High Performance Three‐Dimensional Chemical Sensor Platform Using Reduced Graphene Oxide Formed on High Aspect‐Ratio Micro‐Pillars

The sensing performance of chemical sensors can be achieved not only by modification or hybridization of sensing materials but also through new design in device geometry. The performance of a chemical sensing device can be enhenced from a simple three‐dimensional (3D) chemiresistor‐based gas sensor platform with an increased surface area by forming networked, self‐assembled reduced graphene oxide (R‐GO) nanosheets on 3D SU8 micro‐pillar arrays. The 3D R‐GO sensor is highly responsive to low concentration of ammonia (NH₃) and nitrogen dioxide (NO₂) diluted in dry air at room temperature. Compared to the two‐dimensional planar R‐GO sensor structure, as the result of the increase in sensing area and interaction cross‐section of R‐GO on the same device area, the 3D R‐GO gas sensors show improved sensing performance with faster response (about 2%/s exposure), higher sensitivity, and even a possibly lower limit of detection towards NH₃ at room temperature.     

Flexible Transparent Reduced Graphene Oxide Sensor Coupled with Organic Dye Molecules for Rapid Dual‐Mode Ammonia Gas Detection

Flexible chemical sensors utilizing chemically sensitive nanomaterials are of great interest for wearable sensing applications. However, obtaining high performance flexible chemical sensors with high sensitivity, fast response, transparency, stability, and workability at ambient conditions is still challenging. Herein, a newly designed flexible and transparent chemical sensor of reduced graphene oxide (R‐GO) coupled with organic dye molecules (bromophenol blue) is introduced. This device has promising properties such as high mechanical flexibility (>5000 bending cycles with a bending radius of 0.95 cm) and optical transparency (>60% in the visible region). Furthermore, stacking the water‐trapping dye layer on R‐GO enables a higher response as well as workability in a large relative humidity range (up to 80%), and dual‐mode detection capabilities of colorimetric and electrical sensing for NH₃ gas (5–40 ppm). These advantageous attributes of the flexible and transparent R‐GO sensor coupled with organic dye molecules provide great potential for real‐time monitoring of toxic gas/vapor in future practical chemical sensing at room conditions in wearable electronics.     

基于探针形式的三维硅微力传感器

为满足三维微力测量的需求,以MEMS体硅压阻工艺技术为基础,研制了一种基于微探针形式,具有μN级三维微力测量和传感能力的半导体压阻式三维微力硅微集成传感器。传感器采用相互迟滞的4个单端固支硅悬臂梁,支撑中间的与微力学探针结合在一起的质量悬块的结构形式,在4mm×4mm的硅基半导体芯片上用MEMS体硅工艺集成而成。通过ANSYS数值仿真的方法分析了三维硅微力传感器结构的应力特点,解决了三维微力之间的相互干扰问题,并对传感器性能进行了测试。结果表明,其X、Z方向的线性灵敏度分别为0.1682、0.0106mV/μN,最大非线性度分别为0.19%FS和1.1%FS。该传感器具有高灵敏度、高可靠性、小体积、低成本等特点。     

MoS2 Van der Waals p–n Junctions Enabling Highly Selective Room‐Temperature NO2 Sensor

Van der Waals p–n junctions of 2D materials present great potential for electronic devices due to the fascinating properties at the junction interface. In this work, an efficient gas sensor based on planar 2D van der Waals junctions is reported by stacking n‐type and p‐type atomically thin MoS₂ films, which are synthesized by chemical vapor deposition (CVD) and soft‐chemistry route, respectively. The electrical conductivity of the van der Waals p–n junctions is found to be strongly affected by the exposure to NO₂ at room temperature (RT). The MoS₂ p–n junction sensor exhibits an outstanding sensitivity and selectivity to NO₂ at RT, which are unavailable in sensors based on individual n‐type or p‐type MoS₂. The sensitivity of 20 ppm NO₂ is improved by 60 times compared to a p‐type MoS₂ sensor, and an extremely low limit of detection of 8 ppb is obtained under ultraviolet irradiation. Complete and very fast sensor recovery is achieved within 30 s. These results are superior to most of the previous reports related to NO₂ detection. This work establishes an entirely new sensing platform and proves the feasibility of using such materials for the high‐performance detection of gaseous molecules at RT.     

