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Achieving high signal-to-noise ratio in chemical and biological sensors enables accurate detection of target analytes. Unfortunately, below the limit of detection (LOD), it becomes difficult to detect the presence of small amounts of analytes and extract useful information via any of the conventional methods. In this work, we examine the possibility of extracting "hidden signals" using deep neural network to enhance gas sensing below the LOD region. As a test case system, we conduct experiments for H2 sensing in six different metallic channels (Au, Cu, Mo, Ni, Pt, Pd) and demonstrate that deep neural network can enhance the sensing capabilities for H2 concentration below the LOD. We demonstrate that this technique could be universally used for different types of sensors and target analytes. Our approach can extract new information from the hidden signals, which can be crucial for next-generation chemical sensing applications and analytical chemistry.

Unzipping carbon nanotubes (CNTs) may offer a valuable route to synthesize graphene nanoribbon (GNR) structures with semiconducting properties. Unfortunately, currently available unzipping methods commonly rely on a random harsh chemical reaction and thereby cause significant degradation of the crystalline structure and electrical properties of GNRs. Herein, crystalline semiconducting GNRs are achieved by a synergistic, judiciously designed two-step unzipping method for N-doped CNTs (NCNTs). NCNTs are effectively unzipped by damage-minimized, dopant-specific electrochemical unzipping and subsequent sonochemical treatment into long ribbon-like nanostructures with crystalline basal planes. Owing to the nanoscale dimension originating from the dense nucleation of the unzipping reaction at highly NCNTs, the resultant GNRs demonstrate semiconducting properties, which can be exploited for chemiresistor-type gas-sensing devices and many other applications.

Gas molecules are known to interact with two-dimensional (2D) materials through surface adsorption where the adsorption-induced charge transfer governs the chemiresistive sensing of various gases. Recently, titanium carbide (Ti

The fabrication of p-n heterostructures of a metal oxide semiconductor (MOS) showed that a large amount of heterojunction interfaces is one of the key issues in MOS gas sensor research, since it could significantly enhance the sensing performance. Despite considerable progress in this area, fabrication of an ideal p-n heterojunction sensing channel has been challenging because of morphological limitations of synthetic methods in the conventional bottom-up fabrication based on precursor reductions. In this study, a 10 nm scale p-n heterojunction nanochannel was fabricated with ultrasmall grained WO3/CuO nanopatterns in a large area (centimeter scale) through unique one-step top-down lithographic approaches. The fabricated p-n heterostructure nanochannel showed ultrathinness (20 nm thickness) and high aspect ratio (>10) and consisted of highly dispersed p-type dopants and n-type channel materials. This facile heterojunction nanostructure could induce a high degree of extended depletion layer and efficient catalytic properties within its single-nanochannel surfaces. Accordingly, the WO3/CuO nanochannel exhibited ultrasensitive detection performance toward ethanol (C2H5OH) ( Ra/ Rg = 224 at100 ppb), 12 times higher than that of a pristine WO3 nanochannel. The limit of detection of the sensors was calculated to be below parts per billion levels (0.094 ppb) with significant response amplitudes ( Ra/ Rg = 75), which is the best ethanol-sensing performance among previously reported MOS-based sensors. Our unique lithographic approach for the p-n heterojunction nanochannel is expected to be universally applicable to various heteronanostructures such as the n-n junction, p-p junction, and metal-semiconductor junction without combinatorial limitations.

