Intrinsically Stretchable Floating Gate Memory Transistors for Data Storage of Electronic Skin Devices.

To propel electronic skin (e-skin) to the next level by integrating artificial intelligence features with advanced sensory capabilities, it is imperative to develop stretchable memory device technology. A stretchable memory device for e-skin must offer, in particular, long-term data storage while ensuring the security of personal information under any type of deformation. However, despite the significance of these needs, technology related to stretchable memory devices remains in its infancy. Here, we report an intrinsically stretchable floating gate (FG) polymer memory transistor. The device features a dual-stimuli (optical and electrical) writing system to prevent easy erasure of recorded data. An FG comprising an intermixture of Ag nanoparticles and elastomer and with proper energy-band alignment between the semiconductor and dielectric facilitated sustainable memory performance, while achieving a high memory on/off ratio (>105) and a long retention time (106 s) with the ability to withstand 50% uniaxial or 30% biaxial strain. In addition, our memory transistor exhibited high mechanical durability over multiple stretching cycles (1000 times), along with excellent environmental stability with respect to factors such as temperature, moisture, air, and delamination. Finally, we fabricated a 7 × 7 active-matrix memory transistor array for personalized storage of e-skin data and successfully demonstrated its functionality.

Autonomous self-healing supramolecular polymer transistors for skin electronics.

Skin-like field-effect transistors are key elements of bio-integrated devices for future user-interactive electronic-skin applications. Despite recent rapid developments in skin-like stretchable transistors, imparting self-healing ability while maintaining necessary electrical performance to these transistors remains a challenge. Herein, we describe a stretchable polymer transistor capable of autonomous self-healing. The active material consists of a blend of an electrically insulating supramolecular polymer with either semiconducting polymers or vapor-deposited metal nanoclusters. A key feature is to employ the same supramolecular self-healing polymer matrix for all active layers, i.e., conductor/semiconductor/dielectric layers, in the skin-like transistor. This provides adhesion and intimate contact between layers, which facilitates effective charge injection and transport under strain after self-healing. Finally, we fabricate skin-like self-healing circuits, including NAND and NOR gates and inverters, both of which are critical components of arithmetic logic units. This work greatly advances practical self-healing skin electronics.

Kinetically controlled metal-elastomer nanophases for environmentally resilient stretchable electronics.

Nanophase mixtures, leveraging the complementary strengths of each component, are vital for composites to overcome limitations posed by single elemental materials. Among these, metal-elastomer nanophases are particularly important, holding various practical applications for stretchable electronics. However, the methodology and understanding of nanophase mixing metals and elastomers are limited due to difficulties in blending caused by thermodynamic incompatibility. Here, we present a controlled method using kinetics to mix metal atoms with elastomeric chains on the nanoscale. We find that the chain migration flux and metal deposition rate are key factors, allowing the formation of reticular nanophases when kinetically in-phase. Moreover, we observe spontaneous structural evolution, resulting in gyrified structures akin to the human brain. The hybridized gyrified reticular nanophases exhibit strain-invariant metallic electrical conductivity up to 156% areal strain, unparalleled durability in organic solvents and aqueous environments with pH 2-13, and high mechanical robustness, a prerequisite for environmentally resilient devices.

Near-Infrared Transparent Transition-Metal-Doped Indium Oxide Thin-Film Heater for LiDAR.

The evolving need for all-weather light detection and ranging (LiDAR) sensors and cameras for autonomous vehicles, remote sensing surveillance, and space exploration has spurred the development of transparent heaters. While LiDAR photon sources have shifted from the visible to the near-infrared (NIR) range, the use of transparent conductive oxides (TCOs) for heaters leads to significant optical losses due to their high plasmonic absorption and reflection in the NIR range. Although different TCO compositions can be employed to preserve transparency and electrical conductivity in this range, the choice of dopants, their concentrations, and the underlying mechanisms remain largely unknown. In this study, we present TCOs specifically designed for NIR applications with a focus on identifying new compositions that strike a balance between NIR transparency and electrical conductivity. We present a 4B-6B transition-metal-doped indium oxide thin-film heater that exhibits impressive NIR transmittance (>90%) surpassing that of commonly used indium tin oxide films. By incorporating effective dopants such as titanium, hafnium, and tungsten, we successfully reduced the resistivity and enhanced the electrical conductivity of indium oxide films. To enhance the practical utility of the film, we implemented post-treatments comprising argon plasma treatment and encapsulation with low-molecular-weight poly(dimethylsiloxane), which resulted in significantly improved performance. The optimized film exhibited a sheet resistance of 520 Ω/sq and excellent optical transmittance at 850 nm (89.1%), 905 nm (89.7%), and 1550 nm (92%). Moreover, we successfully integrated defogging and defrosting capabilities into a commercial LiDAR camera and demonstrated its reliable operation in challenging environments.

