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).
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.
We have applied spark ablation technology for producing nanoparticles from platinum ingots (purity of 99.97 wt. %) as a feed material by using air as a carrier gas. A maximum production rate of about 400 mg/h was achieved with an energy per pulse of 0.5 J and a pulse repetition rate of 250 Hz. The synthesized nanomaterial, composed of an amorphous platinum oxide PtO (83 wt. %) and a crystalline metallic platinum (17 wt. %), was used for formulating functional colloidal ink. Annealing of the deposited ink at 750 °C resulted in the formation of a polycrystalline material comprising 99.7 wt. % of platinum. To demonstrate the possibility of application of the formulated ink in printed electronics, we have patterned conductive lines and microheaters on alumina substrates and 20 μm thick low-temperature co-fired ceramic (LTCC) membranes with the use of aerosol jet printing technology. The power consumption of microheaters fabricated on LTCC membranes was found to be about 140 mW at a temperature of the hot part of 500 °C, thus allowing one to consider these structures as promising micro-hotplates for metal oxide semiconductor (MOS) gas sensors. The catalytic activity of the synthesized nanoparticles was demonstrated by measuring the resistance transients of the non-sintered microheaters upon exposure to 2500 ppm of hydrogen.
In this paper, we describe a technique for the qualitative and quantitative analysis of such gas mixtures as “hydrogen sulfide in air” and “methane in air” using temperature modulation of a single metal oxide sensor. Using regression analysis in the principal components plane (PC1, PC2), we performed a selective determination of analytes on the minimum set of their concentrations in the training set, which is essential for solving practical problems. An important feature of this work is the difference in test gas concentrations from their concentrations in the training set. For the qualitative analysis of gas mixtures in a wide range of concentrations, we have developed an improved method for processing arrays of multidimensional data. For this improvement, we form a Mahalanobis neighborhood for polynomial regression lines constructed from the projection of training samples for each analyte on the (PC1, PC2) plane. Using the temperature modulation mode for the metal oxide sensor allowed us to increase its response when determining hydrogen sulfide by two to four orders of magnitude compared with the constant temperature mode.