Sol–gel synthesis and characterization of the delafossite CuAlO2

Abstract

Nanocrystalline CuAlO2 is synthesized by sol–gel method using ethylene glycol as solvent. The stages of formation are followed by thermal analysis. The X-ray diffraction pattern of the powder heat-treated at 1100 °C shows a single phase, indexed in a rhombohedral symmetry (R 3¯¯¯ m). The apparent crystallite size (57 ± 8 nm) is determined from the Williamson–Hall plot. The direct optical transition (=3.69 eV), evaluated from the diffuse reflectance spectrum, is attributed to the charge transfer (O2−: 2p → Cu+: 4s). The oxide is p-type semiconductor, and the conduction occurs predominantly by small polaron hopping between mixed valences Cu2+/+, due to oxygen insertion in the layered crystal. The photoelectrochemical characterization gives a flat band of 0.20 VSCE and a hole density of 1.13 × 1018 cm−3. The semicircle centered on the real axis, in the electrochemical impedance spectroscopy (EIS), is due to the absence of constant phase element with a pure capacitive behavior. The straight line at 35° at low frequencies is attributed to the diffusion in the layered structure.