Kirigami Photopiezo Catalysts for Self-Sustainable Environment Remediation.

Photo(electro)-piezo catalysis has emerged as one of the most effective strategies for sustainable environmental remediation. While various (nano)materials have been investigated for enhancing the intrinsic properties related to the interfacial band structure, increasing the efficiency by integration of materials with rational design for stress-strain applications has not yet been considered. Herein, we introduce kirigami strain engineering to photopiezo catalysts for enhancing efficiency by increasing the magnitude of applied strain and density of bends. Macroscale stretching motion is converted into localized bending by a pliable kirigami structure using similar or even lower input energy, which can be easily modulated by natural waves. The kirigami structure leads to a significant enhancement (∼250%) in the degradation of dyes, and we discovered the significant contribution of the oxygen reduction pathway in the charge-transfer mechanism, which corresponds to the observed enhancement. The photopiezo catalytic effects of kirigami were further highlighted by the small water reservoir test, showing its feasibility in nature for self-sustainable environmental remediation that can be modulated using motions of winds, waves, and life vibrations.

Subaqueous 3D stem cell spheroid levitation culture using anti-gravity bioreactor based on sound wave superposition.

BACKGROUND: Recently, various studies have revealed that 3D cell spheroids have several advantages over 2D cells in stem cell culture. However, conventional 3D spheroid culture methods have some disadvantages and limitations such as time required for spheroid formation and complexity of the experimental process. Here, we used acoustic levitation as cell culture platform to overcome the limitation of conventional 3D culture methods. METHODS: In our anti-gravity bioreactor, continuous standing sonic waves created pressure field for 3D culture of human mesenchymal stem cells (hMSCs). hMSCs were trapped and aggerated in pressure field and consequently formed spheroids. The structure, viability, gene and protein expression of spheroids formed in the anti-gravity bioreactor were analyzed by electron microscope, immunostaining, polymerase chain reaction, and western blot. We injected hMSC spheroids fabricated by anti-gravity bioreactor into the mouse hindlimb ischemia model. Limb salvage was quantified to evaluate therapeutic efficacy of hMSC spheroids. RESULTS: The acoustic levitation in anti-gravity bioreactor made spheroids faster and more compact compared to the conventional hanging drop method, which resulted in the upregulation of angiogenic paracrine factors of hMSCs, such as vascular endothelial growth factor and angiopoietin 2. Injected hMSCs spheroids cultured in the anti-gravity bioreactor exhibited improved therapeutic efficacy, including the degree of limb salvage, capillary formation, and attenuation of fibrosis and inflammation, for mouse hindlimb ischemia model compared to spheroids formed by the conventional hanging drop method. CONCLUSION: Our stem cell culture system using acoustic levitation will be proposed as a new platform for the future 3D cell culture system.

Subaqueous free-standing 3D cell culture system for ultrafast cell compaction, mechano-inductive immune control, and improving therapeutic angiogenesis.

Conventional 3D cell culture methods require a comprehensive complement in labor-intensive and time-consuming processes along with in vivo circumstantial mimicking. Here, we describe a subaqueous free-standing 3D cell culture (FS) device that can induce the omnidirectional environment and generate ultrafast human adipose-derived stem cells (hADSCs) that efficiently aggregate with compaction using acoustic pressure. The cell culture conditions were optimized using the FS device and identified the underlying molecular mechanisms. Unique phenomena in cell aggregation have led to extraordinary cellular behavior that can upregulate cell compaction, mechanosensitive immune control, and therapeutic angiogenesis. Therefore, we designated the resulting cell aggregates as "pressuroid." Notably, external acoustic stimulation produced by the FS device affected the pressuroids. Furthermore, the pressuroids exhibited upregulation in mechanosensitive genes and proteins, PIEZO1/2. CyclinD1 and PCNA, which are strongly associated with cell adhesion and proliferation, were elevated by PIEZO1/2. In addition, we found that pressuroids significantly increase angiogenic paracrine factor secretion, promote cell adhesion molecule expression, and enhance M2 immune modulation of Thp1 cells. Altogether, we have concluded that our pressuroid would suggest a more effective therapy method for future cell therapy than the conventional one.

