Comparative study of structural and optical properties of zirconium-doped indium oxide synthesized by solid state reactions and sol-gel technique

In the present work the effect of zirconium doping (1.5 at.%) on the structural and optical properties of indium zirconium oxide was studied. Zr-doped indium oxides were prepared by using two different methods, solid state reactions and sol-gel technique. The compositions with bixbyite structure have been synthesized by two different methods, solid state reactions in air and sol-gel process. X-ray powder diffraction (XRPD) used for phases analysis confirm the validity of the cubic bixbyite-type structure of In2O3. The optical properties of the prepared composition were considered in terms of their diffuse reflectance spectra (DRS). The morphology of crystals was evidenced by SEM analyses and reveal agglomeration of particles with their size ranges in the micrometer domain. Introduction Transparent conducting oxides (TCOs) are an important class of materials which have attracted much attention in the last years due to their main properties, low resistivity and high optical transparency. The dominant TCOs are mainly zinc oxide (ZnO), indium oxide (In2O3) and tin oxide (SnO2), as well as subsequent mixtures of these, such as well-known indium tin oxide (ITO) [1]. In2O3, a wide-bandgap n-type semiconductor, is widely used in various applications due to their properties including solar applications, the transparent electrodes in various optoelectronic devices, the flat panel liquid crystals displays, the barrier layers in tunnel junctions, the active layers of gas sensors or the material for ultraviolet lasers [2]. Therefore, the physical properties of the In2O3, like high electrical conductivity and optical transparency in the visible range, strongly depend on the preparation method. For this reason there are many investigations which are studying their properties in dependence on the synthesis methods. These methods include physical methods such as sputtering, evaporation, pulsed laser deposition, spray pyrolysis, as well as chemical methods like chemical pyrolysis, chemical vapor deposition, sol-gel, bath deposition and electroplating [3–8]. On the other hand electrical properties of In2O3 can be improved by doping with metallic donor impurity. For this reason the system ZrO2–In2O3 was mostly investigated [810]. Powder Metallurgy and Advanced Materials – RoPM&AM 2017 Materials Research Forum LLC Materials Research Proceedings 8 (2018) 167-172 doi: http://dx.doi.org/10.21741/9781945291999-19 168 In the present paper we comparatively investigated the structural evolution, optical and morphological properties of indium zirconium oxide prepared by two methods, solid state synthesis and sol-gel route. Materials and Methods Synthesis Two different preparation methods were employed in the synthesis of zirconium-doped indium oxide: solid state synthesis and sol-gel method. Compositions belonging to In2-xZrxO3 (0.025 ≤ x ≤ 0.15) system with the bixbyite structure were prepared by solid state reactions from mixtures of pure In2O3 (Alfa Aesar 99.995%) and ZrO2 (Alfa Aesar 99%) at 1400 °C, in air. In the sol-gel synthesis indium (III) nitrate hydrate (In(NO3)2·xH2O) was used as a precursor and zirconium (IV) chloride (ZrCl4) as a doping source at the molar ratios required to obtain In2O3 doped with 1.5 at % ZrO2. Aqueous solutions of the two salts were stirred on a warming plate at 80 °C in order to mix the solution uniformly. The sol was prepared using isopropyl alcohol as solvent and ethylene glycol or sucrose as polymerization agent. The sucrose solution was added gradually into the aqueous solutions under stirring until colloidal suspensions were obtained. The sol continuously transformed into wet gel and then dried gel under heating at 100 °C during 24h. The resulted dried materials were annealed at 600 °C in air for one hour to form the required Zrdoped indium oxide. Fig. 1 presents schematic flow chart of indium zirconium oxide obtained by solid state synthesis.