Multioxide combinatorial libraries: fusing synthetic approaches and additive technologies for highly orthogonal electronic noses.

This study evaluates the performance advancement of electronic noses, on-chip engineered multisensor systems, exploiting a combinatorial approach. We analyze a spectrum of metal oxide semiconductor materials produced by individual methods of liquid-phase synthesis and a combination of chemical deposition and sol-gel methods with hydrothermal treatment. These methods are demonstrated to enable obtaining a fairly wide range of nanomaterials that differ significantly in chemical composition, crystal structure, and morphological features. While synthesis routes foster diversity in material properties, microplotter printing ensures targeted precision in making on-chip arrays for evaluation of a combinatorial selectivity concept in the task of organic vapor, like alcohol homologs, acetone, and benzene, classification. The synthesized nanomaterials demonstrate a high chemiresistive response, with a limit of detection beyond ppm level. A specific combination of materials is demonstrated to be relevant when the number of sensors is low; however, such importance diminishes with an increase in the number of sensors. We show that on-chip material combinations could favor selectivity to a specific analyte, disregarding the others. Hence, modern synthesis methods and printing protocols supported by combinatorial analysis might pave the way for fabricating on-chip orthogonal multisensor systems.

Atmospheric Pressure Solvothermal Synthesis of Nanoscale SnO2 and Its Application in Microextrusion Printing of a Thick-Film Chemosensor Material for Effective Ethanol Detection.

The atmospheric pressure solvothermal (APS) synthesis of nanocrystalline SnO2 (average size of coherent scattering regions (CSR)-7.5 ± 0.6 nm) using tin acetylacetonate as a precursor was studied. The resulting nanopowder was used as a functional ink component in microextrusion printing of a tin dioxide thick film on the surface of a Pt/Al2O3/Pt chip. Synchronous thermal analysis shows that the resulting semiproduct is transformed completely into tin dioxide nanopowder at 400 °C within 1 h. The SnO2 powder and the resulting film were shown to have a cassiterite-type structure according to X-ray diffraction analysis, and IR spectroscopy was used to establish the set of functional groups in the material composition. The microstructural features of the tin dioxide powder were analyzed using scanning (SEM) and transmission (TEM) electron microscopy: the average size of the oxide powder particles was 8.2 ± 0.7 nm. Various atomic force microscopy (AFM) techniques were employed to investigate the topography of the oxide film and to build maps of surface capacitance and potential distribution. The temperature dependence of the electrical conductivity of the printed SnO2 film was studied using impedance spectroscopy. The chemosensory properties of the formed material when detecting H2, CO, NH3, C6H6, C3H6O and C2H5OH, including at varying humidity, were also examined. It was demonstrated that the obtained SnO2 film has an increased sensitivity (the sensory response value was 1.4-63.5) and selectivity for detection of 4-100 ppm C2H5OH at an operating temperature of 200 °C.

Printing Technologies as an Emerging Approach in Gas Sensors: Survey of Literature.

Herein, we review printing technologies which are commonly approbated at recent time in the course of fabricating gas sensors and multisensor arrays, mainly of chemiresistive type. The most important characteristics of the receptor materials, which need to be addressed in order to achieve a high efficiency of chemisensor devices, are considered. The printing technologies are comparatively analyzed with regard to, (i) the rheological properties of the employed inks representing both reagent solutions or organometallic precursors and disperse systems, (ii) the printing speed and resolution, and (iii) the thickness of the formed coatings to highlight benefits and drawbacks of the methods. Particular attention is given to protocols suitable for manufacturing single miniature devices with unique characteristics under a large-scale production of gas sensors where the receptor materials could be rather quickly tuned to modify their geometry and morphology. We address the most convenient approaches to the rapid printing single-crystal multisensor arrays at lab-on-chip paradigm with sufficiently high resolution, employing receptor layers with various chemical composition which could replace in nearest future the single-sensor units for advancing a selectivity.

Pen plotter printing of ITO thin film as a highly CO sensitive component of a resistive gas sensor.

In2O3-10%SnO2 (ITO) thin films on various substrates have been obtained by pen plotter printing using a solution of hydrolytically active heteroligand complexes [M(C5H7O2)x(C4H9O)y] (where М = In3+ and Sn4+) as a functional ink. According to XRD and Raman spectroscopy, it has been established that the film has a bixbyite structure (space group Ia3/Th7), consists of particles with an average size of about 20 nm (according to SEM and AFM) and has a band gap of 3.57 eV. In order to obtain the ITO film, the temperature dependence of resistivity characterised by a minimum at 150 °C has been determined, and its gas-sensitive properties have been studied. It has been shown that the greatest resistive response is observed to carbon monoxide at 200 °C, and the film has a high sensitivity to low concentrations of CO. Two possible models describing the dependence of the sensory response on the CO concentration have been suggested. The mechanisms of defect formation in the ITO film structure and CO detection, including in a humid environment, have been considered in detail.