High Zr doping effects on the microstructural and optical properties of Mn₃ O₄ thin films along with ethanol sensing

Transition metal oxides as transparent conducting oxides (TCOs) films, with high optical transparency (≥82%), various valence states and p-type conductivity are used in a several physical domains. This work covers the physical study of Zr doped Mn₃O₄ semiconductor thin films using a spray pyrolysis method where Zr content varies in starting solutions from 0 to 20at.%. The impact of this work is to offer some understanding of microscopic effects of relatively high doping Zr and then correlate these effects with the macroscopic properties for interesting applications especially gas sensor. In fact, the addition of Zr ions pointed out the reduction of crystallite size (24.1 (nm)) with 20at.% doping allowing a better adsorption of gas molecules. In addition, it promotes the increase of optical gap (2.92eV) with 6at.% doping which is a useful parameter for some optical devices. X-ray diffraction (XRD), Raman spectroscopy, FTIR spectroscopy, atomic force microscopy (AFM) and EDAX techniques were used. It is found that these films crystallized in spinel type tetragonal hausmmanite structure. The gas sensing activity of these thin films (0, 6, 12 and 20at.% Zr) was examined with Ethanol. The performances of these last four sensing layers were compared. All the tests were performed at different working temperatures T_work=125, 150, 175 and 225°C and under two gas concentrations: 0.1% and 0.5% ethanol using dry air as carrier gas. The films exhibited noticeably ethanol sensing especially the sample doped with 6% of zirconium exhibits the most excellent sensing performance since it showed a clear response already at a low ethanol concentration of 0.1%.