An Ultrasensitive Organic Semiconductor NO2 Sensor Based on Crystalline TIPS‐Pentacene Films

Organic semiconductor gas sensor is one of the promising candidates of room temperature operated gas sensors with high selectivity. However, for a long time the performance of organic semiconductor sensors, especially for the detection of oxidizing gases, is far behind that of the traditional metal oxide gas sensors. Although intensive attempts have been made to address the problem, the performance and the understanding of the sensing mechanism are still far from sufficient. Herein, an ultrasensitive organic semiconductor NO₂ sensor based on 6,13‐bis(triisopropylsilylethynyl)­pentacene (TIPS‐petacene) is reported. The device achieves a sensitivity over 1000%/ppm and fast response/recovery, together with a low limit of detection (LOD) of 20 ppb, all of which reach the level of metal oxide sensors. After a comprehensive analysis on the morphology and electrical properties of the organic films, it is revealed that the ultrahigh performance is largely related to the film charge transport ability, which was less concerned in the studies previously. And the combination of efficient charge transport and low original charge carrier concentration is demonstrated to be an effective access to obtain high performance organic semiconductor gas sensors.     

Superior Self‐Powered Room‐Temperature Chemical Sensing with Light‐Activated Inorganic Halides Perovskites

Hybrid halide perovskite is one of the promising light absorber and is intensively investigated for many optoelectronic applications. Here, the first prototype of a self‐powered inorganic halides perovskite for chemical gas sensing at room temperature under visible‐light irradiation is presented. These devices consist of porous network of CsPbBr₃ (CPB) and can generate an open‐circuit voltage of 0.87 V under visible‐light irradiation, which can be used to detect various concentrations of O₂ and parts per million concentrations of medically relevant volatile organic compounds such as acetone and ethanol with very quick response and recovery time. It is observed that O₂ gas can passivate the surface trap sites in CPB and the ambipolar charge transport in the perovskite layer results in a distinct sensing mechanism compared with established semiconductors with symmetric electrical response to both oxidizing and reducing gases. The platform of CPB‐based gas sensor provides new insights for the emerging area of wearable sensors for personalized and preventive medicine.     

An integrated solution for NOx‐reduction and ‐control under lean‐burn conditions

Upcoming emission regulations order highly effective NO_x‐reduction systems in lean‐burn engines requiring new catalytic materials and integrated control of the reduction process. Thus, new approaches for NO_x‐reduction and its monitoring over an On‐Board‐Diagnostic (OBD) system are suggested throughout the globe. A promising attempt is the development of a catalytic system having an integrated NO_x‐sensor, based on selective catalytic reduction process and impedance sensors. The study displays the results achieved both with a perovskite type of self‐regenerative catalyst functioning by H₂‐reductant and with impedance NO_x‐sensors. The catalysts were tested at the temperature range of 150 °C to 360 °C yielding NO_x conversion rates of 92 % with high selectivity to N₂. Impedance sensors having NiCr₂O₄‐ and NiO‐SE and PYSZ‐ and FYSZ‐electrolytes are developed and tested at 600 °C under lean atmosphere (5 vol. % O₂). Better sensing behaviour towards NO and lower cross‐selectivity towards O₂, CO, CO₂ and CH₄ have been observed with sensors having NiO‐SE.     

UV–Ozone Interfacial Modification in Organic Transistors for High‐Sensitivity NO2 Detection

A new type of nitrogen dioxide (NO₂) gas sensor based on copper phthalocyanine (CuPc) thin film transistors (TFTs) with a simple, low‐cost UV–ozone (UVO)‐treated polymeric gate dielectric is reported here. The NO₂ sensitivity of these TFTs with the dielectric surface UVO treatment is ≈400× greater for [NO₂] = 30 ppm than for those without UVO treatment. Importantly, the sensitivity is ≈50× greater for [NO₂] = 1 ppm with the UVO‐treated TFTs, and a limit of detection of ≈400 ppb is achieved with this sensing platform. The morphology, microstructure, and chemical composition of the gate dielectric and CuPc films are analyzed by atomic force microscopy, grazing incident X‐ray diffraction, X‐ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy, revealing that the enhanced sensing performance originates from UVO‐derived hydroxylated species on the dielectric surface and not from chemical reactions between NO₂ and the dielectric/semiconductor components. This work demonstrates that dielectric/semiconductor interface engineering is essential for readily manufacturable high‐performance TFT‐based gas sensors.     

