Operando Investigation of WS2 Gas Sensors: Simultaneous Ambient Pressure X-ray Photoelectron Spectroscopy and Electrical Characterization in Unveiling Sensing Mechanisms during Toxic Gas Exposure.

Ambient pressure X-ray photoelectron spectroscopy (APXPS) is combined with simultaneous electrical measurements and supported by density functional theory calculations to investigate the sensing mechanism of tungsten disulfide (WS2)-based gas sensors in an operando dynamic experiment. This approach allows for the direct correlation between changes in the surface potential and the resistivity of the WS2 sensing active layer under realistic operating conditions. Focusing on the toxic gases NO2 and NH3, we concurrently demonstrate the distinct chemical interactions between oxidizing or reducing agents and the WS2 active layer and their effect on the sensor response. The experimental setup mimics standard electrical measurements on chemiresistors, exposing the sample to dry air and introducing the target gas analyte at different concentrations. This methodology applied to NH3 concentrations of 100, 230, and 760 and 14 ppm of NO2 establishes a benchmark for future APXPS studies on sensing devices, providing fast acquisition times and a 1:1 correlation between electrical response and spectroscopy data in operando conditions. Our findings contribute to a deeper understanding of the sensing mechanism in 2D transition metal dichalcogenides, paving the way for optimizing chemiresistor sensors for various industrial applications and wireless platforms with low energy consumption.

Hydrogen Sensing Mechanism of WS2 Gas Sensors Analyzed with DFT and NAP-XPS.

Nanostructured tungsten disulfide (WS2) is one of the most promising candidates for being used as active nanomaterial in chemiresistive gas sensors, as it responds to hydrogen gas at room temperature. This study analyzes the hydrogen sensing mechanism of a nanostructured WS2 layer using near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and density functional theory (DFT). The W 4f and S 2p NAP-XPS spectra suggest that hydrogen makes physisorption on the WS2 active surface at room temperature and chemisorption on tungsten atoms at temperatures above 150 °C. DFT calculations show that a hydrogen molecule physically adsorbs on the defect-free WS2 monolayer, while it splits and makes chemical bonds with the nearest tungsten atoms on the sulfur point defect. The hydrogen adsorption on the sulfur defect causes a large charge transfer from the WS2 monolayer to the adsorbed hydrogen. In addition, it decreases the intensity of the in-gap state, which is generated by the sulfur point defect. Furthermore, the calculations explain the increase in the resistance of the gas sensor when hydrogen interacts with the WS2 active layer.

Three-Dimensional Assemblies of Edge-Enriched WSe2 Nanoflowers for Selectively Detecting Ammonia or Nitrogen Dioxide.

Herein, we present, for the first time, a chemoresistive-type gas sensor composed of two-dimensional WSe2, fabricated by a simple selenization of tungsten trioxide (WO3) nanowires at atmospheric pressure. The morphological, structural, and chemical composition investigation shows the growth of vertically oriented three-dimensional (3D) assemblies of edge-enriched WSe2 nanoplatelets arrayed in a nanoflower shape. The gas sensing properties of flowered nanoplatelets (2H-WSe2) are investigated thoroughly toward specific gases (NH3 and NO2) at different operating temperatures. The integration of 3D WSe2 with unique structural arrangements resulted in exceptional gas sensing characteristics with dual selectivity toward NH3 and NO2 gases. Selectivity can be tuned by selecting its operating temperature (150 °C for NH3 and 100 °C for NO2). For instance, the sensor has shown stable and reproducible responses (24.5%) toward 40 ppm NH3 vapor detection with an experimental LoD < 2 ppm at moderate temperatures. The gas detecting capabilities for CO, H2, C6H6, and NO2 were also investigated to better comprehend the selectivity of the nanoflower sensor. Sensors showed repeatable responses with high sensitivity to NO2 molecules at a substantially lower operating temperature (100 °C) (even at room temperature) and LoD < 0.1 ppm. However, the gas sensing properties reveal high selectivity toward NH3 gas at moderate operating temperatures. Moreover, the sensor demonstrated high resilience against ambient humidity (Rh = 50%), demonstrating its remarkable stability toward NH3 gas detection. Considering the detection of NO2 in a humid ambient atmosphere, there was a modest increase in the sensor response (5.5%). Furthermore, four-month long-term stability assessments were also taken toward NH3 gas detection, and sensors showed excellent response stability. Therefore, this study highlights the practical application of the 2H variant of WSe2 nanoflower gas sensors for NH3 vapor detection.

Embedded Transdermal Alcohol Detection via a Finger Using SnO2 Gas Sensors.

In this paper, we report the fabrication and characterization of a portable transdermal alcohol sensing device via a human finger, using tin dioxide (SnO2) chemoresistive gas sensors. Compared to conventional detectors, this non-invasive technique allowed us the continuous monitoring of alcohol with low cost and simple fabrication process. The sensing layers used in this work were fabricated by using the reactive radio frequency (RF) magnetron sputtering technique. Their structure and morphology were investigated by means of X-ray spectroscopy (XRD) and scanning electron microscopy (SEM), respectively. The results indicated that the annealing time has an important impact on the sensor sensitivity. Before performing the transdermal measurements, the sensors were exposed to a wide range of ethanol concentrations and the results displayed good responses with high sensitivity, stability, and a rapid detection time. Moreover, against high relative humidity (50% and 70%), the sensors remained resistant by showing a slight change in their gas sensing performances. A volunteer (an adult researcher from our volunteer group) drank 50 mL of tequila in order to realize the transdermal alcohol monitoring. Fifteen minutes later, the volunteer's skin started to evacuate alcohol and the sensor resistance began to decline. Simultaneously, breath alcohol measurements were attained using a DRAGER 6820 certified breathalyzer. The results demonstrated a clear correlation between the alcohol concentration in the blood, breath, and via perspiration, which validated the embedded transdermal alcohol device reported in this work.

Aerosol assisted chemical vapour deposition of gas sensitive SnO2 and Au-functionalised SnO2 nanorods via a non-catalysed vapour solid (VS) mechanism.

Tin oxide nanorods (NRs) are vapour synthesised at relatively lower temperatures than previously reported and without the need for substrate pre-treatment, via a vapour-solid mechanism enabled using an aerosol-assisted chemical vapour deposition method. Results demonstrate that the growth of SnO2 NRs is promoted by a compression of the nucleation rate parallel to the substrate and a decrease of the energy barrier for growth perpendicular to the substrate, which are controlled via the deposition conditions. This method provides both single-step formation of the SnO2 NRs and their integration with silicon micromachined platforms, but also allows for in-situ functionalization of the NRs with gold nanoparticles via co-deposition with a gold precursor. The functional properties are demonstrated for gas sensing, with microsensors using functionalised NRs demonstrating enhanced sensing properties towards H2 compared to those based on non-functionalised NRs.