Influence of particle sizes on the electronic behavior of ZnxCo1- xFe2O4 spinels (x=0.2, 0.3)

The effect of composition and particle size on the electrical and magnetic behavior of ZnxCo1 xFe2O4 spinels (x = 0.2 and 0.3) has been studied. Powdered samples of these ferrites have been synthetized by the liquid mix technique and hydrothermal method (in sub and supercritical conditions), leading to average particle sizes of ca. 50 and 10 nm, respectively. They have been characterized by means of X-ray diffraction, Thermogravimetric analysis, Energy-Dispersive X-ray Spectroscopy and impedance and magnetic measurements. Permittivity values up to ca. 500 were registered at 375 K, which remained almost constant at moderate frequencies, between 103 and 106 Hz. Stabilization of polarization phenomena is very sensitive to grain size and composition. Dielectric behavior evolves to a relaxor ferroelectric response when grain size becomes nanometric and, particularly, when the sample shows high monodispersion. The conduction mechanism and type of majority charge carriers have been established from Seebeck measurements. The x = 0.3 sample, prepared in supercritical water for the first time, exhibits homogeneous particle size distribution, superparamagnetic behavior and Curie temperature lower than those corresponding to similar microsized samples. The electronic response of the ferrites obtained in supercritical conditions is interpreted considering the possible short scale polarization of nanodomains. (c) 2014 Elsevier B. V. All rights reserved.