Self‐Formed Channel Devices Based on Vertically Grown 2D Materials with Large‐Surface‐Area and Their Potential for Chemical Sensor Applications

2D layered materials with sensitive surfaces are promising materials for use in chemical sensing devices, owing to their extremely large surface‐to‐volume ratios. However, most chemical sensors based on 2D materials are used in the form of laterally defined active channels, in which the active area is limited to the actual device dimensions. Therefore, a novel approach for fabricating self‐formed active‐channel devices is proposed based on 2D semiconductor materials with very large surface areas, and their potential gas sensing ability is examined. First, the vertical growth phenomenon of SnS₂ nanocrystals is investigated with large surface area via metal‐assisted growth using prepatterned metal electrodes, and then self‐formed active‐channel devices are suggested without additional pattering through the selective synthesis of SnS₂ nanosheets on prepatterned metal electrodes. The self‐formed active‐channel device exhibits extremely high response values (>2000% at 10 ppm) for NO₂ along with excellent NO₂ selectivity. Moreover, the NO₂ gas response of the gas sensing device with vertically self‐formed SnS₂ nanosheets is more than two orders of magnitude higher than that of a similar exfoliated SnS₂‐based device. These results indicate that the facile device fabrication method would be applicable to various systems in which surface area plays an important role.     

Detection of NO2 Down to One ppb Using Ion‐in‐Conjugation‐Inspired Polymer

Nitrogen dioxide (NO₂) emission has severe impact on human health and the ecological environment and effective monitoring of NO₂ requires the detection limit (limit of detection) of several parts‐per‐billion (ppb). All organic semiconductor‐based NO₂ sensors fail to reach such a level. In this work, using an ion‐in‐conjugation inspired‐polymer (poly(3,3′‐diaminobenzidine‐squarine, noted as PDBS) as the sensory material, NO₂ can be detected as low as 1 ppb, which is the lowest among all reported organic NO₂ sensors. In addition, the sensor has high sensitivity, good reversibility, and long‐time stability with a period longer than 120 d. Theoretical calculations reveal that PDBS offers unreacted amine and zwitterionic groups, which can offer both the H‐bonding and ion‐dipole interaction to NO₂. The moderate binding energies (≈0.6 eV) offer high sensitivity, selectivity as well as good reversibility. The results demonstrate that the ion‐in‐conjugation can be employed to greatly improve sensitivity and selectivity in organic gas sensors by inducing both H‐bonding and ion‐dipole attraction.     

Effect of annealing temperature on the characteristics and sensing properties of WO<Subscript>3</Subscript> nanowires

A uniform WO₃ nanowire structure was prepared by two-step thermal oxidation method on Si substrate. WO₃ nanowires show different morphology and crystal structures after annealing at different temperatures. The influence of annealing temperature on WO₃ nanowires was investigated by SEM, TEM and XRD. Higher crystallization property and lower surface state was obtained with higher annealing temperature. The gas sensing properties of the WO₃ nanowires with various annealing temperatures to NO₂ with the concentration ranging from 1 to 4 ppm were examined at different temperatures ranging from room temperature to 200 °C. The results indicate that WO₃ nanowires can greatly lower the working temperature of sensors and sensors based on WO₃ nanowires show p-type or n-type sensing behaviors depending on annealing temperatures. Possible sensing mechanism of p-type WO₃ nanowires and the influence of annealing temperature on sensing types was explained. This work might supply new ideas about gas sensing mechanisms and open a new way to develop p-type WO₃ sensing materials.     

