Sol-gel TiO2 films as NO2 gas sensors

TiO2 films were prepared by a sol-gel technique with commercial TiO2 powder as a source material (P25 Degussa AG). After a special treatment, printing paste was prepared. The TiO2 layers were formed by means of drop-coating on Si-control wafers and on the Au-electrodes of quartz resonators. The surface morphology of the films was examined by scanning electron microscopy (SEM). Their structure was studied by Raman spectroscopy and the surface composition was determined by X-ray photoelectron spectroscopy (XPS). The layers had a grain-like surface morphology and consisted mainly of anatase TiO2 phase. The sensitivity of the TiO2 films to NO2 was assessed by the quartz crystal microbalance (QCM) technique. To this end, the films were deposited on both sides of a 16-MHz QCM. The sensing characteristic of the TiO2-QCM structure was investigated by measuring the resonant frequency shift (Delta F) of the QCM due to the mass loading caused by NO2 adsorption. The Sauerbrey equation was applied to establish the correlation between the QCM frequency changes measured after exposure to different NO2 concentrations and the mass-loading of the QCM. The experiments were carried out in a dynamic mode on a special laboratory setup with complete control of the process parameters. The TiO2 films were tested in the NO2 concentration interval from 10 ppm to 5000 ppm. It was found that a TiO2 loading of the QCM by 5.76 kHz corresponded to a system sensitive to NO2 concentrations above 250 ppm. On the basis of the frequency-time characteristics (FTCs) measured, Delta F at different NO2 concentrations was defined, the adsorption/desorption cycles were studied and the response and recovery times were estimated. The results obtained show that the process is reversible in the NO2 interval investigated. The results further suggested that TiO2 films prepared by a sol-gel method on a QCM can be used as a sensor element for NO2 detection.