Ultrathin Copper Monosulfide Films for an Optically Semitransparent, Highly Selective Ammonia Chemosensor.

Transition-metal sulfides are emerging as promising materials for chemiresistive gas sensors─a field still dominated by semiconducting metal oxides. Despite the availability of materials with tunable electronic, optical, physical, and chemical properties, few studies have moved beyond synthesis to provide strategies for enhancing gas sensing performance through material modification. Here, we present a simple, scalable synthetic strategy for developing an optically semitransparent, flexible NH3 gas sensor with a highly uniform, ultrathin CuS (covellite) active sensing layer. The optical and chemical properties of the CuS were precisely controlled near the percolation threshold of thin-film formation by varying key experimental parameters such as the Cu film thickness (<10 nm) and the sulfurization time (∼90 s) under ambient conditions. Experimental and computational studies of CuS and its NH3 sensing characteristics identify key physicochemical properties. The controlled surface chemistry and morphology of the ultrathin CuS layer demonstrate its effectiveness in functional NH3 sensing devices, which achieve a calculated detection limit of 1.38 ppm for NH3 gas at 150 °C, along with exceptional mechanical robustness and optical semitransparency in the visible-light spectrum.

Compression-sensitive smart windows: inclined pores for dynamic transparency changes.

Smart windows, capable of tailoring light transmission, can significantly reduce energy consumption in building services. While mechano-responsive windows activated by strains are promising candidates, they face long-lasting challenges in which the space for the light scatterer's operation has to be enlarged along with the window size, undermining the practicality. Recent attempts to tackle this challenge inevitably generate side effects with compromised performance in light modulation. Here, we introduce a cuttlefish-inspired design to enable the closing and opening of pores within the 3D porous structure by through-thickness compression, offering opacity and transparency upon release and compression. By changing the activation mode from the conventional in-plane to through-thickness direction, the space requirement is intrinsically decoupled from the lateral size of the scatterer. Central to our design is the asymmetry of pore orientation in the 3D porous structure. These inclined pores against the normal direction increase the opaqueness upon release and improve light modulation sensitivity to compression, enabling transmittance regulation upon compression by an infinitesimal displacement of 50 µm. This work establishes a milestone for smart window technologies and will drive advancements in the development of opto-electric devices.

Functional bio-inspired hybrid fliers with separated ring and leading edge vortices.

Recent advances in passive flying systems inspired by wind-dispersed seeds contribute to increasing interest in their use for remote sensing applications across large spatial domains in the Lagrangian frame of reference. These concepts create possibilities for developing and studying structures with performance characteristics and operating mechanisms that lie beyond those found in nature. Here, we demonstrate a hybrid flier system, fabricated through a process of controlled buckling, to yield unusual geometries optimized for flight. Specifically, these constructs simultaneously exploit distinct fluid phenomena, including separated vortex rings from features that resemble those of dandelion seeds and the leading-edge vortices derived from behaviors of maple seeds. Advanced experimental measurements and computational simulations of the aerodynamics and induced flow physics of these hybrid fliers establish a concise, scalable analytical framework for understanding their flight mechanisms. Demonstrations with functional payloads in various forms, including bioresorbable, colorimetric, gas-sensing, and light-emitting platforms, illustrate examples with diverse capabilities in sensing and tracking.

High figure-of-merit for ZnO nanostructures by interfacing lowly-oxidized graphene quantum dots.

Thermoelectric technology has potential for converting waste heat into electricity. Although traditional thermoelectric materials exhibit extremely high thermoelectric performances, their scarcity and toxicity limit their applications. Zinc oxide (ZnO) emerges as a promising alternative owing to its high thermal stability and relatively high Seebeck coefficient, while also being earth-abundant and nontoxic. However, its high thermal conductivity (>40 W m-1K-1) remains a challenge. In this study, we use a multi-step strategy to achieve a significantly high dimensionless figure-of-merit (zT) value of approximately 0.486 at 580 K (estimated value) by interfacing graphene quantum dots with 3D nanostructured ZnO. Here, we show the fabrication of graphene quantum dots interfaced 3D ZnO, yielding the highest zT value ever reported for ZnO counterparts; specifically, our experimental results indicate that the fabricated 3D GQD@ZnO exhibited a significantly low thermal conductivity of 0.785 W m-1K-1 (estimated value) and a remarkably high Seebeck coefficient of - 556 µV K-1 at 580 K.

Rational design of hybrid sensor arrays combined synergistically with machine learning for rapid response to a hazardous gas leak environment in chemical plants.

