked Perovskite Nanoparticles under Harsh Environments over 1.5 Years.

Organic-inorganic hybrid perovskite nanoparticles (NPs) are a very strong candidate emitter that can meet the high luminescence efficiency and high color standard of Rec.2020. However, the instability of perovskite NPs is the most critical unsolved problem that limits their practical application. Here, an extremely stable crosslinked perovskite NP (CPN) is reported that maintains high photoluminescence quantum yield for 1.5 years (>600 d) in air and in harsher liquid environments (e.g., in water, acid, or base solutions, and in various polar solvents), and for more than 100 d under 85 °C and 85% relative humidity without additional encapsulation. Unsaturated hydrocarbons in both the acid and base ligands of NPs are chemically crosslinked with a methacrylate-functionalized matrix, which prevents decomposition of the perovskite crystals. Counterintuitively, water vapor permeating through the crosslinked matrix chemically passivates surface defects in the NPs and reduces nonradiative recombination. Green-emitting and white-emitting flexible large-area displays are demonstrated, which are stable for >400 d in air and in water. The high stability of the CPN in water enables biocompatible cell proliferation which is usually impossible when toxic Pb elements are present. The stable materials design strategies provide a breakthrough toward commercialization of perovskite NPs in displays and bio-related applications.

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.

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.

Photo-Patternable Quantum Dots/Siloxane Composite with Long-Term Stability for Quantum Dot Color Filters.

Incorporation of quantum dots (QDs) into color filters (CFs) are desired for less energy loss and wider viewing angle compared to a conventional display. However, aggregation and vulnerability to heat, moisture, and chemicals in the photo-patternable matrix are critical issues of the QD-CFs with high QDs concentration. Herein, we fabricated red (10 wt %) and green (20 wt %) QD-CFs using photolithography of QD/siloxane ink containing secondary thiol monomer. Ligand-exchanged QDs were chemically incorporated in methacrylate oligosiloxane resin. QD/siloxane composite showed superior stability under harsh heat and moisture (85 °C/5% RH and 85 °C/85% RH) conditions and chemicals (EtOH, HCl, and NaOH) compared to conventional QD/PR (commercial negative photoresist). QD-CFs (10 µm thick) effectively converted blue light emitted from LED chip into red and green light, and the obtained white PL through QD-CF showed wide color gamut, which was 108% relative to NTSC. From these advantages, QD/siloxane composite will be beneficial as color-conversion photoresists are to be used as color filters in liquid crystal displays, micro light-emitting diodes, and organic light-emitting diodes.

Exceptionally stable quantum dot/siloxane hybrid encapsulation material for white light-emitting diodes with a wide color gamut.

Herein, we report a luminescent light-emitting diode (LED) encapsulating material using a thermally curable quantum dot (QD)/siloxane hybrid (TSE-QD) color converter, which has superior long-term stability even at elevated temperatures, in high humidity, and in various chemicals. The TSE-QD is cured by a thermal-induced hydrosilylation reaction of an in situ sol-gel synthesized QD dispersed siloxane resin (QD/siloxane resin) without additional ligand-exchange processes. QDs are successfully encapsulated by highly condensed and linear structured siloxane networks with additional chemical linkages between the surface ligands of the QDs and organic functional groups of the siloxane matrix. Moreover, QDs are uniformly distributed within the siloxane matrix retaining their optical properties during the fabrication processes of the TSE-QD. The result is that the stability, as evaluated by the photoluminescence (PL) quantum yield (QY), is greatly improved under harsh conditions, for example, 120 °C/5% relative humidity (RH), ethanol and acetone for 30 days. Based on the exceptionally stable TSE-QD, we demonstrate a white LED using a blue LED chip directly encapsulated by a yellow emitting TSE-QD that shows excellent spectral stability, outstanding reliability at 85 °C/85% RH and a wide color gamut (116% of NTSC).

Two-Step-Enhanced Stability of Quantum Dots via Silica and Siloxane Encapsulation for the Long-Term Operation of Light-Emitting Diodes.

