Abstract

The results of experimental investigation of the chemical phase composition, crystal structure, and magnetic properties of the manganite La0.70Sr0.30MnO3−γ (0 ≤ γ ≤ 0.25) with perovskite structure depending on the concentration of oxygen vacancies are presented. It is found that the mean grain size of the stoichiometric solid solution of La0.70Sr0.30MnO3 amounts approximately to 10 μm, while the grain size for anion-deficient solid solutions of La0.70Sr0.30MnO3−γ is approximately 5 μm. It is found that samples with 0 ≤ γ ≤ 0.13 have a rhombohedral unit cell (with space group $$R\bar 3c$$ , Z = 2), while samples with γ ≥ 0.20 have a tetragonal unit cell (space group I4/mcm, Z = 2). It is proved experimentally that the magnetic phase state of the manganite La0.70Sr0.30MnO3−γ changes upon a decrease in the oxygen content. It is shown that anion-deficient solid solutions of La0.70Sr0.30MnO3−γ experience a number of successive magnetic phase transformations in the ground state from a ferromagnet (0 ≤ γ ≤ 0.05) to a charge-disordered antiferromagnet (γ = 0.25) via an inhomogeneous magnetic state similar to a cluster spin glass (0.13 ≤ γ ≤ 0.20). The mean size of ferromagnetic clusters (r ≈ 50 nm) in the spin glass state is estimated. It is shown that oxygen vacancies make a substantial contribution to the formation of magnetic properties of manganites. The generalized magnetic characteristics are presented in the form of concentration dependences of the spontaneous magnetic moment, coercive force, and the critical temperature of the magnetic transition. The most probable mechanism of formation of the magnetic phase state in Sr-substituted anion-deficient manganites is considered. It is assumed that in the absence of orbital ordering, a decrease in the magnetic ion coordination number leads to sign reversal in indirect superexchange interactions Mn3+-O-Mn3+.

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