Combinations of semiconductor metal oxide (SMO) sensors, electrochemical (EC) sensors, and photoionization detection (PID) sensors were used to discriminate chemical hazards on the basis of machine learning. Sensing data inputs were exploited in the form of either numerical or image data formats, and the classification of chemical hazards with high accuracy was achieved in both cases. Even a small amount of gas sensing or purging data (input for ∼30 s) input can be exploited in machine-learning-based gas discrimination. SMO sensors exhibit high performance even in a single-sensor mode, presumably because of the intrinsic cross-sensitivity of metal oxides, which is otherwise considered a major disadvantage of SMO sensors. EC sensors were enhanced through synergistic integration of sensor combinations with machine learning. For precision detection of multiple target analytes, a minimum number of sensors can be proposed for gas detection/discrimination by combining sensors with dissimilar operating principles. The Type I hybrid sensor combines one SMO sensor, one EC sensor, and one PID sensor and is used to identify NH3 gas mixed with sulfur compounds in simulations of NH3 gas leak accidents in chemical plants. The portable remote sensing module made with a Type I hybrid sensor and LTE module can identify mixed NH3 gas with a detection time of 60 s, demonstrating the potential of the proposed system to quickly respond to hazardous gas leak accidents and prevent additional damage to the environment.

Investigation of Laser-Induced Graphene (LIG) on a Flexible Substrate and Its Functionalization by Metal Doping for Gas-Sensing Applications.

Graphene materials synthesized using direct laser writing (laser-induced graphene; LIG) make favorable sensor materials because of their large surface area, ease of fabrication, and cost-effectiveness. In particular, LIG decorated with metal nanoparticles (NPs) has been used in various sensors, including chemical sensors and electronic and electrochemical biosensors. However, the effect of metal decoration on LIG sensors remains controversial; hypotheses based on computational simulations do not always match the experimental results, and even the experimental results reported by different researchers have not been consistent. In the present study, we explored the effects of metal decorations on LIG gas sensors, with NO2 and NH3 gases as the representative oxidizing and reducing agents, respectively. To eliminate the unwanted side effects arising from metal salt residues, metal NPs were directly deposited via vacuum evaporation. Although the gas sensitivities of the sensors deteriorate upon metal decoration irrespective of the metal work function, in the case of NO2 gas, they improve upon metal decoration in the case of NH3 exposure. A careful investigation of the chemical structure and morphology of the metal NPs in the LIG sensors shows that the spontaneous oxidation of metal NPs with a low work function changes the behavior of the LIG gas sensors and that the sensors' behaviors under NO2 and NH3 gases follow different principles.

Unusual Raman Enhancement Effect of Ultrathin Copper Sulfide.

In surface-enhanced Raman spectroscopy (SERS), 2D materials are explored as substrates owing to their chemical stability and reproducibility. However, they exhibit lower enhancement factors (EFs) compared to noble metal-based SERS substrates. This study demonstrates the application of ultrathin covellite copper sulfide (CuS) as a cost-effective SERS substrate with a high EF value of 7.2 × 104 . The CuS substrate is readily synthesized by sulfurizing a Cu thin film at room temperature, exhibiting a Raman signal enhancement comparable to that of an Au noble metal substrate of similar thickness. Furthermore, computational simulations using the density functional theory are employed and time-resolved photoluminescence measurements are performed to investigate the enhancement mechanisms. The results indicate that polar covalent bonds (Cu─S) and strong interlayer interactions in the ultrathin CuS substrate increase the probability of charge transfer between the analyte molecules and the CuS surface, thereby producing enhanced SERS signals. The CuS SERS substrate demonstrates the selective detection of various dye molecules, including rhodamine 6G, methylene blue, and safranine O. Furthermore, the simplicity of CuS synthesis facilitates large-scale production of SERS substrates with high spatial uniformity, exhibiting a signal variation of less than 5% on a 4-inch wafer.

Enhanced Thermal Pad Composites Using Densely Aligned MgO Nanowires.

Owing to the increasing demand for the miniaturization and integration of electronic devices, thermal interface materials (TIMs) are crucial components for removing heat and improving the lifetime and safety of electronic devices. Among these, thermal pads are reusable alternatives to thermal paste-type TIMs; however, conventional thermal pads comprise a homogeneous polymer with low thermal conductivity. Composite materials of thermally conducting fillers and polymer matrices are considered suitable alternatives to high-performance pad materials owing to their controllable thermal properties. However, they degrade the thermal performance of the filler materials at high loading ratios via aggregation. In this study, we propose novel nanocomposites using densely aligned MgO nanowire fillers and polydimethylsiloxane (PDMS) matrices. The developed nanocomposites ensured the enhanced thermal conducting properties, while maintaining mechanical flexibility. The three-step preparation process involves the (i) fabrication of the MgO structure using a freeze dryer; (ii) compression of the MgO structure; and (iii) the infiltration of PDMS in the structure. The resulting aligned composites exhibited a superior thermal conductivity (approximately 1.18 W m-1K-1) to that of pure PDMS and composites with the same filler ratios of randomly distributed MgO fillers. Additionally, the MgO/PDMS composites exhibited adequate electrical insulating properties, with a room-temperature resistivity of 7.92 × 1015 Ω∙cm.

