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.

Microplotter printing of planar solid electrolytes in the CeO2-Y2O3 system.

The formation process for planar solid electrolytes in the CeO2-Y2O3 system has been studied using efficient, high-performance, high-resolution microplotter printing technology, using functional ink based on nanopowders (the average size of crystallites was 12-15 nm) of a similar composition obtained by programmed coprecipitation of metal hydroxides. The dependence of the microstructure of the oxide nanoparticles obtained and their crystal structure on yttrium concentration has been studied using a wide range of methods. According to X-ray diffraction (XRD), the nanopowders and coatings produced are single-phase, with a cubic crystal structure of the fluorite type, and the electronic state and content of cerium and yttrium in the printed coatings have been determined using X-ray photoelectron spectroscopy (XPS). The results of scanning electron (SEM) and atomic force microscopy (AFM) have shown that the coatings produced are homogeneous, they do not contain defects in the form of fractures and the height difference over an area of 1 µm2 is 30-45 nm. The local electrophysical characteristics of the oxide coatings produced (the work function of the coating surface, capacitance values, maps of the surface potential and capacitive contrast distribution over the surface) have been studied using Kelvin-probe force microscopy (KPFM) and scanning capacitive microscopy (SCM). Using impedance spectroscopy, the dependence of the electrophysical characteristics of printed planar solid electrolytes in the CeO2-Y2O3 system on yttrium content has been determined and the prospects of the technology developed for the manufacture of modern, intermediate-temperature, solid oxide fuel cells have been demonstrated.

Hydrothermal Synthesis of Ag Thin Films and Their SERS Application.

In this article, a facile, one-step method for the formation of silver thin-film nanostructures on the surface of Al2O3 substrates using the hydrothermal method is proposed. The dependence of the SERS effect intensity of the formed films during the detection of methylene blue (MB) low concentrations on the synthesis conditions, additional temperature treatment, and laser radiation wavelength (532 and 780 nm) in comparison with similar dye films on commercial SERS substrates is shown. The detection limit of the analyte used for the indicated lasers is estimated. The effect of the synthesis temperature on the particle size, crystal structure, and microstructure features of the obtained thin films based on silver nanoparticles is demonstrated. Using spreading resistance microscopy, the interface between the substrate and Ag particles is studied, and the dependence of the size of the corresponding gap between them and the nature of microstructural defects on the parameters of hydrothermal treatment of reaction systems in the presence of Al2O3 substrates is shown. As a result of the study, the factors associated with the properties of the obtained SERS substrates and the parameters of recording the spectra, which affect the amplification factor of the spectral lines intensity of the analyte, are revealed.

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.

Microplotter-Printed On-Chip Combinatorial Library of Ink-Derived Multiple Metal Oxides as an "Electronic Olfaction" Unit.

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 MnOx, 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.