Two-dimensional (2D) transition metal carbides (MXenes) exhibit outstanding performances in many applications, such as energy storage, optoelectronics, and electrocatalysts. However, colloidal solutions of Ti3C2Tx MXene flakes deteriorate rapidly under ambient conditions due to the conversion of the titanium carbide to titanium dioxide. Here, we discuss the dominant factors influencing the rate of oxidation of Ti3C2Tx MXene flakes, and present guidelines for their storage with the aim of maintaining the intrinsic properties of the as-prepared material. The oxidation stability of the Ti3C2Tx flakes is dramatically improved in a system where water molecules and temperature were well-controlled. It was found that aqueous solutions of Ti3C2Tx MXene can be chemically stable for more than 39 weeks when the storage temperature (−80 °C) is sufficiently low to cease the oxidation processes. It was also found that if the Ti3C2Tx flakes are dispersed in ethanol, the degradation process can be significantly delayed even at 5 °C. Moreover, the oxidation stability of the Ti3C2Tx flakes is dramatically improved in both cases, even in the presence of oxygen-containing atmosphere. We demonstrate practical applications of our approach by employing Ti3C2Tx in a gas sensor showing that when oxidation is inhibited, the device can retain the original electrical properties after 5 weeks of storage.

The chili pepper (Capsicum annuum L.) is a food source that is rich in flavonoids such as luteolin and apigenin. Flavonoids are known to have anti-inflammatory and antioxidant activities, however, studies on the flavonoids composition identified and the anti-inflammatory and antioxidant effects in pepper leaves (PL) and fruits (PF) are insufficient. In the present study, we investigated the antioxidant and anti-inflammatory effects in vitro, and the flavonoids contents of the PL and PF. Pepper extracts showed radical scavenging activities and ameliorated the lipopolysaccharide (LPS)-stimulated inflammatory response by decreasing nitric oxide production and interluekin-6 and tumor necrosis factor alpha levels in RAW 264.7 cells, with more effective activities noted for PL than for PF. Furthermore, PL extracts markedly inhibited the LPS-induced production of reactive oxygen species accumulation. The flavonoid profile and content of pepper were dependent on the part, with PL showing higher total flavonoids than PF. In particular, the content of luteolin glycosides in PL was twice that in PF. Thus, PL may be useful to prevent oxidative stress and inflammation-related diseases.

Fluorescent nanosensors hold promise to address analytical challenges in the biopharmaceutical industry. The monitoring of therapeutic protein critical quality attributes such as aggregation is a long-standing challenge requiring low detection limits and multiplexing of different product parameters. However, general approaches for interfacing nanosensors to the biopharmaceutical process remain minimally explored to date. Herein, we design and fabricate a integrated fiber optic nanosensor element, measuring sensitivity, response time, and stability for applications to the rapid process monitoring. The fiber optic-nanosensor interface, or optode, consists of label-free nIR fluorescent single-walled carbon nanotube transducers embedded within a protective yet porous hydrogel attached to the end of the fiber waveguide. The optode platform is shown to be capable of differentiating the aggregation status of human immunoglobulin G, reporting the relative fraction of monomers and dimer aggregates with sizes 5.6 and 9.6 nm, respectively, in under 5 min of analysis time. We introduce a lab-on-fiber design with potential for at-line monitoring with integration of 3D-printed miniaturized sensor tips having high mechanical flexibility. A parallel measurement of fluctuations in laser excitation allows for intensity normalization and significantly lower noise level (3.7 times improved) when using lower quality lasers, improving the cost effectiveness of the platform. As an application, we demonstrate the capability of the fully integrated lab-on-fiber system to rapidly monitor various bioanalytes including serotonin, norepinephrine, adrenaline, and hydrogen peroxide, in addition to proteins and their aggregation states. These results in total constitute an effective form factor for nanosensor-based transducers for applications in industrial process monitoring.