Piezocatalytic 2D WS2 Nanosheets for Ultrasound-Triggered and Mitochondria-Targeted Piezodynamic Cancer Therapy Synergized with Energy Metabolism-Targeted Chemotherapy.

Piezoelectric nanomaterials that can generate reactive oxygen species (ROS) by piezoelectric polarization under an external mechanical force have emerged as an effective platform for cancer therapy. In this study, piezoelectric 2D WS2 nanosheets are functionalized with mitochondria-targeting triphenylphosphonium (TPP) for ultrasound (US)-triggered, mitochondria-targeted piezodynamic cancer therapy. In addition, a glycolysis inhibitor (FX11) that can inhibit cellular energy metabolism is loaded into TPP- and poly(ethylene glycol) (PEG)-conjugated WS2 nanosheet (TPEG-WS2 ) to potentiate its therapeutic efficacy. Upon US irradiation, the sono-excited electrons and holes generated in the WS2 are efficiently separated by piezoelectric polarization, which subsequently promotes the production of ROS. FX11-loaded TPEG-WS2 (FX11@TPEG-WS2 ) selectively accumulates in the mitochondria of human breast cancer cells. In addition, FX11@TPEG-WS2 effectively inhibits the production of adenosine triphosphate . Thus, FX11@TPEG-WS2 exhibits outstanding anticancer effects under US irradiation. An in vivo study using tumor-xenograft mice demonstrates that FX11@TPEG-WS2 effectively accumulated in the tumors. Its tumor accumulation is visualized using in vivo computed tomography . Notably, FX11@TPEG-WS2 with US irradiation remarkably suppresses the tumor growth of mice without systemic toxicity. This study demonstrates that the combination of piezodynamic therapy and energy metabolism-targeted chemotherapy using mitochondria-targeting 2D WS2 is a novel strategy for the selective and effective treatment of tumors.

Mechanically robust stretchable semiconductor metallization for skin-inspired organic transistors.

Despite recent remarkable advances in stretchable organic thin-film field-effect transistors (OTFTs), the development of stretchable metallization remains a challenge. Here, we report a highly stretchable and robust metallization on an elastomeric semiconductor film based on metal-elastic semiconductor intermixing. We found that vaporized silver (Ag) atom with higher diffusivity than other noble metals (Au and Cu) forms a continuous intermixing layer during thermal evaporation, enabling highly stretchable metallization. The Ag metallization maintains a high conductivity (>104 S/cm) even under 100% strain and successfully preserves its conductivity without delamination even after 10,000 stretching cycles at 100% strain and several adhesive tape tests. Moreover, a native silver oxide layer formed on the intermixed Ag clusters facilitates efficient hole injection into the elastomeric semiconductor, which transcends previously reported stretchable source and drain electrodes for OTFTs.

Antioxidant Triggered Metallic 1T' Phase Transformations of Chemically Exfoliated Tungsten Disulfide (WS2 ) Nanosheets.

Developing facile methods for inducing phase transformation between metallic and semiconducting 2D transition metal dichalcogenide (TMDC) materials is crucial toward leveraging their use in cutting-edge energy devices. Herein, 2H-to-1T' phase transformations in chemically exfoliated Tungsten Disulfide (WS2 ) nanosheet films, triggered by antioxidants toward highly conductive 2D TMDC electrode materials, are introduced. It is found that antioxidants cause residual LiOx compounds to reduce to Li metal, subsequently inducing 1T' phase transformations in layered WS2 nanosheets, resulting in significantly enhanced conductivity across the overall films. Both thermoelectric devices and supercapacitors are fabricated utilizing the highly conductive 1T' phase WS2 nanosheet films as a working electrode, allowing for outstanding performance due to the increased conductivity of the WS2 nanosheet films. The method constitutes a facile approach toward the use of chemically exfoliated 1T' TMDC nanosheets for highly efficient energy device applications.

