Nanocrystalline tin dioxide (SnO(2)) ultra-thin films were obtained employing a straightforward solution-based route that involves the calcination of bridged polystannoxane films processed by the sol-gel process from bis(triprop-1-ynylstannyl)alkylene and -arylene precursors. These films have been thoroughly characterized by FTIR, contact angle measurements, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force (AFM) and scanning electron (SEM) microscopies. Annealing at a high temperature gave 30-35 nm thick cassiterite SnO(2) films with a mean crystallite size ranging from 4 to 7 nm depending on the nature of the organic linker in the distannylated compound used as a precursor. In the presence of H(2) and CO gases, these layers led to highly sensitive, reversible and reproducible responses. The sensing properties were discussed in regard to the crystallinity and porosity of the sensing body that can be tuned by the nature of the precursor employed. Organometallic chemistry combined with the sol-gel process therefore offers new possibilities toward metal oxide nanostructures for the reproducible and sensitive detection of combustible and toxic gases.
Hydrolysis-condensation of bis(triprop-1-ynylstannyl)butylene led to nanostructured bridged polystannoxane films yielding tin dioxide thin layers upon UV-treatment or annealing in air. According to Fourier transform infrared (FTIR) spectroscopy, contact angle measurements, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning electron microscopy (SEM) data, the films were composed of a network of aggregated "pseudo-particles", as calcination at 600 °C is required to form cassiterite nanocrystalline SnO2 particles. In the presence of reductive gases such as H2 and CO, these films gave rise to highly sensitive, reversible, and reproducible responses. The best selectivity toward H2 was reached at 150 °C with the hybrid thin films that do not show any response to CO at 20-200 °C. On the other hand, the SnO2 films prepared at 600 °C are more sensitive to H2 than to CO with best operating temperature in the 300-350 °C range. This organometallic approach provides an entirely new class of gas-sensing materials based on a class II organic-inorganic hybrid layer, along with a new way to include organic functionality in gas sensing metal oxides.
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