Precise control of the size and interfaces of Pd grains is very important for designing a high-performance H2 sensing channel because the transition of the Pd phase from α to β occurs through units of single grains. However, unfortunately, the grain controllability of previous approaches has been limited to grains exceeding 10 nm in size and simple macroscopic channel structures have only shown monotonic response behavior for a wide concentration range of H2. In this work, for the first time, we found that Pd channels that are precisely grain-controlled show very different H2 sensing behavior. They display dual-switching response behavior with simultaneous variation of the positive and negative response direction within single sensor. The Pd nanopattern channel having smallest grain size/interface among previous works could be fabricated via unique lithographic approaches involving low-energy plasma (Ar+) bombardment. The ultrasmall grain size (5 nm) and narrow interface gap (

Strong acidic gases such as CO2, SO2, and NO2 are harsh air pollutants with major human health threatening factors, and as such, developing new tools to monitor and to quickly sense these gases is critically required. However, it is difficult to selectively detect the acidic air pollutants with single channel material due to the similar chemistry shared by acidic molecules. In this work, three acidic gases (i.e., CO2, SO2, and NO2) are selectively discriminated using single channel material with precise moiety design. By changing the composition ratio of primary (1°), secondary (2°), and tertiary (3°) amines of polyethylenimine (PEI) on CNT channels, unprecedented high selectivity between CO2 and SO2 is achieved. Using in situ FT-IR characterizations, the distinct adsorption phenomenon of acidic gases on each amine moiety is precisely demonstrated. Our approach is the first attempt at controlling gas adsorption selectivity of solid-state sensor via modulating chemical moiety level within the single channe...

Achieving high sensitivity in solid-state gas sensors can allow the precise detection of chemical agents. In particular, detection of volatile organic compounds (VOCs) at the parts per billion (ppb) level is critical for the early diagnosis of diseases. To obtain high sensitivity, two requirements need to be simultaneously satisfied: (i) low electrical noise and (ii) strong signal, which existing sensor materials cannot meet. Here, we demonstrate that 2D metal carbide MXenes, which possess high metallic conductivity for low noise and a fully functionalized surface for a strong signal, greatly outperform the sensitivity of conventional semiconductor channel materials. Ti3C2Tx MXene gas sensors exhibited a very low limit of detection of 50–100 ppb for VOC gases at room temperature. Also, the extremely low noise led to a signal-to-noise ratio 2 orders of magnitude higher than that of other 2D materials, surpassing the best sensors known. Our results provide insight in utilizing highly functionalized metallic...

Herein, we present a demonstration of the usability of the chemical sensing properties of transition metal carbides (TMCs) as gas sensing channels. Two phases of nanostructured molybdenum carbide (α-MoC1−x and β-Mo2C) with high porosities were perfectly synthesized by a temperature-programmed reduction (TPR) method, and they showed distinct metallic characteristics due to different density of states (DOS) localization status. The molybdenum carbide sensors showed novel gas sensing characteristics which have not been shown by previous typical sensing materials: predominantly, an unprecedentedly high signal-to-noise ratio (SNR) with the ability to detect the ppb levels of NH3 and NO2 was achieved, which is attributed to a combination of high electrical conductivity and superior catalytic properties. In addition to high sensitivity, unlike previous channel materials, the molybdenum carbide sensors showed very high ambient stability. The electrical conductivity and sensing performance are well preserved for half-year ambient exposure without any oxidation or degradation of channel materials, due to the good corrosion resistance and low chemical reactivity of molybdenum carbides. In addition, a versatile gas sensing response is observed according to the crystal phase of molybdenum carbides due to the distinct DOS of α-MoC1−x and β-Mo2C. We believe that this observation of new chemical sensing materials can shed light on the superior potential of TMCs for highly sensitive and stable low-power operating internet-of-things (IoT) sensors. In addition, owing to their ultra-high chemical stability and high melting temperature, TMCs can be utilized as channel materials for sensors in harsh operating conditions.

In this work, the effects of noble metal (Au and Pt) incorporation into black phosphorus (BP) were first investigated. Several important sensing results were observed as a result of the incorporation of Au or Pt into the BP surface. First, prior to incorporation, pristine BP only detects paramagnetic molecules, e.g., NO2 or NO. However, after incorporation with Pt, low concentration of H2 can be detected with high response amplitude. Furthermore, the H2 sensing performance reported in this study was found to be most sensitive as compared with that observed for a previously reported 2D H2 gas sensor. The second significant result was obtained after incorporation with Au, where the work function of BP was varied by the transfer of electrons from the Au nanoparticles, thereby inducing the effects of n-doping on p-type pristine BP. Accordingly, the response behavior of BP to oxidizing gas changed from a p-type response (negative resistance variation) to an n-type response (positive resistance variation). In a...

