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.

One-step synthesis of photoluminescent nanofluids by direct loading of reactively sputtered cubic ZrN nanoparticles into organic liquids.

ZrN nanofluids may exhibit unique optoelectronic properties because of the matching of the solar spectrum with interband transitions and localized surface plasmon resonance (LSPR). Nevertheless, these nanofluids have scarcely been investigated, mainly because of the complexity of the current synthetic routes that involve aggressive chemicals and high temperatures. This work aims to validate reactive dc magnetron sputtering of zirconium in Ar/N2 as an environmentally benign, annealing-free method to produce 22 nm-sized, highly crystalline, stoichiometric, electrically conductive, and plasmonic ZrN nanoparticles (NPs) of cubic shape and to load them into vacuum-compatible liquids of different chemical compositions (polyethylene glycol (PEG), paraffin, and pentaphenyl trimethyl trisiloxane (PTT)) in one step. The nanofluids demonstrate LSPR in the red/near-IR range that gives them a bluish color in transmittance. The nanofluids also demonstrate complex photoluminescence behavior such that ZrN NPs enhance the photoluminescence (PL) intensity of paraffin and PEG, whereas the PL of PTT remains almost invariable. Based on DFT calculations, different energetic barriers to charge transfer between ZrN and the organic molecules are suggested as the main factors that influence the observed optoelectronic response. Overall, our study provides a novel approach to the synthesis of transition metal nitride nanofluids in an environmentally friendly manner, deepens the understanding of the interactions between ZrN and organic molecules, and unveils new optoelectronic phenomena in such systems.

Polar Polymorphism: A New Intermediate Structure toward the Thin-Film Phase in Asymmetric Benzothieno[3,2-b][1]-benzothiophene Derivatives.

Understanding structure and polymorphism is relevant for any organic device optimization, and it is of particular relevance in 7-decyl-2-phenyl[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-10) since high carrier mobility in Ph-BTBT-10 thin films has been linked to the structural transformation from the metastable thin-film phase to the thermodynamically stable bilayer structure via thermal annealing. We combine here a systematic nanoscale morphological analysis with local Kelvin probe force microcopy (KPFM) that demonstrates the formation of a polar polymorph in thin films as an intermediate structure for thicknesses lower than 20 nm. The polar structure develops with thickness a variable amount of structural defects in the form of individual flipped molecules (point defects) or sizable polar domains, and evolves toward the reported nonpolar thin-film phase. The direct experimental evidence is supported by electronic structure density functional theory calculations. The structure of the film has dramatic effects on the electronic properties, leading to a decrease in the film work function (by up to 1 eV) and a considerable broadening of the occupied molecular orbitals, attributed to electrostatic disorder. From an advanced characterization point of view, KPFM stands out as a valuable tool for evaluating electrostatic disorder and the conceivable emergence of polar polymorphs in organic thin films. The emergence of polar assemblies introduces a critical consideration for other asymmetric BTBT derivatives, which may be pivotal to understanding the structure-property relationships in organic field-effect transistors (OFETs). A precise determination of any polar assemblies close to the dielectric interface is critical for the judicious design and upgrading of high-performance OFETs.