Nanostructure engineering in organic semiconductor devices toward interface matching.

The performance of organic semiconductor devices with heterojunctions between the organic semiconductors and electrodes can be improved by reducing the contact resistance. In this study, we have developed nanopatterned electrodes that gradually change the impedance at the interface between the metal and organic semiconductor in organic devices, which were fabricated in periodic patterns using nanoimprint lithography. The imprint pattern spacing was changed to control the interface between the metal and organic semiconductor to ensure smooth carrier injection. We analyzed the carrier injection based on the pattern spacing of the electrode interface using electrical current-voltage and capacitance-frequency measurements in the diode. Subsequently, we analyzed the improved current mechanism through numerical simulation. Therefore, this study suggests the possibility of designing the interface of an organic device using the nanostructure between the organic semiconductor and carrier injection electrode.

Correction: A wearable colorimetric sweat pH sensor-based smart textile for health state diagnosis.

Correction for 'A wearable colorimetric sweat pH sensor-based smart textile for health state diagnosis' by Ji-Hwan Ha et al., Mater. Horiz., 2023, 10, 4163-4171, https://doi.org/10.1039/d3mh00340j.

A wearable colorimetric sweat pH sensor-based smart textile for health state diagnosis.

Sweat pH is an important indicator for diagnosing disease states, such as cystic fibrosis. However, conventional pH sensors are composed of large brittle mechanical parts and need additional instruments to read signals. These pH sensors have limitations for practical wearable applications. In this study, we propose wearable colorimetric sweat pH sensors based on curcumin and thermoplastic-polyurethane (C-TPU) electrospun-fibers to diagnose disease states by sweat pH monitoring. This sensor aids in pH monitoring by changing color in response to chemical structure variation from enol to di-keto form via H-atom separation. Its chemical structure variation changes the visible color due to light absorbance and reflectance changes. Furthermore, it can rapidly and sensitively detect sweat pH due to its superior permeability and wettability. By O2 plasma activation and thermal pressing, this colorimetric pH sensor can be easily attached to various fabric substrates such as swaddling and patient clothing via surface modification and mechanical interlocking of C-TPU. Furthermore, the diagnosable clothing is durable and reusable enough to neutral washing conditions due to the reversible pH colorimetric sensing performance by restoring the enol form of curcumin. This study contributes to the development of smart diagnostic clothing for cystic fibrosis patients who require continuous sweat pH monitoring.

Portable Iontophoresis Device for Efficient Drug Delivery.

The timely delivery of drugs to specific locations in the body is imperative to ensure the efficacy of treatment. This study introduces a portable facial device that can deliver drugs efficiently using iontophoresis. Two types of power supplies-direct current and pulse ionization supplies-were manufactured by injection molding. Electrical stimulation elements, which contained Ag metal wires, were woven into facial mask packs. The diffusion phenomenon in the skin and iontophoresis were numerically modeled. Injection molding was simulated before the device was manufactured. Analysis using rhodamine B demonstrated a remarkable increase in the moisture content of the skin and effective absorption of the drug under an applied electric field upon the application of iontophoresis. The proposed concept and design constitute a new method of achieving effective drug absorption with wearable devices.

Functional Asymmetry-Enabled Self-Adhesive Film via Phase Separation of Binary Polymer Mixtures for Soft Bio-Integrated Electronics.

Biocompatible adhesive films are important for many applications (e.g., wearable devices, implantable devices, and attachable sensors). In particular, achieving self-adhesion on one side of a film with biocompatible materials is a compelling goal in adhesion science. Herein, we report a simple and easy manufacturing process using water-soluble hyaluronic acid (HA) that allows adhesiveness on only one side using binary polymer mixtures based on a phase-separation strategy with an elastomer. HA influx allows for the entangled polymer chains of the elastomer to spontaneously deform, permitting tunable mechanical elasticity, conformability, and adhesion. The proposed adhesive film enables the transfer of nanopatterning and the attachment of various surfaces without the use of additional chemicals. In addition, the film can be used for measuring epidermal biopotential and for skin fixation of drug devices. Therefore, the developed facile asymmetric adhesion can block the interferences of other materials on the unnecessary adhesion side, providing considerable potential for the development of functional, multifunctional, and smart bioadhesives.

Wafer-scale, highly uniform, and well-arrayed suspended nanostructures for enhancing the performance of electronic devices.

Suspended nanostructures play an important role in enhancing the performance of a diverse group of nanodevices. However, realizing a good arrangement and suspension for nanostructures of various shapes remains a significant challenge. Herein, a rapid and simple method for fabricating wafer-scale, highly uniform, well-arrayed suspended nanostructures via nanowelding lithography is reported. Suspended nanostructures with various shapes (nanowires, nanoholes, nanomesh, and nanofilms) and materials (gold, silver, and palladium metals) were employed to demonstrate the applicability of our method. Moreover, gas sensors and thermoacoustic speakers with suspended nanowires outperformed those with unsuspended nanostructures. The proposed method is expected to help advance the development of future nanodevices based on suspended nanostructures.