Controlling the charge concentrations of two-dimensional (2D) materials is a critical requirement for realizing versatility and potential application of these materials in high-performance electronics and sensors. In order to exploit the novel chemical-sensing characteristics of 2D materials for sensitive and selective sensors, various functionalization methods are needed to ensure efficient doping of channels based on 2D materials. In the present study, the gas-sensing performance of MoS2 has been significantly enhanced by controlled Au nanoparticle functionalization. By using the difference in reduction potential between the Au precursor and MoS2 work functions, MoS2 prepared by chemical exfoliation process was decorated with nanoparticles with sizes of tens of nanometers. The n-doping effect of Au nanoparticles was observed, that is, these particles were found to have facilitated in electron charge transfer from Au to MoS2. The controlled n-doping effect enables the tuning of the sensing of hydrocarbon...

Weavable sensing fibers with superior mechanical strength and sensing functionality are crucial for the realization of wearable textile sensors. However, in the fabrication of previously reported wearable sensing fibers, additional processes such as reduction, doping, and coating were essential to satisfy both requirements. The sensing fibers should be continuously synthesized in a scalable process for commercial applications with high reliability and productivity, which was challenging. In this study, we first synthesize mass-producible wearable sensing fibers with good mechanical properties and sensing functionality without additional processes by incorporating carbon nanotubes (CNTs) into distinct nanocellulose. Nanocellulose extracted from tunicate (TCNF) is homogeneously composited with single-walled CNTs, and composite fibers (TCNF/CNT) are continuously produced in aligned directions by wet spinning, facilitating liquid-crystal properties. The TCNF/CNT fibers exhibit a superior gas (NO2)-sensing performance with high selectivity and sensitivity (parts-per-billion detection). In addition, the TCNF/CNT fibers can endure complex and harsh distortions maintaining their intrinsic sensing properties and can be perfectly integrated with conventional fabrics using a direct weaving process. Our meter-scale scalable synthesis of functional composite fibers is expected to provide a mass production platform of versatile wearable sensors.

As neural stem cells (NSCs) interact with biophysical cues from their niche during development, it is important to understand the biomolecular mechanism of how the NSCs process these biophysical cues to regulate their behaviors. In particular, anisotropic geometric cues in micro-/nanoscale have been utilized to investigate the biophysical effect of the structure on NSCs behaviors. Here, a series of new nanoscale anisotropic wrinkle structures with the a range of wavelength scales (from 50 nm to 37 μm) was developed to demonstrate the effect of the anisotropic nanostructure on the fate commitment of NSCs. Intriguingly, two distinct characteristic length scales promoted the neurogenesis. Each wavelength scale showed a striking variation in terms of dependency on the directionality of the structures, suggesting the existence of at least two different ways in the processing of anisotropic geometries for neurogenesis. Furthermore, the combined effect of the two distinctive length scales was observed by employing hierarchical multiscale wrinkle structures with two characteristic neurogenesis-promoting wavelengths. Taken together, the wrinkle structure system developed in this study can serve as an effective platform to advance the understanding of how cells sense anisotropic geometries for their specific cellular behaviors. Furthermore, this could provide clues for improving nerve regeneration system of stem cell therapies.