Self-Assembled 2D Networks of Metal Oxide Nanomaterials Enabling Sub-ppm Level Breathalyzers.

For extremely sensitive acetone sensors, here, we introduced an alcohol-assisted surfactant-free Langmuir-Blodgett process to rapidly assemble a single-layered two-dimensional (2D) network as a suitable percolation strategy of metal oxide semiconductor nanomaterials. The single-layered 2D network formation mechanism was investigated using zinc oxide (ZnO) nanobeads (NBs). Furthermore, the correlation between the response of the gas sensor and the average percolation number of the ZnO NBs, controlled by multi-stacking the 2D network, was investigated. It was inferred that a reduction in the number of percolations led to maximization of the response. Additionally, the versatility of the optimal percolation strategy was experimentally verified by confirming similar results to that achieved with ZnO NBs when utilizing different sizes, shapes, and compositions of metal oxides. Finally, the practical effectiveness of our extremely sensitive strategy was solidified by illustrating the response enhancement in a commercial exhalation diagnostic system that measures the amount of acetone in only 1 mL of exhalation.

Phase-dependent gas sensitivity of MoS2 chemical sensors investigated with phase-locked MoS2.

In the present study, phase-dependent gas sensitivities of MoS2 chemical sensors were examined. While 1T-phase MoS2 (1T-MoS2) has shown better chemical sensitivity than has 2H-phase MoS2 (2H-MoS2), the instability of the 1T phase has been hindering applications of 1T-MoS2 as chemical sensors. Here, the chemical sensitivity of MoS2 locked in its 1T phase by using a ZnO phase lock was investigated. To develop MoS2 chemical sensors locked in the 1T phase, we synthesized a multi-dimensional nanomaterial by growing ZnO nanorods onto MoS2 nanosheets (ZnO@1T-MoS2). Raman spectroscopy and x-ray photoelectron spectroscopy analyses of such phase-locked 1T-MoS2 subjected to flash light irradiation 100 times confirmed its robustness. ZnO nanomaterials hybridized on MoS2 nanosheets not only froze the MoS2 at its 1T phase, but also increased the active surface area for chemical sensing. The resulting hybridized material showed better response, namely better sensitivity, to NO2 gas exposure at room temperature than did 1T-MoS2 and 2H-MoS2. This result indicated that increased surface area and heterojunction formation between MoS2 and ZnO constitute a more promising route for improving sensitivity than using the 1T phase itself.

Scratch to sensitize: scratch-induced sensitivity enhancement in semiconductor thin-film sensors.

Semiconductor gas sensors are advantageous in miniaturization and can be used in a wide range of applications, yet consume large power due to high operating temperature. Here we demonstrated the ability of nanoscale scratches produced with mechanical abrasion to enhance the chemical sensitivity of thin-film-type semiconductor sensors. Well-aligned arrays of scratches parallel to the electrical current direction between the source and drain electrodes were made, using typical polishing machines with diamond suspensions, on semiconductor thin films produced with various deposition methods such as atomic layer deposition (ALD), sputtering, and the sol-gel technique. Processing with sharp diamond microparticles left nano-grooves on the surface, together with changes in chemical composition. For all of the tested metal oxide thin films, the introduction of scratches yielded increased quantities of oxygen vacancies and metallic components. Scratched ZnO devices exhibited superior performance even at room temperature, as predicted by a computational simulation that showed increased binding energy of gas molecules on defects. The scratch technique shown in the present study may be used to produce dense arrays of nanometer-scale, chemically functionalized line patterns on substrates larger than a few tens of centimeters with minimum cost, which in turn may be used in a variety of applications including massive arrays of sensors displaying high sensitivity.

Optical Tunneling Mediated Sub-Skin-Depth High Emissivity Tungsten Radiators.