Biocompatible All-in-One Adhesive Needle-Free Cup Patch for Enhancing Transdermal Drug Delivery.

Patch-type drug delivery has garnered increased attention as an attractive alternative to the existing drug delivery techniques. Thus far, needle phobia and efficient drug delivery remain huge challenges. To address the issue of needle phobia and enhance drug delivery, we developed a needle-free and self-adhesive microcup patch that can be loaded with an ultrathin salmon DNA (SDNA) drug carrier film. This physically integrated system can facilitate efficient skin penetration of drugs loaded into the microcup patch. The system consists of three main components, namely, a cup that acts as a drug reservoir, an adhesive system that attaches the patch to the skin, and physical stimulants that can be used to increase the efficiency of drug delivery. In addition, an ultrathin SDNA/drug film allows the retention of the drug in the cup and its efficient release by dissolution in the presence of moisture. This latter feature has been validated using gelatin as a skin mimic. The cup design itself has been validated by comparing its deformation and displacement with those of a cylindrical structure. Integration of the self-adhesive microcup patch with both ultrasonic waves and an electric current allows the model drug to penetrate the stratum corneum of the skin barrier and the whole epidermis, thereby enhancing transdermal drug delivery and reducing skin irritation. This system can be used as a wearable biomedical device for efficient transdermal and needle-free drug delivery.

Biocompatible Nanotransfer Printing Based on Water Bridge Formation in Hyaluronic Acid and Its Application to Smart Contact Lenses.

Many conventional micropatterning and nanopatterning techniques employ toxic chemicals, rendering them nonbiocompatible and unsuited for biodevice production. Herein the formation of water bridges on the surface of hyaluronic acid (HA) films is exploited to develop a transfer-based nanopatterning method applicable to diverse structures and materials. The HA film surface, made deformable via water bridge generation, is brought into contact with a functional material and subjected to thermal treatment, which results in film shrinkage, allowing a robust pattern transfer. The proposed biocompatible method, which avoids the use of extra chemicals, enables the transfer of nanoscale, microscale, and thin-film structures as well as functional materials such as metals and metal oxides. A nanopatterned HA film is transferred onto a moisture-containing contact lens to fabricate smart contact lenses with unique optical characteristics of rationally designed optical nanopatterns. These lenses demonstrated binocular parallax-induced stereoscopy via nanoline array polarization and acted as cutoff filters, with nanodot arrays, capable of treating Irlen syndrome.

Large-Area Nanogap-Controlled 3D Nanoarchitectures Fabricated via Layer-by-Layer Nanoimprint.

The fabrication of large-area and flexible nanostructures currently presents various challenges related to the special requirements for 3D multilayer nanostructures, ultrasmall nanogaps, and size-controlled nanomeshes. To overcome these rigorous challenges, a simple method for fabricating wafer-scale, ultrasmall nanogaps on a flexible substrate using a temperature above the glass transition temperature (Tg) of the substrate and by layer-by-layer nanoimprinting is proposed here. The size of the nanogaps can be easily controlled by adjusting the pressure, heating time, and heating temperature. In addition, 3D multilayer nanostructures and nanocomposites with 2, 3, 5, 7, and 20 layers were fabricated using this method. The fabricated nanogaps with sizes ranging from approximately 1 to 40 nm were observed via high-resolution transmission electron microscopy (HRTEM). The multilayered nanostructures were evaluated using focused ion beam (FIB) technology. Compared with conventional methods, our method could not only easily control the size of the nanogaps on the flexible large-area substrate but could also achieve fast, simple, and cost-effective fabrication of 3D multilayer nanostructures and nanocomposites without any post-treatment. Moreover, a transparent electrode and nanoheater were fabricated and evaluated. Finally, surface-enhanced Raman scattering substrates with different nanogaps were evaluated using rhodamine 6G. In conclusion, it is believed that the proposed method can solve the problems related to the high requirements of nanofabrication and can be applied in the detection of small molecules and for manufacturing flexible electronics and soft actuators.

Shape-Controlled and Well-Arrayed Heterogeneous Nanostructures via Melting Point Modulation at the Nanoscale.