Ultrathin Metal Film on Graphene for Percolation-Threshold-Limited Thermal Emissivity Control.

Translucent Au/graphene hybrid films are shown to be effective in reducing thermal emission from the underlying surfaces when the deposition thickness of Au is close to the percolation threshold. The critical Au deposition thickness for an abrupt change in emissivity is reduced from 15 nm (Si substrate) to a percolation-threshold-limited thickness of 8.5 nm (graphene/Si substrate) because of the chemical inertness of graphene leading to the deposited Au atoms forming a thin, crystalline layer. The effect of the graphene layer on the optical properties of the hybrid film is highlighted by a drastic increase in infrared absorptivity, whereas the visible absorptivity is marginally affected by the presence of a graphene layer. The level of thermal emission from the Au/graphene hybrid films with the percolation-threshold-limited Au thickness is stable even with high background temperatures of up to 300 °C and mechanical strains of ≈4%. As an example of a thermal management application, an anti-counterfeiting device is demonstrated; thermal-camouflage-masked text fabricated with an Au/graphene hybrid film is discernible only using a thermographic camera. Ultrathin metal film assisted by a graphene layer will provide a facile platform for thermal management with semi-transparency, flexibility, and transferability to arbitrary surfaces.

Role of graphene quantum dots with discrete band gaps on SnO2 nanodomes for NO2 gas sensors with an ultralow detection limit.

NO2 is a major air pollutant that should be monitored due to its harmful effects on the environment and human health. Semiconducting metal oxide-based gas sensors have been widely explored owing to their superior sensitivity towards NO2, but their high operating temperature (>200 °C) and low selectivity still limit their practical use in sensor devices. In this study, we decorated graphene quantum dots (GQDs) with discrete band gaps onto tin oxide nanodomes (GQD@SnO2 nanodomes), enabling room temperature (RT) sensing towards 5 ppm NO2 gas with a noticeable response ((Ra/Rg) - 1 = 4.8), which cannot be matched using pristine SnO2 nanodomes. In addition, the GQD@SnO2 nanodome based gas sensor shows an extremely low detection limit of 1.1 ppb and high selectivity compared to other pollutant gases (H2S, CO, C7H8, NH3, and CH3COCH3). The oxygen functional groups in GQDs specifically enhance NO2 accessibility by increasing the adsorption energy. Strong electron transfer from SnO2 to GQDs widens the electron depletion layer at SnO2, thereby improving the gas response over a broad temperature range (RT-150 °C). This result provides a basic perspective for utilizing zero-dimensional GQDs in high-performance gas sensors operating over a wide range of temperatures.

Responsive materials and mechanisms as thermal safety systems for skin-interfaced electronic devices.

Soft, wireless physiological sensors that gently adhere to the skin are capable of continuous clinical-grade health monitoring in hospital and/or home settings, of particular value to critically ill infants and other vulnerable patients, but they present risks for injury upon thermal failure. This paper introduces an active materials approach that automatically minimizes such risks, to complement traditional schemes that rely on integrated sensors and electronic control circuits. The strategy exploits thin, flexible bladders that contain small volumes of liquid with boiling points a few degrees above body temperature. When the heat exceeds the safe range, vaporization rapidly forms highly effective, thermally insulating structures and delaminates the device from the skin, thereby eliminating any danger to the skin. Experimental and computational thermomechanical studies and demonstrations in a skin-interfaced mechano-acoustic sensor illustrate the effectiveness of this simple thermal safety system and suggest its applicability to nearly any class of skin-integrated device technology.

Ultrasensitive biosensing platform for Mycobacterium tuberculosis detection based on functionalized graphene devices.

