On the incorporation of nickel into hexagonal barium titanate: magnetic properties and electron paramagnetic resonance (EPR)

Abstract

Systematic measurements of the magnetic moment of hexagonal 6H-BaTiO3 + 0.04 BaO + x NiO (0.005 ≤ x ≤ 0.02) ceramics were performed to study the influence of Ni ions on the magnetic properties. By temperature-dependent measurements of the paramagnetic susceptibility at 90 kOe, the Ni2+ ion was identified as the majority defect in air-sintered Ni-doped hexagonal barium titanate. Q-band EPR investigations of a 2.0 mol% Ni-doped single crystal revealed three different Ni centers located at Ti sites: first, Ni3+ ions at Ti sites in intact oxygen octahedra, second, Ni3+ associated with an oxygen vacancy and third, the presence of Ni2+ centers leading to a forbidden transition. The Ni3+—VO associate characterized by a vacancy in the face-sharing oxygen plane of the oxygen octahedra can be ruled out. The crystal field parameters of the Ni2+ defect were estimated by a combined fitting of the paramagnetic susceptibility and the EPR fine structure parameter D to $$B_{0}^{4}$$ B 0 4 ≈ −17,300 cm−1, $$\left| {B_{0}^{2} } \right|$$ B 0 2 ≈ 2500 cm−1 and $$B_{3}^{4}$$ B 3 4 ≈ 19,000 cm−1.

Ruddlesden–Popper Oxyfluorides La2Ni1–xCuxO3F2 (0 ≤ x ≤ 1): Impact of the Ni/Cu Ratio on the Thermal Stability and Magnetic Properties

“…This is not surprising because for both ions crystal field effects need to be taken into account. While in a (basically) octahedral coordination, increased μ B values are expected (as found, e.g., for Ni 2+ in 6H-BaTiO 3 ); the situation becomes more complex for crystal fields of lower symmetry. Furthermore, the underlying models are valid only for diluted magnetic systems, whereas strong interionic interactions occur in the materials studied here.…”