Despite innovative optical properties of quantum dots (QDs) for QDs-converted light-emitting diodes (QD-LEDs), the vulnerability of the QDs, against heat and moisture, has been a critical issue for commercialization and long-term use. To overcome the instabilities, we fabricated a thermally and photostable QDs-embedded silica/siloxane (S-QD/siloxane) film by embedding QDs in silica and siloxane encapsulation through a two-step sol-gel reaction. S-QDs were stably dispersed in the oligo-siloxane resin with even a QD concentration of 5 wt % without aggregation. The two-step physical barriers of silica and siloxane acted to decrease the toxicity of QDs and improve the stability against heat and moisture [85 °C/5% relative humidity (RH), 85 °C/85% RH, and 120 °C/5% RH], light (50 and 100 mA), and chemicals (ethanol, HCl, and NaOH). Our S-QD/siloxane film was applied as a color-conversion material on a blue LED chip without additional solidification and encapsulation processes for red and white QD-LEDs, exhibiting a wider color gamut (107% in CIE 1931) compared to NTSC. These enhancements indicate that our S-QD/siloxane film is a suitable material for long-term operation of QD-enhanced films and QD-LEDs in next-generation displays.

Siloxane-Encapsulated Upconversion Nanoparticle Hybrid Composite with Highly Stable Photoluminescence against Heat and Moisture.

Herein, we report a siloxane-encapsulated upconversion nanoparticle hybrid composite (SE-UCNP), which exhibits excellent photoluminescence (PL) stability for over 40 days even at an elevated temperature, in high humidity, and in harsh chemicals. The SE-UCNP is synthesized through UV-induced free-radical polymerization of a sol-gel-derived UCNP-containing oligosiloxane resin (UCNP-oligosiloxane). The siloxane matrix with a random network structure by Si-O-Si bonds successfully encapsulates the UCNPs with chemical linkages between the siloxane matrix and organic ligands on UCNPs. This encapsulation results in surface passivation retaining the intrinsic fluorescent properties of UCNPs under severe conditions (e.g., 85 °C/85% relative humidity) and a wide range of pH (from 1 to 14). As an application example, we fabricate a two-color binary microbarcode based on SE-UCNP via a low-cost transfer printing process. Under near-infrared irradiation, the binary sequences in our barcode are readable enough to identify objects using a mobile phone camera. The hybridization of UCNPs with a siloxane matrix provides the capacity for highly stable UCNP-based applications in real environments.

Printing of wirelessly rechargeable solid-state supercapacitors for soft, smart contact lenses with continuous operations.

Recent advances in smart contact lenses are essential to the realization of medical applications and vision imaging for augmented reality through wireless communication systems. However, previous research on smart contact lenses has been driven by a wired system or wireless power transfer with temporal and spatial restrictions, which can limit their continuous use and require energy storage devices. Also, the rigidity, heat, and large sizes of conventional batteries are not suitable for the soft, smart contact lens. Here, we describe a human pilot trial of a soft, smart contact lens with a wirelessly rechargeable, solid-state supercapacitor for continuous operation. After printing the supercapacitor, all device components (antenna, rectifier, and light-emitting diode) are fully integrated with stretchable structures for this soft lens without obstructing vision. The good reliability against thermal and electromagnetic radiations and the results of the in vivo tests provide the substantial promise of future smart contact lenses.

Glass-Fabric Reinforced Ag Nanowire/Siloxane Composite Heater Substrate: Sub-10 nm Metal@Metal Oxide Nanosheet for Sensitive Flexible Sensing Platform.

The development of flexible chemiresistors is imperative for real-time monitoring of air quality and/or human physical conditions without space constraints. However, critical challenges such as poor sensing characteristics, vulnerability under toxic chemicals, and weak reliability hinder their practical use. In this work, for the first time, an ultrasensitive flexible sensing platform is reported by assembling Pt loaded thin-layered (≈10 nm) SnO2 nanosheets (Pt-SnO2 NSs) based 2D sensing layers on Ag nanowires embedded glass-fabric reinforced vinyl-phenyl siloxane hybrid composite substrate (AgNW-GFRVPH film) as a heater. The thermally stable AgNW-GFRVPH film based heater is fabricated by free radical polymerization of vinyl groups in vinyl-phenyl oligosiloxane and phenyltris(dimethylvinylsiloxy)silane with Ag NW and glass-fabric, showing outstanding heat generation (≈200 °C), high dimensional stability (13 ppm °C-1), and good thermal stability (≈350 °C). The Pt-SnO2 NSs, which are synthesized by calcination of Sn precursor coated graphene oxide (GO) sheets and subsequent Pt functionalization, exhibit high mechanical flexibility and superior response (Rair/Rgas = 4.84) to 1 ppm level dimethyl sulfide. Taking these advantages, GO-templated oxide NSs combined with a highly stable AgNW-GFRVPH film heater exhibits the best dimethyl sulfide sensing performance compared to state-of-the-art flexible chemiresistors, enabling them as a superior flexible gas sensing platform.