Modulation of Agglomeration of Vertical Porous Silicon Nanowires and the Effect on Gas‐Sensing Response

Porous silicon nanowires (PSiNWs) array is a promising material for development of integrated gas sensors operating at room temperature. This work reports the fabrication of PSiNWs assembly with different structural features and its effect on gas‐sensing performance. Bundling and well separating PSiNWs arrays are fabricated by MACE method, respectively, based on the effective modulation of surface wettability of the initial Si substrate. The HF pretreatment creates a hydrophobic surface favorable for deposition of irregular Ag nanoflakes and then for the formation of bundling PSiNWs array. In contrast, the PSiNWs with well lateral separation are formed based on the predeposited uniform Ag nanoparticles on a hydrophilic Si surface. The PSiNWs array featured by tip‐clusters is proved to be highly effective in achieving highly sensitive and rapid response to NO₂ gas at room temperature. Satisfying dynamic characteristic and selectivity are meanwhile observed for the bundling array. The formation of the bundling or separating of PSiNWs is discussed in terms of the force balance of individual nanowire, which is further correlated with non‐uniform distribution of Ag nanoclusters caused by H‐termination. Meanwhile, high sensing performance of bundling nanowires is analyzed based on the structural promotion of the unique configuration of tip‐cluster to sensing response.

     

Stabilizing MoS2 Nanosheets through SnO2 Nanocrystal Decoration for High‐Performance Gas Sensing in Air

The unique properties of MoS₂ nanosheets make them a promising candidate for high‐performance room temperature sensing. However, the properties of pristine MoS₂ nanosheets are strongly influenced by the significant adsorption of oxygen in an air environment, which leads to instability of the MoS₂ sensing device, and all sensing results on MoS₂ reported to date were exclusively obtained in an inert atmosphere. This significantly limits the practical sensor application of MoS₂ in an air environment. Herein, a novel nanohybrid of SnO₂ nanocrystal (NC)‐decorated crumpled MoS₂ nanosheet (MoS₂/SnO₂) and its exciting air‐stable property for room temperature sensing of NO₂ are reported. Interestingly, the SnO₂ NCs serve as strong p‐type dopants for MoS₂, leading to p‐type channels in the MoS₂ nanosheets. The SnO₂ NCs also significantly enhance the stability of MoS₂ nanosheets in dry air. As a result, unlike other MoS₂ sensors operated in an inert gas (e.g. N₂), the nanohybrids exhibit high sensitivity, excellent selectivity, and repeatability to NO₂ under a practical dry air environment. This work suggests that NC decoration significantly tunes the properties of MoS₂ nanosheets for various applications.     

Self‐Powered Chemical Sensing Driven by Graphene‐Based Photovoltaic Heterojunctions with Chemically Tunable Built‐In Potentials

Ultralow power chemical sensing is essential toward realizing the Internet of Things. However, electrically driven sensors must consume power to generate an electrical readout. Here, a different class of self‐powered chemical sensing platform based on unconventional photovoltaic heterojunctions consisting of a top graphene (Gr) layer in contact with underlying photoactive semiconductors including bulk silicon and layered transition metal dichalcogenides is proposed. Owing to the chemically tunable electrochemical potential of Gr, the built‐in potential at the junction is effectively modulated by absorbed gas molecules in a predictable manner depending on their redox characteristics. Such ability distinctive from bulk photovoltaic counterparts enables photovoltaic‐driven chemical sensing without electric power consumption. Furthermore, it is demonstrated that the hydrogen (H₂) sensing properties are independent of the light intensity, but sensitive to the gas concentration down to the 1 ppm level at room temperature. These results present an innovative strategy to realize extremely energy‐efficient sensors, providing an important advancement for future ubiquitous sensing.     