Semiconductor‐Type MEMS Gas Sensor for Real‐Time Environmental Monitoring Applications

Low power consuming and highly responsive semiconductor‐type microelectromechanical systems (MEMS) gas sensors are fabricated for real‐time environmental monitoring applications. This subsystem is developed using a gas sensor module, a Bluetooth module, and a personal digital assistant (PDA) phone. The gas sensor module consists of a NO₂ or CO gas sensor and signal processing chips. The MEMS gas sensor is composed of a microheater, a sensing electrode, and sensing material. Metal oxide nanopowder is drop‐coated onto a substrate using a microheater and integrated into the gas sensor module. The change in resistance of the metal oxide nanopowder from exposure to oxidizing or deoxidizing gases is utilized as the principle mechanism of this gas sensor operation. The variation detected in the gas sensor module is transferred to the PDA phone by way of the Bluetooth module.     

Ultrasensitive Detection of VOCs Using a High‐Resolution CuO/Cu2O/Ag Nanopattern Sensor

The p‐type semiconducting copper oxides (CuO and Cu₂O) are promising materials for gas sensors, owing to their characteristic oxygen adsorption properties and low operation temperature. In this study, the sensing performance of a CuO‐based chemiresistor is significantly enhanced by incorporating Ag nanoparticles on high‐resolution p‐type CuO/Cu₂O nanopattern channels. The high‐resolution CuO/Cu₂O/Ag nanochannel is fabricated using a unique top‐down nanolithographic approach. The gas response (ΔR/R_a) of the CuO/Cu₂O/Ag gas sensor increases by a maximum factor of 7.3 for various volatile organic compounds compared with a pristine CuO/Cu₂O gas sensor. The sensors exhibit remarkable sensitivity (ΔR/R_a = 8.04) at 125 parts per billion (ppb) for acetone analytes. As far as it is known, this is the highest sensitivity achieved for p‐type metal oxide semiconductor (MOS)‐based gas sensors compared to previous studies. Furthermore, the outstanding gas responses observed in this study are superior to the most of n‐type MOS‐based gas sensors. The high sensitivity of the sensor is attributed to i) the high resolution (≈30 nm), high aspect ratio (≈12), and ultrasmall grain boundaries (≈10 nm) of the CuO/Cu₂O nanopatterns and ii) the electronic sensitization and chemical sensitization effects induced by incorporating Ag nanoparticles on the CuO/Cu₂O channels.     

Facile Synthesis of 3D Graphene Flowers for Ultrasensitive and Highly Reversible Gas Sensing

Fabrication of nanostructured graphene (Gr) for gas sensing applications has become increasingly attractive. For the first time, 3D graphene flowers (GF) cluster patterns are grown directly on an Ni foam substrate by inexpensive homebuilt microwave plasma‐enhanced chemical vapor deposition (MPCVD) using the gas mixture H₂/C₂H₄O₂@Ar as a precursor. The interim morphologies of the synthesized GF are investigated and the growth mechanism of the GF film is proposed. The GF are decomposed to few‐layer Gr sheets by ultrasonication in ethanol. For the first time, MPCVD‐synthesized Gr is exploited to fabricate a gas sensor that exhibits an ultrahigh sensitivity of 133.2 ppm^?1 to NO₂. Outstanding sensor responses of 1411% and 101% to 10 ppm and 200 ppb NO₂, respectively, are achieved. Furthermore, a low theoretical detection limit of 785 ppt NO₂ is achieved. An ultrafast (within 2 s) recovery is observed at room temperature, and an imbedded microheater is employed to improve the selectivity of NO₂ detection relative to humidity. This work represents a simple, clean, and efficient route to synthesize large‐area cauliflower Gr for gas detection with high performance, including ultrahigh sensitivity, good selectivity, fast recovery, and reversibility.     

Multifunctional ZnO‐Nanowire‐Based Sensor

A simple fabrication of ZnO‐nanowire‐based device and their implementation as a pH sensor, temperature sensor, and photo detector is reported. The presented multifunctional ZnO multiple‐nanowire sensor platform contains a Au finger structure, which is realized by conventional photolithography on a SiO₂ substrate. The nanowires are grown using thermal chemical vapor deposition. In order to detect the physical signals, changes in electrical signals were measured (conductance and current). For temperature sensing, the current behavior from 90 to 380 K under vacuum conditions exhibit a tunneling behavior between spaced nanowires. For photo sensing, the current response between the “on” and “off” states of light was measured when exposed to different wavelengths ranging from UV to visible light. Finally, for pH sensing the conductance was measured between a pH of 5 and 8.5. The ZnO nanowires were protected from chemical attacks by a thin layer of C₄F₈‐plasma‐based coating.     