A novel method for fabricating shape-controlled and well-arrayed heterogeneous nanostructures by altering the melting point of the metal thin film at the nanoscale is proposed. Silver nanofilms (AgNFs) are transformed into silver nanoislands (AgNIs), silver nanoparticles (AgNPs), and silver nanogaps (AgNGs) that are well-ordered and repositioned inside the gold nanoholes (AuNHs) depending on the diameter of the AuNHs, the thickness of the AgNF, and the heating temperature (120-200 °C). This method demonstrates the ability to fabricate uniform, stable, and unique structures with a fast, simple, and mass-producible process. For demonstrating the diverse applicability of the developed structures, high-density AgNGs inside the AuNHs are utilized as surface-enhanced Raman spectroscopy (SERS) substrates. These AgNGs-based SERS substrates exhibit a performance enhancement, which is 1.06 × 106 times greater than that of a metal film, with a relative standard deviation of 19.8%. The developed AgNP/AgNI structures are also used as nonreproducible anti-counterfeiting signs, and the anti-counterfeiting/readout system is demonstrated via image processing. Therefore, our method could play a vital role in the nanofabrication of high-demand nanostructures.

Effective Dispensing Methods for Loading Drugs Only to the Tip of DNA Microneedles.

Here, we propose a novel and simple method to efficiently capture the diffusion of fluorescein isothiocyanate (FITC)-dextran from a biocompatible substance and load the drug only to the tip of DNA microneedles. A dispensing and suction method was chosen to fabricate the designed microneedles with efficient amounts of FITC as the drug model. Importantly, the vacuum process, which could influence the capturing of FITC diffusion from the tip, was evaluated during the manufacturing process. In addition, the simulations were consistent with the experimental results and showed apparent diffusion. Moreover, dextrans of different molecular weights labeled with FITC were chosen to fabricate the tip of microneedles for demonstrating their applicability. Finally, a micro-jetting system with a micro-nozzle (diameter: 80 µm) was developed to achieve the accurate and rapid loading of small amounts of FITC using the anti-diffusion and micro-jetting methods. Our method not only uses a simple and fast manufacturing process, but also fabricates the tips of microneedles more efficiently with FITC compared with the existing methods. We believe that the proposed method is essential for the clinical applications of the microneedle drug delivery platform.

3D Layer-By-Layer Pd-Containing Nanocomposite Platforms for Enhancing the Performance of Hydrogen Sensors.

Herein, a nanowelding technique is adopted to fabricate three-dimensional layer-by-layer Pd-containing nanocomposite structures with special properties. Nanowires fabricated from noble metals (Pd, Pt, Au, and Ag) were used to prepare Pd-Pd nanostructures and Pd-Au, Pd-Pt, Pd-Ag, and Pd-Pt-Au nanocomposite structures by controlling the welding temperature. The recrystallization behavior of the welded composite materials was observed and analyzed. In addition, their excellent mechanical and electrical properties were confirmed by performing 10,000 bending test cycles and measuring the resistances. Finally, flexible and wearable nanoheaters and gas sensors were fabricated using our proposed method. In comparison with conventional techniques, our proposed method can not only easily achieve sensors with a large surface area and flexibility but also improve their performance through the addition of catalyst metals. A gas sensor fabricated using the Pd-Au nanocomposites demonstrated 3.9-fold and 1.1-fold faster H2 recovery and response, respectively, than a pure Pd-Pd gas sensor device. Moreover, the Pd-Ag nanocomposite exhibited a high sensitivity of 5.5% (better than that of other fabricated gas sensors) for 1.6% H2 concentration. Therefore, we believe that the fabricated nanocomposites appear promising for wide applications in wearable gas sensors, flexible optical devices, and flexible catalytic devices.

Ultrasonically and Iontophoretically Enhanced Drug-Delivery System Based on Dissolving Microneedle Patches.

A multifunctional system comprised of hyaluronic acid microneedles was developed as an effective transdermal delivery platform for rapid local delivery. The microneedles can regulate the filling amount on the tip, by controlling the concentration of hyaluronic acid solution. Ultrasonication induces dissolution of the HA microneedles via vibration of acoustic pressure, and AC iontophoresis improves the electrostatic force-driven diffusion of HA ions and rhodamine B. The effect of ultrasound on rhodamine release was analyzed in vitro using a gelatin hydrogel. The frequency and voltage dependence of the AC on the ion induction transfer was also evaluated experimentally. The results showed that the permeability of the material acts as a key material property. The delivery system based on ultrasonication and iontophoresis in microneedles increases permeation, thus resulting in shorter initial delivery time than that required by delivery systems based on passive or ultrasonication alone. This study highlights the significance of the combination between ultrasonic waves and iontophoresis for improving the efficiency of the microneedles, by shortening the reaction duration. We anticipate that this system can be extended to macromolecular and dependence delivery, based on drug response time.

Nanotransfer Printing on Textile Substrate with Water-Soluble Polymer Nanotemplate.