Gas sensors based on doped-CNT/SnO2 composites for NO2 detection at room temperature

For the first time nitrogen or boron doped carbon nanotubes were added into a SnO₂ matrix to develop a new hybrid CNTs/SnO₂ gas sensors. The hybrid sensor is utilised to detect low ppb concentrations of NO₂ in air, by measuring resistance changes of thin CNTs/SnO₂ films. The tests are performed at room temperature. For comparison, pure SnO₂ and N or B-substituted CNT sensors are also examined. Comparative gas sensing results reveal that the CNTs/SnO₂ hybrid sensors exhibit much higher response towards NO₂, at least by a factor of 10, and good baseline recovery properties at room temperature than the blank SnO₂ and the N or B-substituted CNT sensors. This finding shows that doping SnO₂ with low quantity of CNTs doped with heteroatoms can dramatically improve sensitivity.     

A New Strategy for Humidity Independent Oxide Chemiresistors: Dynamic Self‐Refreshing of In2O3 Sensing Surface Assisted by Layer‐by‐Layer Coated CeO2 Nanoclusters

The humidity dependence of the gas sensing characteristics of metal oxide semiconductors has been one of the greatest obstacles for gas sensor applications during the last five decades because ambient humidity dynamically changes with the environmental conditions. Herein, a new and novel strategy is reported to eliminate the humidity dependence of the gas sensing characteristics of oxide chemiresistors via dynamic self‐refreshing of the sensing surface affected by water vapor chemisorption. The sensor resistance and gas response of pure In₂O₃ hollow spheres significantly change and deteriorate in humid atmospheres. In contrast, the humidity dependence becomes negligible when an optimal concentration of CeO₂ nanoclusters is uniformly loaded onto In₂O₃ hollow spheres via layer‐by‐layer (LBL) assembly. Moreover, In₂O₃ sensors LBL‐coated with CeO₂ nanoclusters show fast response/recovery, low detection limit (500 ppb), and high selectivity to acetone even in highly humid conditions (relative humidity 80%). The mechanism underlying the dynamic refreshing of the In₂O₃ sensing surfaces regardless of humidity variation is investigated in relation to the role of CeO₂ and the chemical interaction among CeO₂, In₂O₃, and water vapor. This strategy can be widely used to design high performance gas sensors including disease diagnosis via breath analysis and pollutant monitoring.     

Controllable Synthesis of 3D Ni(OH)2 and NiO Nanowalls on Various Substrates for High‐Performance Nanosensors

Large‐area and uniform three‐dimensional (3D) β‐Ni(OH)₂ and NiO nanowalls were synthesized on a variety of rigid and flexible substrates via a simple aqueous chemical deposition process. The β‐Ni(OH)₂ nanowalls consist of single‐crystal Ni(OH)₂ nanosheets that were vertically grown on different substrates. The height, crystallinity, and morphology of the Ni(OH)₂ nanowalls can be readily modified by adjusting the reaction time and concentration of the NiCl₂ solution. The synthesis mechanism of the Ni(OH)₂ nanowalls was determined through heterogeneous nucleation and subsequent oriented crystal growth. 3D NiO nanowalls were obtained by thermal decomposition of the Ni(OH)₂ nanowalls at 400 °C in Ar atmosphere. Highly sensitive, selective gas sensors and electrochemical sensors based on these NiO nanowalls were developed. The chemiresistive gas sensors based on the NiO nanowalls grown on ceramic substrates exhibited an excellent performance with low detection limit for formaldehyde (8 ppb) and NO₂ (15 ppb). The electrochemical sensor based on the NiO nanowalls grown on an FTO glass substrate had a superior selectivity to non‐enzymatic glucose with a detection limit of 200 nm .     