Tuberculosis (TB) has high morbidity as a chronic infectious disease transmitted mainly through the respiratory tract. However, the conventional diagnosis methods for TB are time-consuming and require specialists, making the diagnosis of TB with point-of-care (POC) detection difficult. Here, we developed a graphene-based field-effect transistor (GFET) biosensor for detecting the MPT64 protein of Mycobacterium tuberculosis with high sensitivity as a POC detection platform for TB. For effective conjugation of antibodies, the graphene channels of the GFET were functionalized by immobilizing 1,5-diaminonaphthalene (1,5-DAN) and glutaraldehyde linker molecules onto the graphene surface. The successful immobilization of linker molecules with spatial uniformity on the graphene surface and subsequent antibody conjugation were confirmed by Raman spectroscopy and X-ray photoelectron spectroscopy. The GFET functionalized with MPT64 antibodies showed MPT64 detection with a detection limit of 1 fg/mL in real-time, indicating that the GFET biosensor is highly sensitive. Compared to rapid detection tests (RDT) and enzyme-linked immunosorbent assays, the GFET biosensor platform developed in this study showed much higher sensitivity but much smaller dynamic range. Due to its high sensitivity, the GFET biosensor platform can bridge the gap between time-consuming molecular diagnostics and low-sensitivity RDT, potentially aiding in early detection or management of relapses in infectious diseases.

Multifunctional-high resolution imaging plate based on hydrophilic graphene for digital pathology.

In the present study, we showed that hydrophilic graphene can serve as an ideal imaging plate for biological specimens. Graphene being a single-atom-thick semi-metal with low secondary electron emission, array tomography analysis of serial sections of biological specimens on a graphene substrate showed excellent image quality with improvedz-axis resolution, without including any conductive surface coatings. However, the hydrophobic nature of graphene makes the placement of biological specimens difficult; graphene functionalized with polydimethylsiloxane oligomer was fabricated using a simple soft lithography technique and then processed with oxygen plasma to provide hydrophilic graphene with minimal damage to graphene. High-quality scanning electron microscopy images of biological specimens free from charging effects or distortion were obtained, and the optical transparency of graphene enabled fluorescence imaging of the specimen; high-resolution correlated electron and light microscopy analysis of the specimen became possible with the hydrophilic graphene plate.

Thermally switchable, crystallizable oil and silicone composite adhesives for skin-interfaced wearable devices.

Continuous health monitoring is essential for clinical care, especially for patients in neonatal and pediatric intensive care units. Monitoring currently requires wired biosensors affixed to the skin with strong adhesives that can cause irritation and iatrogenic injuries during removal. Emerging wireless alternatives are attractive, but requirements for skin adhesives remain. Here, we present a materials strategy enabling wirelessly triggered reductions in adhesive strength to eliminate the possibility for injury during removal. The materials involve silicone composites loaded with crystallizable oils with melting temperatures close to, but above, surface body temperature. This solid/liquid phase transition occurs upon heating, reducing the adhesion at the skin interface by more than 75%. Experimental and computational studies reveal insights into effects of oil mixed randomly and patterned deterministically into the composite. Demonstrations in skin-integrated sensors that include wirelessly controlled heating and adhesion reduction illustrate the broad utility of these ideas in clinical-grade health monitoring.

Photolithographic realization of target nanostructures in 3D space by inverse design of phase modulation.

The mass production of precise three-dimensional (3D) nanopatterns has long been the ultimate goal of fabrication technology. While interference lithography and proximity-field nanopatterning (PnP) may provide partial solutions, their setup complexity and limited range of realizable structures, respectively, remain the main problems. Here, we tackle these challenges by applying an inverse design to the PnP process. Our inverse design platform based on the adjoint method can efficiently find optimal phase masks for diverse target lattices and motifs. We fabricate a 2D rectangular array of nanochannels, which has not been reported for conventional PnP with normally incident light, as a proof of concept. With further demonstration of material conversion, our work provides versatile platforms for nanomaterial fabrication.

A Skin-Interfaced, Miniaturized Microfluidic Analysis and Delivery System for Colorimetric Measurements of Nutrients in Sweat and Supply of Vitamins Through the Skin.

Nutrients play critical roles in maintaining core physiological functions and in preventing diseases. Technologies for delivering these nutrients and for monitoring their concentrations can help to ensure proper nutritional balance. Eccrine sweat is a potentially attractive class of biofluid for monitoring purposes due to the ability to capture sweat easily and noninvasively from nearly any region of the body using skin-integrated microfluidic technologies. Here, a miniaturized system of this type is presented that allows simple, rapid colorimetric assessments of the concentrations of multiple essential nutrients in sweat, simultaneously and without any supporting electronics - vitamin C, calcium, zinc, and iron. A transdermal patch integrated directly with the microfluidics supports passive, sustained delivery of these species to the body throughout a period of wear. Comparisons of measurement results to those from traditional lab analysis methods demonstrate the accuracy and reliability of this platform. On-body tests with human subjects reveal correlations between the time dynamics of concentrations of these nutrients in sweat and those of the corresponding concentrations in blood. Studies conducted before and after consuming certain foods and beverages highlight practical capabilities in monitoring nutritional balance, with strong potential to serve as a basis for guiding personalized dietary choices.