基于微环腔型光滤波器的新型气体传感器研究

基于微环腔型光学滤波是一项正在发展中的新型气体传感技术,在工业生产、环境保护和医学等领域具有广阔的应用前景.利用微环状波导腔构成气室的吸收光谱型气体传感器具有结构紧凑、波长选择性良好等优点.通过气体吸收光谱及微环腔特性的计算和分析,对基于微环腔型光滤波器的新型气体检测传感系统的设计进行了研究和探索,分析了微环尺寸与其谐振波长、自由光谱范围之间的关系.     

Helical 3D‐Printed Metal Electrodes as Custom‐Shaped 3D Platform for Electrochemical Devices

3D‐printing represents an emerging technology that can revolutionize the way object and functional devices are fabricated. Here the use of metal 3D printing is demonstrated to fabricate bespoke electrochemical stainless steel electrodes that can be used as platform for different electrochemical applications ranging from electrochemical capacitors, oxygen evolution catalyst, and pH sensor by means of an effective and controlled deposition of IrO₂ films. The electrodes have been characterized by scanning electrode microscopy and energy dispersive X‐ray spectroscopy before the electrochemical testing. Excellent pseudocapacitive as well as catalytic properties have been achieved with these 3D printed steel‐IrO₂ electrodes in alkaline solutions. These electrodes also demonstrate Nernstian behavior as pH sensor. This work represents a breakthrough in on‐site prototyping and fabrication of highly tailored electrochemical devices with complex 3D shapes which facilitate specific functions and properties.     

The Art of Integrated Functionalization: Super Stable Black Phosphorus Achieved through Metal‐Organic Framework Coating

Black phosphorus (BP) is a promising 2D nanomaterial with a great potential in various areas, while its intrinsic instability greatly suppresses practical applications, particularly under harsh conditions (e.g., high temperature). Herein, BP functionalization with Al ion is achieved in an integrated manner through MIL‐53 metal‐organic framework (MOF) coating, which greatly improves both ambient and thermal stability of BP. For the obtained MIL‐53 coated BP (BP@MIL‐53), abundant Al ion within MIL‐53 interacts with the lone pair electrons of BP, and subsequently decreases the BP surface electron density, reducing the reactivity of BP toward O₂ and H₂O. The MOF growth crosslinks the Al ion on the BP surface, and achieves integrated functionalization to withstand the detachment of individual Al ion from the BP surface. The noncovalent bond of BP? Al and highly porous structure of MIL‐53 preserve the physical/chemical properties of BP to the maximum, and render BP@MIL‐53 with super‐stability. This functionalization strategy extends the applications of BP based devices under high temperature conditions. As a proof of concept, BP@MIL‐53 is further utilized as a NO₂ gas sensor under relatively high operating temperatures. The BP@MIL‐53 sensor exhibits fast response, outstanding selectivity, and high recovery dynamic process in contrast to bare BP sensor.     

Single‐Step Deposition of Au‐ and Pt‐Nanoparticle‐Functionalized Tungsten Oxide Nanoneedles Synthesized Via Aerosol‐Assisted CVD,and Used for Fabrication of Selective Gas Microsensor Arrays

Tungsten oxide nanostructures functionalized with gold or platinum NPs are synthesized and integrated, using a single‐step method via aerosol‐assisted chemical vapour deposition, onto micro‐electromechanical system (MEMS)‐based gas‐sensor platforms. This co‐deposition method is demonstrated to be an effective route to incorporate metal nanoparticles (NP) or combinations of metal NPs into nanostructured materials, resulting in an attractive way of tuning functionality in metal oxides (MOX). The results show variations in electronic and sensing properties of tungsten oxide according to the metal NPs introduced, which are used to discriminate effectively analytes (C₂H₅OH, H₂, and CO) that are present in proton‐exchange fuel cells. Improved sensing characteristics, in particular to H₂, are observed at 250 °C with Pt‐functionalized tungsten oxide films, whereas non‐functionalized tungsten oxide films show responses to low concentrations of CO at low temperatures. Differences in the sensing characteristics of these films are attributed to the different reactivities of metal NPs (Au and Pt), and to the degree of electronic interaction at the MOX/metal NP interface. The method presented in this work has advantages over other methods of integrating nanomaterials and devices, of having fewer processing steps, relatively low processing temperature, and no requirement for substrate pre‐treatment.     