TiO2‐Decorated Graphite Nanoplatelet Nanocomposites for High‐Temperature Sensor Applications

Temperature and/or composition mapping inside high temperature energy conversion and storage devices are challenging, yet of critical importance to improve the material design for optimum performance. Here, the great potential of TiO₂ nanoparticle (NP)‐decorated graphite nanoplatelet (GNP) nanocomposites as high temperature thermal senors or gas sensors is reported. Effects of the GNP substrate on phonon confinement in Raman spectrum, grain growth, and phase stability of anatase TiO₂ NPs at high temperatures are systematically studied. Thermally sensitive Raman signatures, indicating the ultrafast grain growth of TiO₂ NPs in response to short thermal shock treatments (0.1–25 s) at high temperatures, are exploited for high temperature thermal sensing applications. A very high accuracy of nearly 98% in temperature measurements is demonstrated for a given short‐time thermal exposure. Thermal stability of anatase TiO₂ NPs against transformation into the rutile phase in TiO₂‐GNP nancomposites is substantially increased by controlling the surface area of the substrate, which would significantly improve the performance of TiO₂‐based high temperature gas sensors.     

Flexible Metal–Organic Framework‐Based Mixed‐Matrix Membranes: A New Platform for H2S Sensors

Metal–organic framework (MOF)–polymer mixed‐matrix membranes (MMMs) have shown great potential and superior performance in gas separations. However, their sensing application has not been fully established yet. Herein, a rare example of using flexible MOF‐based MMMs as a fluorescent turn‐on sensor for the detection of hydrogen sulfide (H₂S) is reported. These MOF‐based MMMs are readily prepared by mixing a highly stable aluminum‐based nano‐MOF (Al‐MIL‐53‐NO₂) into poly(vinylidene fluoride) with high loadings up to 70%. Unlike the intrinsic fragility and poor processability of pure‐MOF membranes, these MMMs exhibit desirable flexibility and processability that are more suitable for practical sensing applications. The uniform distribution of Al‐MIL‐53‐NO₂ particles combined with the permanent pores of MOFs enable these MMMs to show good water permeation flux and consequently have a full contact between the analyte and MOFs. The developed MMM sensor (70% MOF loading) thus shows a highly remarkable detection selectivity and sensitivity for H₂S with an exceptionally low detection limit around 92.31 × 10^?9m , three orders of magnitude lower than the reported powder‐form MOFs. This work demonstrates that it is feasible to develop flexible luminescent MOF‐based MMMs as a novel platform for chemical sensing applications.     

Gas sensing characteristics of MEMS gas sensor arrays in binary mixed-gas system

MOS gas sensor arrays based on MEMS gas sensor platforms were developed for the detection of carbon monoxide (CO), nitrogen oxides (NO_x) and ammonia (NH₃), and their gas sensing characteristics in binary mixed-gas system were investigated. Three gas sensing materials with nano-sized particles for these target gases, Pd–SnO₂ for CO, In₂O₃ for NO_x and Ru–WO₃ for NH₃ were synthesized using a sol–gel method. All the sensors showed good properties for their target gases at the optimum points for micro-heater operation. From the experimental data in MEMS gas sensor arrays in a binary mixed system, the gas sensing behavior and sensor response in mixed gas systems were scrutinized. The gas sensing behaviors to the mixed gas systems suggested that specific adsorption and selective activation of adsorption sites might occur in gas mixtures and offer the priority for the adsorption of specific gas. Thorough analysis of the sensing performance of the sensor arrays will make it possible to discriminate the components in gas mixtures as well as their concentrations.     

Harnessing the Influence of Reactive Edges and Defects of Graphene Substrates for Achieving Complete Cycle of Room‐Temperature Molecular Sensing

Molecular doping and detection are at the forefront of graphene research, a topic of great interest in physical and materials science. Molecules adsorb strongly on graphene, leading to a change in electrical conductivity at room temperature. However, a common impediment for practical applications reported by all studies to date is the excessively slow rate of desorption of important reactive gases such as ammonia and nitrogen dioxide. Annealing at high temperatures, or exposure to strong ultraviolet light under vacuum, is employed to facilitate desorption of these gases. In this article, the molecules adsorbed on graphene nanoflakes and on chemically derived graphene‐nanomesh flakes are displaced rapidly at room temperature in air by the use of gaseous polar molecules such as water and ethanol. The mechanism for desorption is proposed to arise from the electrostatic forces exerted by the polar molecules, which decouples the overlap between substrate defect states, molecule states, and graphene states near the Fermi level. Using chemiresistors prepared from water‐based dispersions of single‐layer graphene on mesoporous alumina membranes, the study further shows that the edges of the graphene flakes (showing p‐type responses to NO₂ and NH₃) and the edges of graphene nanomesh structures (showing n‐type responses to NO₂ and NH₃) have enhanced sensitivity. The measured responses towards gases are comparable to or better than those which have been obtained using devices that are more sophisticated. The higher sensitivity and rapid regeneration of the sensor at room temperature provides a clear advancement towards practical molecule detection using graphene‐based materials.     