Interdigitated Three-Dimensional Heterogeneous Nanocomposites for High-Performance Mechanochromic Smart Membranes.

Mechanochromic smart membranes capable of optical modulation have great potential in smart windows, artificial skins, and camouflage. However, the realization of high-contrast optical modulation based on light scattering activated at a low strain remains challenging. Here, we present a strategy for designing mechanochromic scattering membranes by introducing a Young's modulus mismatch between the two interdigitated polydimethylsiloxane phases with weak interfaces in a periodic three-dimensional (3D) structure. The refractive index-matched interfaces of the nanocomposite provide a high optical transparency of 93%. Experimental and computational studies reveal that the 3D heterogeneity facilitates the generation of numerous nanoscale debonds or "nanogaps" at the modulus-mismatching interfaces, enabling incident light scattering under tension. The heterogeneous scatterer delivers both a high transmittance contrast of >50% achieved at 15% strain and a maximum contrast of 82%. When used as a smart window, the membrane demonstrates effective diffusion of transmitting sunlight, leading to moderate indoor illumination by eliminating extremely bright or dark spots. At the other extreme, such a 3D heterogeneous design with strongly bonded interfaces can enhance the coloration sensitivity of mechanophore-dyed nanocomposites. This work presents insights into the design principles of advanced mechanochromic smart membranes.

Rationally Designed TiO2 Nanostructures of Continuous Pore Network for Fast-Responding and Highly Sensitive Acetone Sensor.

For the last several years, indoor air quality monitoring has been a significant issue due to the increasing time portion of indoor human activities. Especially, the early detection of volatile organic compounds potentially harmful to the human body by the prolonged exposure is the primary concern for public human health, and such technology is imperatively desired. In this study, highly porous and periodic 3D TiO2 nanostructures are designed and studied for this concern. Specifically, extremely high gas molecule accessibility throughout the whole nanostructures and precisely controlled internecks of 3D TiO2 nanostructures can achieve an unprecedented gas response of 299 to 50 ppm CH3 COCH3 with an extremely fast response time of less than 1s. The systematic approach to utilize the whole inner and outer surfaces of the gas sensing materials and periodically formed internecks to localize the current paths in this study can provide highly promising perspectives to advance the development of chemoresistive gas sensors using metal oxide nanostructures for the Internet of Everything application.

Bitter Flavored, Soft Composites for Wearables Designed to Reduce Risks of Choking in Infants.

Wireless, skin-integrated devices for continuous, clinical-quality monitoring of vital signs have the potential to greatly improve the care of patients in neonatal and pediatric intensive-care units. These same technologies can also be used in the home, across a broad spectrum of ages, from beginning to end of life. Although miniaturized forms of such devices minimize patient burden and improve compliance, they represent life-threatening choking hazards for infants. A materials strategy is presented here to address this concern. Specifically, composite materials are introduced as soft encapsulating layers and gentle adhesives that release chemical compounds designed to elicit an intense bitter taste when placed in the mouth. Reflexive reactions to this sensation strongly reduce the potential for ingestion, as a safety feature. The materials systems described involve a non-toxic bitterant (denatonium benzoate) as a dopant in an elastomeric (poly(dimethylsiloxane)) or hydrogel matrix. Experimental and computational studies of these composite materials and the kinetics of release of the bitterant define the key properties. Incorporation into various wireless skin-integrated sensors demonstrates their utility in functional systems. This simple strategy offers valuable protective capabilities, with broad practical relevance to the welfare of children monitored with wearable devices.

Optically Activated 3D Thin-Shell TiO2 for Super-Sensitive Chemoresistive Responses: Toward Visible Light Activation.

One of the well-known strategies for achieving high-performance light-activated gas sensors is to design a nanostructure for effective surface responses with its geometric advances. However, no study has gone beyond the benefits of the large surface area and provided fundamental strategies to offer a rational structure for increasing their optical and chemical performances. Here, a new class of UV-activated sensing nanoarchitecture made of highly periodic 3D TiO2, which facilitates 55 times enhanced light absorption by confining the incident light in the nanostructure, is prepared as an active gas channel. The key parameters, such as the total 3D TiO2 film and thin-shell thicknesses, are precisely optimized by finite element analysis. Collectively, this fundamental design leads to ultrahigh chemoresistive response to NO2 with a theoretical detection limit of ≈200 ppt. The demonstration of high responses with visible light illumination proposes a future perspective for light-activated gas sensors based on semiconducting oxides.