Effect of rare earth (Ho and Er) co-substitution on the magnetic and dielectric properties of nanocrystalline cobalt ferrites

Abstract

Nanocrystalline cobalt ferrites co-substituted with rare earth Ho and Er (CoFe2-2xHoxErxO4, 0 ≤x≤0.10) have been synthesized via the sol-gel method. X-ray Diffraction (XRD) confirmed the single-phase spinel structure with reduced crystallite sizes (65 nm–12 nm), micro-strain (ε) and increased lattice constant (a) with Ho–Er co-substitution. Rietveld refinement and theoretical computation revealed Ho and Er occupancy at octahedral sites and Fe and Co ions redistribution between the tetrahedral and octahedral sites. Infrared spectroscopy, Field Emission Scanning Electron Microscopy (FESEM), Energy Dispersive X-ray spectroscopy (EDX) and X-ray Photoelectron Spectroscopy (XPS) supported the formation of the desired spinel structure, aggregated spherical morphology, chemical stoichiometry and elemental states. Magnetic measurements showed a systematic decrease in saturation magnetization (Ms), magnetocrystalline anisotropy (K1), coercivity (Hc) and Curie temperature (Tc) with Ho–Er co-substitution. Electron Spin Resonance (ESR) exhibited asymmetric resonance peaks, reduced resonance field (Hr), linewidth (ΔHpp) and deviation in Lande g values. Impedance spectroscopy revealed two conduction mechanisms (holes and electrons) with distinct activation energies (EaI and EaII). Modulus spectrum analysis confirmed the thermally activated sample-electrode effects and the Nyquist plots indicated the dominant contribution of the grain boundary resistance to the conduction process. A notable enhancement in the dielectric constant (ε′) was observed with Ho–Er co-substitution. The ac conductivity (σac) followed the Jonscher Power Law (JPL). The temperature-dependent frequency exponent s(T), suggests the existence of two conduction mechanisms: non-overlapping small polaron tunneling (NSPT) and correlated barrier hopping (CBH).