Information
about the surrounding atmosphere at a real timescale
significantly relies on available gas sensors to be efficiently combined
into multisensor arrays as electronic olfaction units. However, the
array’s performance is challenged by the ability to provide
orthogonal responses from the employed sensors at a reasonable cost.
This issue becomes more demanded when the arrays are designed under
an on-chip paradigm to meet a number of emerging calls either in the
internet-of-things industry or in situ noninvasive diagnostics of
human breath, to name a few, for small-sized low-powered detectors.
The recent advances in additive manufacturing provide a solid top-down
background to develop such chip-based gas-analytical systems under
low-cost technology protocols. Here, we employ hydrolytically active
heteroligand complexes of metals as ink components for microplotter
patterning a multioxide combinatorial library of chemiresistive type
at a single chip equipped with multiple electrodes. To primarily test
the performance of such a multisensor array, various semiconducting
oxides of the p- and n-conductance
origins based on pristine and mixed nanocrystalline MnO
x
, TiO2, ZrO2, CeO2, ZnO, Cr2O3, Co3O4,
and SnO2 thin films, of up to 70 nm thick, have been printed
over hundred μm areas and their micronanostructure and fabrication
conditions are thoroughly assessed. The developed multioxide library
is shown to deliver at a range of operating temperatures, up to 400
°C, highly sensitive and highly selective vector signals to different,
but chemically akin, alcohol vapors (methanol, ethanol, isopropanol,
and n-butanol) as examples at low ppm concentrations
when mixed with air. The suggested approach provides us a promising
way to achieve cost-effective and well-performed electronic olfaction
devices matured from the diverse chemiresistive responses of the printed
nanocrystalline oxides.
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).
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