Solution precursor synthesis and magnetic properties of Eu1−xCaxTiO3

Europium titanate, EuTiO₃, is a paraelectric/antiferromagnetic cubic perovskite with T_N=5.5 K. It is predicted that compressive strain could induce simultaneous ferroelectricity and ferromagnetism in this material, leading to multiferroic behavior. As an alternative to epitaxial strain, we explored lattice contraction via chemical substitution of Eu²⁺ with the smaller Ca²⁺ cation as a mechanism to tune the magnetic properties of EuTiO₃. A modified sol-gel process was used to form homogeneously mixed precursors containing Eu³⁺, Ca²⁺, and Ti⁴⁺, and reductive annealing was used to transform these precursors into crystalline powders of Eu_1−xCa_xTiO₃ with x=0.00, 0.05, 0.10, 0.15, 0.25, 0.35, 0.50, 0.55, 0.60, 0.65, 0.80, and 1.00. Powder XRD data indicated that a continuous Eu_1−xCa_xTiO₃ solid solution was readily accessible, and the lattice constants agreed well with those predicted by Vegard's law. SEM imaging and EDS element mapping indicated a homogeneous distribution of Eu, Ca, and Ti throughout the polycrystalline sample, and the actual Eu:Ca ratio agreed well with the nominal stoichiometry. Measurements of magnetic susceptibility vs. temperature indicated antiferromagnetic ordering in samples with x≤0.60, with T_N decreasing from 5.4 K in EuTiO₃ to 2.6 K in Eu_0.40Ca_0.60TiO₃. No antiferromagnetic ordering above 1.8 K was detected in samples with x>0.60.