Reducing Humidity Response of Gas Sensors for Medical Applications: Use of Spark Discharge Synthesis of Metal Oxide Nanoparticles.

The application of gas sensors in breath analysis is an important trend in the early diagnostics of different diseases including lung cancer, ulcers, and enteric infection. However, traditional methods of synthesis of metal oxide gas-sensing materials for semiconductor sensors based on wet sol-gel processes give relatively high sensitivity of the gas sensor to changing humidity. The sol-gel process leading to the formation of superficial hydroxyl groups on oxide particles is responsible for the strong response of the sensing material to this factor. In our work, we investigated the possibility to synthesize metal oxide materials with reduced sensitivity to water vapors. Dry synthesis of SnO2 nanoparticles was implemented in gas phase by spark discharge, enabling the reduction of the hydroxyl concentration on the surface and allowing the production of tin dioxide powder with specific surface area of about 40 m²/g after annealing at 610 °C. The drop in sensor resistance does not exceed 20% when air humidity increases from 40 to 100%, whereas the response to 100 ppm of hydrogen is a factor of 8 with very short response time of about 1 s. The sensor response was tested in mixtures of air with hydrogen, which is the marker of enteric infections and the marker of early stage fire, and in a mixture of air with lactate (marker of stomach cancer) and ammonia gas (marker of Helicobacter pylori, responsible for stomach ulcers).

Interaction of water, hydrogen and their mixtures with SnO2 based materials: the role of surface hydroxyl groups in detection mechanisms.

DRIFTS, TGA and resistance measurements have been used to study the mechanism of water and hydrogen interaction accompanied by a resistance change (sensor signal) of blank and Pd doped SnO(2). It was found that a highly hydroxylated surface of blank SnO(2) reacts with gases through bridging hydroxyl groups, whereas the Pd doped materials interact with hydrogen and water through bridging oxygen. In the case of blank SnO(2) the sensor signal maximum towards H(2) in dry air (R(0)/R(g)) is observed at approximately 345 degrees C, and towards water, at approximately 180 degrees C, which results in high selectivity to hydrogen in the presence of water vapors (minor humidity effect). In contrast, on doping with Pd the response to hydrogen in dry air and to water occurred in the same temperature region (ca. 140 degrees C) leading to low selectivity with a high effect of humidity. An increase in water concentration in the gas phase changes the hydrogen interaction mechanism of Pd doped materials, while that of blank SnO(2) is unchanged. The interaction of hydrogen with the catalyst doped SnO(2) occurs predominantly through hydroxyl groups when the volumetric concentration of water in the gas phase is higher than that of H(2) by a factor of 1000.

Gas sensing properties of individual SnO2 nanowires and SnO2 sol-gel nanocomposites.

This work is an investigation of the properties of semiconductor materials based on metal oxides, their catalytic properties, and their application as gas sensors, which were shown to exhibit high sensitivity, stability, and selectivity to target gases. The aim of this work is the comparison of gas sensing properties of tin dioxide in the form of individual nanowires and nanopowders obtained by sol-gel synthesis. This comparison is necessary because the traditional synthesis procedures of small particle, metal oxide materials seem to be approaching their limit. Because of this, there is increasing interest in the fabrication of functional materials based on nanowires, i.e., quasi-one-dimensional objects. In this work, nanocrystalline tin dioxide samples with different morphology were synthesized. The gas-transport method was used for the fabrication of well-faceted wire-like crystals with diameters ranging between 15-100 nm. The sol-gel method allowed us to obtain fragile gels from powders with grain sizes of about 5 nm. By means of X-ray photoelectron spectroscopy (XPS) it was proven that the nanowires contain considerably smaller amounts of hydroxy groups compared to the nanopowders. This leads to a decrease in the parasitic sensitivity of the sensing materials to humidity. In addition, we demonstrated that the nanowires are characterized by a nearly single-crystalline structure, ensuring higher stability of the sensor response due to the unlikelihood of sample recrystallization. The results from the ammonia detection experiments showed that the ratio of the sensor response to the surface area exhibits similar values for both the individual nanowire and nanopowders-based sensor materials.

Highly Sensitive Air-Stable Easily Processable Gas Sensors Based on Langmuir-Schaefer Monolayer Organic Field-Effect Transistors for Multiparametric H2S and NH3 Real-Time Detection.

A combination of low limit of detection, low power consumption, and portability makes organic field-effect transistor (OFET) chemical sensors promising for various applications in the areas of industrial safety control, food spoilage detection, and medical diagnostics. However, the OFET sensors typically lack air stability and restoration capability at room temperature. Here, we report on a new design of highly sensitive gas sensors based on Langmuir-Schaefer monolayer organic field-effect transistors (LS OFETs) prepared from organosilicon derivative of [1]benzothieno[3,2- b][1]-benzothiophene. The devices fabricated are able to operate in air and allow an ultrafast detection of different analytes at low concentrations down to tens of parts per billion. The sensors are reusable and can be utilized in real-time air-quality monitoring systems. We show that a direct current response of the LS OFET can be split into the alteration of various transistor parameters, responsible for the interactions with different toxic gases. The sensor response acquiring approach developed allows distinguishing two different gases, H2S and NH3, with a single sensing device. The results reported open new perspectives for the OFET-based gas-sensing technology and pave the way for easy detection of the other types of gases, enabling the development of complex air analysis systems based on a single sensor.