Enhancement of electrical conductivity in CoO - SiO₂ nanoglasses and large magnetodielectric effect in ZnO-nanoglass composites

Abstract

Nanoglasses of compositions xCoO·(100-x)SiO₂ (mol. %) with x having values 10, 15, and 20, respectively, were grown within the nanopores of a pellet comprising of ZnO nanoparticles by soaking the latter in a suitable sol followed by necessary heat treatment. Both Co²⁺ and Co³⁺ ions were present and confirmed by X-ray photoelectron spectroscopy, the fraction of Co²⁺ species being ∼ 0.70. Small polaron hopping conduction was found to be present in the nanoglasses. The activation energy in the latter was observed to be smaller (range of 0.32–0.44 eV) than that in the corresponding bulk glass (0.70–0.77 eV). This was caused by the higher free volume in the nanoglass as compared to that of the bulk glass. This was confirmed by the extracted values of intersite separation between cobalt ions, which were higher in the nanoglass. Weak ferromagnetism was exhibited by the nanocomposites. This was ascribed to super exchange interaction between spin moments associated with Co²⁺ and Co³⁺ ions, respectively, leading to an antiferromagnetic spin alignment. The nanocomposites showed magnetodielectric effect with the magnetodielectric parameter having values in the range of 5.5% to 10%. The experimental data were fitted to equations derived from Catalan's model by invoking a negative and a positive magnetoresistance for nanoglasses of compositions having x = 20 and x = 10, respectively. A weak spin-orbit coupling and wave function shrinkage in a magnetic field for strongly localized states, respectively, are believed to cause such behaviour in the nanoglass systems concerned. Direct magnetoresistance measurements were carried out on the nanocomposites containing nanoglasses having 10CoO and 20CoO, respectively. The trend of results obtained indeed confirmed the presence of positive and negative magnetoresistance in the two nanoglasses, respectively. The materials would be suitable for magnetic sensor applications.