In this study, a novel buckled structure of edge-oriented MoS2 films is fabricated for the first time by employing monolayer graphene as the substrate for MoS2 film growth. Compared to typical buckling methods, our technique has several advantages: (1) external forces such as heat and mechanical strain are not applied; (2) uniform and controllable buckling over a large area is possible; and (3) films are able to be transferred to a desired substrate. Dual MoS2 orientation was observed in the buckled film where horizontally aligned MoS2 layers of 7 nm thickness were present near the bottom graphene surface and vertically aligned layers dominated the film toward the outer surface, in which the alignment structure was uniform across the entire film. The catalytic ability of the buckled MoS2 films, measured by performing water-splitting tests in acidic environments, shows a reduced onset potential of -0.2 V versus reversible hydrogen electrode (RHE) compared to -0.32 V versus RHE for pristine MoS2, indicating that the rough surface provided a higher catalytic activity. Our work presents a new method to generate a buckled MoS2 structure, which may be extended to the formation of buckled structures in various 2D materials for future applications.

The development of a simple and cost-effective method for fabricating ≈10 nm scale nanopatterns over large areas is an important issue, owing to the performance enhancement such patterning brings to various applications including sensors, semiconductors, and flexible transparent electrodes. Although nanoimprinting, extreme ultraviolet, electron beams, and scanning probe litho-graphy are candidates for developing such nanopatterns, they are limited to complicated procedures with low throughput and high startup cost, which are difficult to use in various academic and industry fields. Recently, several easy and cost-effective lithographic approaches have been reported to produce ≈10 nm scale patterns without defects over large areas. This includes a method of reducing the size using the narrow edge of a pattern, which has been attracting attention for the past several decades. More recently, secondary sputtering lithography using an ion-bombardment technique was reported as a new method to create high-resolution and high-aspect-ratio structures. Recent progress in simple and cost-effective top-down lithography for ≈10 nm scale nanopatterns via edge and secondary sputtering techniques is reviewed. The principles, technical advances, and applications are demonstrated. Finally, the future direction of edge and secondary sputtering lithography research toward issues to be resolved to broaden applications is discussed.

With growing focus on the use of carbon nanomaterials in chemical sensors, one-dimensional graphene nanoribbon (GNR) has become one of the most attractive channel materials, owing to its enhanced conductance fluctuation by quantum confinement effects and dense, abundant edge sites. Due to the narrow width of a basal plane with one-dimensional morphology, chemical modification of edge sites would greatly affect the electrical channel properties of a GNR. Here, we demonstrate for the first time that chemically functionalizing the edge sites with aminopropylsilane (APS) molecules can significantly enhance the sensing performance of the GNR sensor. The resulting APS-functionalized GNR has a sensitivity ((Δ R/ R

The development of high-performance volatile organic compound (VOC) sensor based on a p-type metal oxide semiconductor (MOS) is one of the important topics in gas sensor research because of its unique sensing characteristics, namely, rapid recovery kinetics, low temperature dependence, high humidity or thermal stability, and high potential for p-n junction applications. Despite intensive efforts made in this area, the applications of such sensors are hindered because of drawbacks related to the low sensitivity and slow response or long recovery time of p-type MOSs. In this study, the VOC sensing performance of a p-type MOS was significantly enhanced by forming a patterned p-type polycrystalline MOS with an ultrathin, high-aspect-ratio (∼25) structure (∼14 nm thickness) composed of ultrasmall grains (∼5 nm size). A high-resolution polycrystalline p-type MOS nanowire array with a grain size of ∼5 nm was fabricated by secondary sputtering via Ar(+) bombardment. Various p-type nanowire arrays of CuO, NiO, and Cr2O3 were easily fabricated by simply changing the sputtering material. The VOC sensor thus fabricated exhibited higher sensitivity (ΔR/Ra = 30 at 1 ppm hexane using NiO channels), as well as faster response or shorter recovery time (∼30 s) than that of previously reported p-type MOS sensors. This result is attributed to the high resolution and small grain size of p-type MOSs, which lead to overlap of fully charged zones; as a result, electrical properties are predominantly determined by surface states. Our new approach may be used as a route for producing high-resolution MOSs with particle sizes of ∼5 nm within a highly ordered, tall nanowire array structure.