Tailoring the spectrum of thermal radiation at high temperatures is a central issue in the study of thermal radiation harnessed energy resources. Although bulk metals with periodic cavities incorporated into their surfaces provide high emissivity, they require a complicated micron metal etch, thereby precluding reliable, continuous operation. Here, we report thermally stable, highly emissive, ultrathin (<20 nm) tungsten (W) radiators that were prepared in a scalable and cost-effective route. Alumina/W/alumina multiwalled, submicron cavity arrays were fabricated sequentially using nanoimprinting lithography, thin film deposition, and calcination processes. To highlight the practical importance of high-temperature radiators, we developed a thermophotovoltaic (TPV) system equipped with fabricated W radiators and low-bandgap GaSb photovoltaic cells. The TPV system produced electric power reliably during repeated temperature cycling between 500 and 1200 K; the power density at 1200 K was fixed to be approximately 1.0 W/cm2. The temperature-dependent electric power was quantitatively reproduced using a one-dimensional energy conversion model. The symmetric configuration of alumina/W/alumina multiwall together with the presence of a void inside each cavity alleviated thermal stress, which was responsible for the stable TPV performance. The short-current-density (JSC) of developed TPV system was augmented significantly by decreasing the W thickness below its skin depth. A 17 nm thick W radiator yielded a 32% enhancement in JSC compared to a 123 nm thick W radiator. Electromagnetic analysis indicated that subskin-depth W cavity arrays led to suppressed surface reflection due to the mitigated screening effect of free electrons, thereby enhancing the absorption of light within each W wall. Such optical tunneling-mediated absorption or radiation was valid for any metal material and morphology (e.g., planar or patterned).

A Disposable Photovoltaic Patch Controlling Cellular Microenvironment for Wound Healing.

Electrical stimulation (ES) is known to affect the wound healing process by modulating skin cell behaviors. However, the conventional clinical devices that can generate ES for promoting wound healing require patient hospitalization due to large-scale of the extracorporeal devices. Herein, we introduce a disposable photovoltaic patch that can be applied to skin wound sites to control cellular microenvironment for promoting wound healing by generating ES. In vitro experiment results show that exogenous ES could enhance cell migration, proliferation, expression of extracellular matrix proteins, and myoblast differentiation of fibroblasts which are critical for wound healing. Our disposable photovoltaic patches were attached to the back of skin wound induced mice. Our patch successfully provided ES, generated by photovoltaic energy harvested from the organic solar cell under visible light illumination. In vivo experiment results show that the patch promoted cutaneous wound healing via enhanced host-inductive cell proliferation, cytokine secretion, and protein synthesis which is critical for wound healing process. Unlike the current treatments for wound healing that engage passive healing processes and often are unsuccessful, our wearable photovoltaic patch can stimulate regenerative activities of endogenous cells and actively contribute to the wound healing processes.

Microstructured void gratings for outcoupling deep-trap guided modes.

Breaking the total internal reflection far above a critical angle (i.e., outcoupling deep-trap guided modes) can dramatically improve existing light-emitting devices. Here, we report a deep-trap guided modes outcoupler using densely arranged microstructured hollow cavities. Measurements of the leaky mode dispersions of hollow-cavity gratings accurately quantify the wavelength-dependent outcoupling strength above a critical angle, which is progressively improved over the full visible spectrum by increasing the packing density. Comparing hollow- and filled-cavity gratings, which have identical morphologies except for their inner materials (void vs. solid sapphire), reveals the effectiveness of using the hollow-cavity grating to outcouple deep-trap guided modes, which results from its enhanced transmittance at near-horizontal incidence. Scattering analysis shows that the outcoupling characteristics of a cavity array are dictated by the forward scattering characteristics of their individual cavities, suggesting the importance of a rationally designed single cavity. We believe that a hollow-cavity array tailored for different structures and spectra will lead to a technological breakthrough in any type of light-emitting device.

Graphene as a thin-film catalyst booster: graphene-catalyst interface plays a critical role.