Transparent Urethane-Siloxane Hybrid Materials for Flexible Cover Windows with Ceramic-Like Strength, yet Polymer-Like Modulus.

Any transition toward an era of flexible electronics will have to overcome the mechanical limitations of materials. Specifically, the attainment of both strength and flexibility, which are generally mutually exclusive, is required including glass-like wear resistance, plastic-like compliance, and a high level of strain. Here, we fabricate a urethane-methacrylate-siloxane hybrid (UMSH) material. It is found that UMSH, with molecule-level hybridization of urethane linkage and methacrylate-siloxane conetworks, demonstrates ceramic-like high strength (574 MPa), yet polymer-like low modulus (8.42 GPa), and even high strain (6.3%) at fracture with excellent optical transparency. This combination of high strength, flexibility, and optical transparency indicates that this is a suitable material for glass substitution and can be used as a transparent flexible cover window for foldable display.

High-Performance and Simply-Synthesized Ladder-Like Structured Methacrylate Siloxane Hybrid Material for Flexible Hard Coating.

A high performance ladder-like structured methacrylate siloxane hybrid material (LMSH) was fabricated via simple hydrolytic sol⁻gel reaction, followed by free-radical polymerization. A structurally ordered siloxane backbone, the ladder-like structure, which is an essential factor for high performance, could be achieved by a short period of sol⁻gel reaction in only 4 h. This results in superior optical (Transmittance > 90% at 550 nm), thermal (T5 wt % decomposition > 400 ℃ ), mechanical properties(elastic recovery = 0.86, hardness = 0.6 GPa) compared to the random- and even commercialized cage-structured silsesquioxane, which also has ordered structure. It was investigated that the fabricated ladder-like structured MSH showed the highest overall density of organic/inorganic co-networks that are originated from highly ordered siloxane network, along with high conversion rate of polymerizable methacrylate groups. Our findings suggest a potential of the ladder-like structured MSH as a powerful alternative for the methacrylate polysilsesquioxane, which can be applied to thermally stable and flexible optical coatings, even with an easier and simpler preparation process.

Flexible Transparent Conductive Films with High Performance and Reliability Using Hybrid Structures of Continuous Metal Nanofiber Networks for Flexible Optoelectronics.

We report an Ag nanofiber-embedded glass-fabric reinforced hybrimer (AgNF-GFRHybrimer) composite film as a reliable and high-performance flexible transparent conducting film. The continuous AgNF network provides superior optoelectronic properties of the composite film by minimizing transmission loss and junction resistance. In addition, the excellent thermal/chemical stability and mechanical durability of the GFRHybrimer matrix provides enhanced mechanical durability and reliability of the final AgNF-GFRHybrimer composite film. To demonstrate the availability of our AgNF-GFRHybrimer composite as a transparent conducting film, we fabricated a flexible organic light-emitting diode (OLED) device on the AgNF-GFRHybrimer film; the OLED showed stable operation during a flexing.

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.

A mechanically enhanced hybrid nano-stratified barrier with a defect suppression mechanism for highly reliable flexible OLEDs.

Understanding the mechanical behaviors of encapsulation barriers under bending stress is important when fabricating flexible organic light-emitting diodes (FOLEDs). The enhanced mechanical characteristics of a nano-stratified barrier were analyzed based on a defect suppression mechanism, and then experimentally demonstrated. Following the Griffith model, naturally-occurring cracks, which were caused by Zn etching at the interface of the nano-stratified structure, can curb the propagation of defects. Cross-section images after bending tests provided remarkable evidence to support the existence of a defect suppression mechanism. Many visible cracks were found in a single Al2O3 layer, but not in the nano-stratified structure, due to the mechanism. The nano-stratified structure also enhanced the barrier's physical properties by changing the crystalline phase of ZnO. In addition, experimental results demonstrated the effect of the mechanism in various ways. The nano-stratified barrier maintained a low water vapor transmission rate after 1000 iterations of a 1 cm bending radius test. Using this mechanically enhanced hybrid nano-stratified barrier, FOLEDs were successfully encapsulated without losing mechanical or electrical performance. Finally, comparative lifetime measurements were conducted to determine reliability. After 2000 hours of constant current driving and 1000 iterations with a 1 cm bending radius, the FOLEDs retained 52.37% of their initial luminance, which is comparable to glass-lid encapsulation, with 55.96% retention. Herein, we report a mechanically enhanced encapsulation technology for FOLEDs using a nano-stratified structure with a defect suppression mechanism.

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.