The growing interest in wearable devices has drawn increased attention to smart textiles, and various transfer methods have therefore been introduced to realize the desired functions using textiles as substrates. However, the existing transfer techniques are not suited for the production of sophisticated nanoscale patterns on textiles, as textile roughness and difficulty of precise pattern size control hinder miniaturization, deteriorate device performance, and complicate the use of optical phenomena such as surface plasmon resonance. To address these limitations, we have developed a method based on simple dissolution of a water-soluble nanopatterned polymer film for the facile transfer of nanostructures of on-film-deposited functional materials onto textile substrates. The above method tolerates a variety of functional materials, e.g., metals and SiO2, and nano/microscale structures, e.g., nanoscale lines, dots, holes, and mesh patterns with a minimum pattern width of 50 nm. The proposed technique is employed to fabricate a palladium nanoscale line array (utilized as a highly sensitive and selective hydrogen sensor) and is shown to be suitable for the production of security patterns on textiles, as it allows the printing of complex nanostructure patterns with electrical and optical functionalities.

Adhesive-Layer-Free and Double-Faced Nanotransfer Lithography for a Flexible Large-Area MetaSurface Hologram.

Herein, we develop an adhesive-free double-faced nanotransfer lithography (ADNT) technique based on the surface deformation of flexible substrates under the conditions of temperature and pressure control and thus address the challenge of realizing the mass production of large-area nanodevices in the fields of optics, metasurfaces, and holograms. During ADNT, which is conducted on a flexible polymer substrate above its glass transition temperature in the absence of adhesive materials and chemical bonding agents, nanostructures from the polymer stamp are attached to the deformed polymer substrate. Various silicon masters are employed to prove our method applicable to arbitrary nanopatterns, and diverse Ag and Au nanostructures are deposited on polymer molds to demonstrate the wide scope of useable metals. Finally, ADNT is used to (i) produce a flexible large-area hologram on the defect-free poly(methyl methacrylate) (PMMA) film and (ii) fabricate a metasurface hologram and a color filter on the front and back surfaces of the PMMA film, respectively, to realize dual functionality. Thus, it is concluded that the use of ADNT can decrease the fabrication time and cost of high-density nanodevices and facilitate their commercialization.

Nanopattern-Embedded Micropillar Structures for Security Identification.

A novel method was developed for fabricating nanopatterns embedded on micropillar-structured surfaces using nanowelding technology for security identification. Commonly used substrates, that is, polyethylene films, glass wafers, Si wafers, and curved surfaces, were employed and their characteristics were evaluated. Cr was deposited onto the selected substrate to strengthen the adhesion force, and an adhesive layer of ultra-thin metal was deposited on top of the Cr layer. Lastly, nanopatterns were embedded on the substrates by nanowelding. The morphologies, cross sections, and three-dimensional (3D) images of the fabricated nanostructures were evaluated, and their crystalline structures and compositions were analyzed. Using the same method, nanopatterns embedded on micropillar-structured surfaces were fabricated for the first time as security patterns to improve security identification. The fabricated security patterns were characterized in three stages. First, micropillar structures and structural color were simply observed via optical microscopy to achieve a preliminary judgment. The appearance of structural color was due to the nanostructures fabricated on the micropillar surface. Next, the designed nanopatterns on the micropillar-structured surfaces were observed by scanning electron microscopy. Lastly, the changes in the spectral peaks were precisely observed using a spectrometer to achieve an enhanced security pattern. The fabricated security patterns can be suitable for valuable products, such as branded wines, watches, and bags. In addition, the proposed method offers a simple approach for transferring metal nanopatterns to common substrates. Moreover, the fabricated security patterns can have potential applications in semiconductor electrodes, transparent electrodes, and security identification codes.

Microneedles integrated with a triboelectric nanogenerator: an electrically active drug delivery system.

In this study, a combined system of microneedles and a triboelectric nanogenerator (TENG) has been developed for drug delivery. A triboelectric device, which converts mechanical energy into alternating current (AC), was chosen to replace the electrophoresis (EP) effect. To directly generate triboelectricity from salmon deoxyribonucleic acid (SDNA)-based microneedles, a triboelectric series of SDNA film and chargeable polymers (polyimide and Teflon) was studied. The electrical output of the two charged polymers was compared to find a material that could be highly charged with SDNA. The electrical output was also compared as a function of the concentration of a drug embedded in the SDNA film, and the results confirmed that drug intercalation affected the carrier diffusion. The mechanical strength of the microneedles was assessed by histological analysis of their penetration into porcine cadaver skin. Furthermore, the output voltage of a system incorporating microneedles and TENG in cadaver skin, and in vitro drug release into gelatin were evaluated to examine potential application as an electrically active drug delivery system. The electrical output voltage of this system was ∼95 V. The mechanism of triboelectric perturbation to the skin has also been discussed. The system developed in this work is a new, facile approach toward effective drug delivery that replaces the existing EP method and expands the application of TENGs.