Recently, high-resolution patterned metal oxide semiconductors (MOS) have gained considerable attention for enhanced gas sensing performance due to their polycrystalline nature, ultrasmall grain size (~5 nm), patternable properties, and high surface-to-volume ratio. Herein, we significantly enhanced the sensing performance of that patterned MOS by galvanic replacement, which allows for selective functionalization on ultrathin Cu2O nanopatterns. Based on the reduction potential energy difference between the base channel material (Cu2O) and the decorated metal ion (Pt2+), Pt could be selectively and precisely decorated onto the desired area of the Cu2O nanochannel array. Overall, the Pt-decorated Cu2O exhibited 11-fold higher NO2 (100 ppm) sensing sensitivity as compared to the non-decorated sensing channel, the while the channel device with excessive Pt doping showed complete loss of sensing properties.

The development of complex nanostructures containing a homo- and heteromixture of two or more metals is a considerable challenge in nanotechnology. However, previous approaches are considerably limited to the number of combinations of metals depending on the compatibility of elements, and to the complex shape control of the nanostructure. In this study, a significant step is taken toward resolving these limitations via the utilization of a low-energy argon-ion bombardment. The multilayer films are etched and re-sputtered on the sidewall of the pre-pattern, which is a secondary sputtering phenomenon. In contrast to the precursor mixing method, most metallic combinations can be fabricated. The degree of mixing is tuned by the control of the sequence and thickness of multilayers. In addition, the feature shape and dimensions are controlled by changing the pre-pattern or by controlling the ion-beam angle. Using this method, the shortest response time (2 s to 1% H2 ) in comparison with those of Pd-based H2 sensors reported previously and a limit of detection below 1 parts per million (ppm) for Pd/Au and Pd/Pt bimetallic line arrays are achieved. This study is expected to realize a family of polyelements that can be used in various applications.

Ultrastable sensing characteristics of the ionic chemiresistor skin (ICS) that is designed by using an intrinsically stretchable thermoplastic polyurethane electrolyte as a volatile organic compound (VOC) sensing channel are described. The hierarchically assembled polymer electrolyte film is observed to be very uniform, transparent, and intrinsically stretchable. Systematic experimental and theoretical studies also reveal that artificial ions are evenly distributed in polyurethane matrix without microscale phase separation, which is essential for implementing high reliability of the ICS devices. The ICS displays highly sensitive and stable sensing of representative VOCs (including toluene, hexane, propanal, ethanol, and acetone) that are found in the exhaled breath of lung cancer patients. In particular, the sensor is found to be fully operational even after being subjected to long-term storage or harsh environmental conditions (relative humidity of 85% or temperature of 100 °C) or severe mechanical deformation (bending to a radius of curvature of 1 mm, or stretching strain of 100%), which can be an effective method to realize a human-adaptive and skin-attachable biosensor platform for daily use and early diagnosis.

The development of high resolution, high aspect ratio metal dichalcogenide nanostructures is one of the most important issues in 2D material researchers due to the potential to exploit their properties into high performance devices. In this study, for the first time a way of fabricating metal dichalcogenide nanostructures with high resolution ( 120) by chemical vapor deposition assisted secondary sputtering phenomenon is reported. This approach can universally synthesize various types of metal dichalcogenides including MoS2, WS2, and SnS2, implying the possibility for further utilization with selenides and tellurides. Also, this method can produce highly periodic complex patterns such as hole–cylinder, concentric rings, and line patterns, which are unprecedented in previous reports. The feature size and aspect ratio of the metal dichalcogenide structures can be manipulated by controlling the dimensions of the photoresist prepatterns, while the pattern resolution and layer orientation can be manipulated by controlling the thickness of the deposited metal film. It is demonstrated that nanostructures with high resolution and high aspect ratio significantly improve gas-sensing properties compared with previous metal dichalcogenide films. It is believed that the method can be a foundation for synthesizing various materials with complex patterns for future applications.