High‐Performance,Transparent Thin Film Hydrogen Gas Sensor Using 2D Electron Gas at Interface of Oxide Thin Film Heterostructure Grown by Atomic Layer Deposition

A high‐performance, transparent, and extremely thin (<15 nm) hydrogen (H₂) gas sensor is developed using 2D electron gas (2DEG) at the interface of an Al₂O₃/TiO₂ thin film heterostructure grown by atomic layer deposition (ALD), without using an epitaxial layer or a single crystalline substrate. Palladium nanoparticles (≈2 nm in thickness) are used on the surface of the Al₂O₃/TiO₂ thin film heterostructure to detect H₂. This extremely thin gas sensor can be fabricated on general substrates such as a quartz, enabling its practical application. Interestingly, the electron density of the Al₂O₃/TiO₂ thin film heterostructure can be tailored using ALD process temperature in contrast to 2DEG at the epitaxial interfaces of the oxide heterostructures such as LaAlO₃/SrTiO₃. This tunability provides the optimal electron density for H₂ detection. The Pd/Al₂O₃/TiO₂ sensor detects H₂ gas quickly with a short response time of <30 s at 300 K which outperforms conventional H₂ gas sensors, indicating that heating modules are not required for the rapid detection of H₂. A wide bandgap (>3.2 eV) with the extremely thin film thickness allows for a transparent sensor (transmittance of 83% in the visible spectrum) and this fabrication scheme enables the development of flexible gas sensors.     

Encapsulation of Semiconductor Gas Sensors with Gas Barrier Films for USN Application

Sensor nodes in ubiquitous sensor networks require autonomous replacement of deteriorated gas sensors with reserved sensors, which has led us to develop an encapsulation technique to avoid poisoning the reserved sensors and an autonomous activation technique to replace a deteriorated sensor with a reserved sensor. Encapsulations of In₂O₃ nanoparticles with poly(ethylene‐co‐vinyl alcohol) (EVOH) or polyvinylidene difluoride (PVDF) as gas barrier layers are reported. The EVOH or PVDF films are used for an encapsulation of In2O3 as a sensing material and are effective in blocking In2O3 from contacting formaldehyde (HCHO) gas. The activation process of In2O3 by removing the EVOH through heating is effective. However, the thermal decomposition of the PVDF affects the property of the In₂O₃ in terms of the gas reactivity. The response of the sensor to HCHO gas after removing the EVOH is 26%, which is not significantly different with the response of 28% in a reference sample that was not treated at all. We believe that the selection of gas barrier materials for the encapsulation and activation of In2O3 should be considered because of the ill effect the byproduct of thermal decomposition has on the sensing materials and other thermal properties of the barrier materials.     

1.5 V Sub‐mW CMOS Interface Circuit for Capacitive Sensor Applications in Ubiquitous Sensor Networks

In this paper, a low‐power CMOS interface circuit is designed and demonstrated for capacitive sensor applications, which is implemented using a standard 0.35‐μm CMOS logic technology. To achieve low‐power performance, the low‐voltage capacitance‐to‐pulse‐width converter based on a self‐reset operation at a supply voltage of 1.5 V is designed and incorporated into a new interface circuit. Moreover, the external pulse signal for the reset operation is made unnecessary by the employment of the self‐reset operation. At a low supply voltage of 1.5 V, the new circuit requires a total power consumption of 0.47 mW with ultra‐low power dissipation of 157 μW of the interface‐circuit core. These results demonstrate that the new interface circuit with self‐reset operation successfully reduces power consumption. In addition, a prototype wireless sensor‐module with the proposed circuit is successfully implemented for practical applications. Consequently, the new CMOS interface circuit can be used for the sensor applications in ubiquitous sensor networks, where low‐power performance is essential.     

A Shape Memory High‐Voltage Supercapacitor with Asymmetric Organic Electrolytes for Driving an Integrated NO2 Gas Sensor

A high‐voltage supercapacitor with shape memory for driving an integrated NO₂ gas sensor is fabricated using a Norland Optical Adhesive 63 polymer substrate, which can recover the original shape after deformation by short‐time heating. The supercapacitor consists of multiwalled carbon nanotube electrodes and organic electrolyte. By using organic electrolyte consisting of adiponitrile, acetonitrile, and dimethyl carbonate in an optimized volume ratio of 1:1:1, a high operation voltage of 2 V is obtained. Furthermore, asymmetric electrolytes with different redox additives of hydroquinone and 1,4‐dihydroxyanthraquinone to the anode and cathode, respectively, enhance both capacitance and energy density by ≈40 times compared to those of supercapacitor without redox additives. The fabricated supercapacitor on the Norland Optical Adhesive 63 polymer substrate retains 95.8% of its initial capacitance after 1000 repetitive bending cycles at a bending radius of 3.8 mm. Furthermore, the folded supercapacitor recovers its shape upon heating at 70 °C for 20 s. In addition, 90% of the initial capacitance is retained even after the 20th shape recovery from folding. The fabricated supercapacitor is used to drive integrated NO₂ gas sensor on the same Norland Optical Adhesive 63 substrate attached onto skin to detect NO₂ gas, regardless of deformation due to elbow movement.     

