Herein, the polycrystalline CuCr2O4 (CCO) electro-ceramic was prepared via the sol-gel self-combustion route. The X-ray powder diffraction analysis at room temperature revealed that the CCO chromite was synthesized in a single phase tetragonally distorted normal spinel structure with I41/amd space group. Transmission electron microscopy (TEM) and selected area electron diffraction (SAED) investigated the polycrystalline nature of the compound. The microstructural analysis by field emission scanning electron microscopy (FESEM) explored the surface morphology of micron-sized grains (Gs) distinguished by well-pronounced grain boundaries (GBs) available for electrical response of the material. The color mapping images of elements by energy-dispersive X-ray spectroscopy (EDS) divulged the homogeneous distribution of elements in the compound. The surface chemistry of the compound was studied by X-ray photoelectron spectroscopy (XPS). This information helped in understanding the electronic states of the ions contributing to the electrical networks and mechanisms responsible for the charge transport within the CCO system. The dielectric relaxation and electrical transport properties were analyzed using complex impedance spectroscopy (CIS) over the experimental range of frequency and temperature from 40 Hz to 1 MHz and 243–493 K, respectively. The experimental complex impedance data were analyzed by RGQGRGBQGB equivalent circuit model which resolved the electro-active contributions of bulk and interface of the CCO spinel to its electrical dynamics. The dispersion in AC conductivity was explained by Jonscher's double power law which provided evidence of small polaron hopping (SPH) as a dominant transport mechanism governing electrical conduction in the compound. The temperature-dependent DC conductivity pattern exhibited an Arrhenius-like behavior that followed Mott and Davis's model of SPH. The analysis of complex electrical modulus M*(ω,T) professed the localized and de-localized movements of the charge carriers. The dielectric permittivity response of CCO followed Havriliak-Negami (HN) phenomenology that divulged the existence of non-Debye type dielectric relaxation processes. The interfacial polarization was observed to be accountable for the dispersion in dielectric loss spectra.
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