Phys Chem Chem Phys. 2022 Aug 12. doi: 10.1039/d2cp01561g. Online ahead of print.
In the present decade, owing to half-metallic ferromagnetism, controlled 3d transition metal-doping based defect engineering in oxide perovskites attracts considerable attention in the pursuit of spintronics. We aim to investigate the electronic structure of Co-doped barium strontium titanate (Ba0.8Sr0.2CoxTi1-xO3 where x = 0, 0.1, 0.2) solid solution. Structural, vibrational and microscopic properties indicate the cationic substitution of Co at the octahedral Ti position along with a displacive kind of tetragonal-to-cubic phase transformation. X-ray photoelectron spectroscopy evidences the reduction in the valence state from Co3+ to Co2+ and Ti K edge X-ray absorption spectroscopy endorses the higher lattice symmetry with increasing Co doping. Orbital hybridization triggered electron hopping between O 2p and Co eg orbitals results in a spin fluctuation from the occupation t62ge0g for x = 0.1 to the occupation t62ge1gL for x = 0.20 (L designates a hole in the O 2p shell) aligned state observed from density functional theory calculations. The dominating crystal field energy as compared to intra-atomic exchange (Hund) energy decides the spin-orbital degeneracy for the Co 3d orbital to induce spin fluctuations.
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