The Role of NiO Doping in Reducing the Impact of Humidity on the Performance of SnO2‐Based Gas Sensors: Synthesis Strategies,and Phenomenological and Spectroscopic Studies

The humidity dependence of the gas‐sensing characteristics in SnO₂‐based sensors, one of the greatest obstacles in gas‐sensor applications, is reduced to a negligible level by NiO doping. In a dry atmosphere, undoped hierarchical SnO₂ nanostructures prepared by the self‐assembly of crystalline nanosheets show a high CO response and a rapid response speed. However, the gas response, response/recovery speeds, and resistance in air are deteriorated or changed significantly in a humid atmosphere. When hierarchical SnO₂ nanostructures are doped with 0.64–1.27 wt% NiO, all of the gas‐sensing characteristics remain similar, even after changing the atmosphere from a dry to wet one. According to diffuse‐reflectance Fourier transform IR measurements, it is found that the most of the water‐driven species are predominantly absorbed not by the SnO₂ but by the NiO, and thus the electrochemical interaction between the humidity and the SnO₂ sensor surface is totally blocked. NiO‐doped hierarchical SnO₂ sensors exhibit an exceptionally fast response speed (1.6 s), a fast recovery speed (2.8 s) and a superior gas response (R_a/R_g = 2.8 at 50 ppm CO (R_a: resistance in air, R_g: resistance in gas)) even in a 25% r.h. atmosphere. The doping of hierarchical SnO₂ nanostructures with NiO is a very‐promising approach to reduce the dependence of the gas‐sensing characteristics on humidity without sacrificing the high gas response, the ultrafast response and the ultrafast recovery.     

Hierarchical Ordered Dual‐Mesoporous Polypyrrole/Graphene Nanosheets as Bi‐Functional Active Materials for High‐Performance Planar Integrated System of Micro‐Supercapacitor and Gas Sensor

Planar integrated systems of micro‐supercapacitors (MSCs) and sensors are of profound importance for 3C electronics, but usually appear poor in compatibility due to the complex connections of device units with multiple mono‐functional materials. Herein, 2D hierarchical ordered dual‐mesoporous polypyrrole/graphene (DM‐PG) nanosheets are developed as bi‐functional active materials for a novel prototype planar integrated system of MSC and NH₃ sensor. Owing to effective coupling of conductive graphene and high‐sensitive pseudocapacitive polypyrrole, well‐defined dual‐mesopores of ≈7 and ≈18 nm, hierarchical mesoporous network, and large surface area of 112 m² g^?1, the resultant DM‐PG nanosheets exhibit extraordinary sensing response to NH₃ as low as 200 ppb, exceptional selectivity toward NH₃ that is much higher than other volatile organic compounds, and outstanding capacitance of 376 F g^?1 at 1 mV s^?1 for supercapacitors, simultaneously surpassing single‐mesoporous and non‐mesoporous counterparts. Importantly, the bi‐functional DM‐PG‐based MSC‐sensor integrated system represents rapid and stable response exposed to 10–40 ppm of NH₃ after only charging for 100 s, remarkable sensitivity of NH₃ detection that is close to DM‐PG‐based MSC‐free sensor, impressive flexibility with ≈82% of initial response value even at 180°, and enhanced overall compatibility, thereby holding great promise for ultrathin, miniaturized, body‐attachable, and portable detection of NH₃.     

A Patterned Graphene/ZnO UV Sensor Driven by Integrated Asymmetric Micro‐Supercapacitors on a Liquid Metal Patterned Foldable Paper

A foldable array of patterned graphene/ZnO nanoparticle UV sensor and asymmetric micro‐supercapacitors (AMSCs) integrated on a paper substrate with patterned liquid metal interconnections is reported. The resistor type UV sensor based on graphene/ZnO nanoparticles is patterned to be driven by the stored energy of the integrated AMSCs. The AMSC consists of MnO₂ nanoball deposited multiwalled carbon nanotubes (MWNTs) and V₂O₅ wrapped MWNTs as positive and negative electrodes, respectively. As an electrolyte, propylene carbonate‐poly(methyl methacrylate)‐LiClO₄, an organic solvent‐based gel, is used. The UV sensor and AMSCs can be easily integrated on a liquid metal, Galinstan, patterned, waterproof mineral paper and show a mechanically stable UV sensing, regardless of repetitive folding cycles. This work demonstrates a novel foldable nanomaterial based sensor system driven by integrated energy storage devices, applicable to future wearable and portable electronics.