Nanostructured Materials for Room‐Temperature Gas Sensors

Sensor technology has an important effect on many aspects in our society, and has gained much progress, propelled by the development of nanoscience and nanotechnology. Current research efforts are directed toward developing high‐performance gas sensors with low operating temperature at low fabrication costs. A gas sensor working at room temperature is very appealing as it provides very low power consumption and does not require a heater for high‐temperature operation, and hence simplifies the fabrication of sensor devices and reduces the operating cost. Nanostructured materials are at the core of the development of any room‐temperature sensing platform. The most important advances with regard to fundamental research, sensing mechanisms, and application of nanostructured materials for room‐temperature conductometric sensor devices are reviewed here. Particular emphasis is given to the relation between the nanostructure and sensor properties in an attempt to address structure–property correlations. Finally, some future research perspectives and new challenges that the field of room‐temperature sensors will have to address are also discussed.     

Influence of effective surface area on gas sensing properties of WO3 sputtered thin films

WO₃ thin films having different effective surface areas were deposited under various discharge gas pressures at room temperature by using reactive magnetron sputtering. The microstructure of WO₃ thin films was investigated by X-ray diffraction, scanning electron microscopy, and by the measurement of physical adsorption isotherms. The effective surface area and pore volume of WO₃ thin films increase with increasing discharge gas pressure from 0.4 to 12 Pa. Gas sensors based on WO₃ thin films show reversible response to NO₂ gas and H₂ gas at an operating temperature of 50-300 °C. The peak sensitivity is found at 200 °C for NO₂ gas and the peak sensitivity appears at 300 °C for H₂ gas. For both kinds of detected gases, the sensor sensitivity increases linearly with an increase of effective surface area of WO₃ thin films. The results demonstrate the importance of achieving high effective surface area on improving the gas sensing performance.     

Li‐Ion Cooperative Migration and Oxy‐Sulfide Synergistic Effect in Li14P2Ge2S16−6xOx Solid‐State‐Electrolyte Enables Extraordinary Conductivity and High Stability

Critical to the development of all‐solid‐state lithium‐ion batteries technology are novel solid‐state electrolytes with high ionic conductivity and robust stability under inorganic solid‐electrolyte operating conditions. Herein, by using density functional theory and molecular dynamics, a mixed oxygen‐sulfur‐based Li‐superionic conductor is screened out from the local chemical structure of β‐Li₃PS₄ to discover novel Li₁₄P₂Ge₂S₈O₈ (LPGSO) with high ionic conductivity and high stability under thermal, moist, and electrochemical conditions, which causes oxygenation at specific sites to improve the stability and selective sulfuration to provide an O‐S mixed path by Li‐S/O structure units with coordination number between 3 and 4 for fast Li‐cooperative conduction. Furthermore, LPGSO exhibits a quasi‐isotropic 3D Li‐ion cooperative diffusion with a lesser migration barrier (≈0.19 eV) compared to its sulfide‐analog Li₁₄P₂Ge₂S₁₆. The theoretical ionic conductivity of this conductor at room temperature is as high as ≈30.0 mS cm^?1, which is among the best in current solid‐state electrolytes. Such an oxy‐sulfide synergistic effect and Li‐ion cooperative migration mechanism would enable the engineering of next‐generation electrolyte materials with desirable safety and high ionic conductivity, for possible application in the near future.