Due to its extreme thinness, graphene can transmit some surface properties of its underlying substrate, a phenomenon referred to as graphene transparency. Here we demonstrate the application of the transparency of graphene as a protector of thin-film catalysts and a booster of their catalytic efficiency. The photocatalytic degradation of dye molecules by ZnO thin films was chosen as a model system. A ZnO thin film coated with monolayer graphene showed greater catalytic efficiency and long-term stability than did bare ZnO. Interestingly, we found the catalytic efficiency of the graphene-coated ZnO thin film to depend critically on the nature of the bottom ZnO layer; graphene transferred to a relatively rough, sputter-coated ZnO thin film showed rather poor catalytic degradation of the dye molecules while a smooth sol-gel-synthesized ZnO covered with monolayer graphene showed enhanced catalytic degradation. Based on a systematic investigation of the interface between graphene and ZnO thin films, we concluded the transparency of graphene to be critically dependent on its interface with a supporting substrate. Graphene supported on an atomically flat substrate was found to efficiently transmit the properties of the substrate, but graphene suspended on a substrate with a rough nanoscale topography was completely opaque to the substrate properties. Our experimental observations revealed the morphology of the substrate to be a key factor affecting the transparency of graphene, and should be taken into account in order to optimally apply graphene as a protector of catalytic thin films and a booster of their catalysis.

Therapeutic Angiogenesis via Solar Cell-Facilitated Electrical Stimulation.

Cell therapy has been suggested as a treatment modality for ischemic diseases, but the poor survival and engraftment of implanted cells limit its therapeutic efficacy. To overcome such limitation, we used electrical stimulation (ES) derived from a wearable solar cell for inducing angiogenesis in ischemic tissue. ES enhanced the secretion of angiogenic growth factors and the migration of mesenchymal stem cells (MSCs), myoblasts, endothelial progenitor cells, and endothelial cells in vitro. In a mouse ischemic hindlimb model, ES generated by a solar cell and applied to the ischemic region promoted migration of MSCs toward the ischemic site and upregulated expression of angiogenic paracrine factors (vascular endothelial, basic fibroblast, and hepatocyte growth factors; and stromal cell-derived factor-1α). Importantly, solar cell-generated ES promoted the formation of capillaries and arterioles at the ischemic region, attenuated muscle necrosis and fibrosis, and eventually prevented loss of the ischemic limb. Solar cell ES therapy showed higher angiogenic efficacy than conventional MSC therapy. This study shows the feasibility of using solar cell ES as a novel treatment for therapeutic angiogenesis.

Stretchable Piezoelectric Substrate Providing Pulsatile Mechanoelectric Cues for Cardiomyogenic Differentiation of Mesenchymal Stem Cells.

Ex vivo induction of cardiomyogenic differentiation of mesenchymal stem cells (MSCs) before implantation would potentiate therapeutic efficacy of stem cell therapies for ischemic heart diseases because MSCs rarely undergo cardiomyogenic differentiation following implantation. In cardiac microenvironments, electric pulse and cyclic mechanical strain are sequentially produced. However, no study has applied the pulsatile mechanoelectric cues (PMEC) to stimulate cardiomyogenic differentiation of MSCs ex vivo. In this study, we developed a stretchable piezoelectric substrate (SPS) that can provide PMEC to human MSCs (hMSCs) for cardiomyogenic differentiation ex vivo. Our data showed that hMSCs subjected to PMEC by SPS underwent promoted cardiac phenotype development: cell alignment and the expression of cardiac markers (i.e., cardiac transcription factors, structural proteins, ion channel proteins, and gap junction proteins). The enhanced cardiac phenotype development was mediated by the upregulation of cardiomyogenic differentiation-related autocrine factor expression, focal adhesion kinase, and extracellular signal-regulated kinases signaling pathways. Thus, SPS providing electrical and mechanical regulation of stem cells may be utilized to potentiate hMSC therapies for myocardial infarction and provide a tool for the study of stem cell biology.

Lattice Transparency of Graphene.

Here, we demonstrated the transparency of graphene to the atomic arrangement of a substrate surface, i.e., the "lattice transparency" of graphene, by using hydrothermally grown ZnO nanorods as a model system. The growth behaviors of ZnO nanocrystals on graphene-coated and uncoated substrates with various crystal structures were investigated. The atomic arrangements of the nucleating ZnO nanocrystals exhibited a close match with those of the respective substrates despite the substrates being bound to the other side of the graphene. By using first-principles calculations based on density functional theory, we confirmed the energetic favorability of the nucleating phase following the atomic arrangement of the substrate even with the graphene layer present in between. In addition to transmitting information about the atomic lattice of the substrate, graphene also protected its surface. This dual role enabled the hydrothermal growth of ZnO nanorods on a Cu substrate, which otherwise dissolved in the reaction conditions when graphene was absent.