Non-stoichiometry, structural defects and properties of LaMnO3+δ with high δ values (0.11≤δ≤0.29)

Abstract

Strongly oxygenated LaMnO_3+δperovskites, with nominal Mn^IV contents up to 58%, have been prepared by thermal decomposition of metal citrates followed by annealings either in air or under high oxygen pressure (200 bar). A high-resolution neutron powder diffraction study of four representative samples with 0.11≤δ≤0.29 reveals the presence of both La and Mn vacancies. Contrary to previous studies, it is found that there are a substantially higher proportion of Mn vacancies, depending rather sensitively on the oxidation conditions. The oxidation state for Mn calculated for the refined stoichiometry La_1–xMn_1–yO₃ is in good agreement with the δ values previously determined by thermal analysis. Further to this, it is also found that as δ increases the Mn–O bond lengths shorten, the Mn–O–Mn angles progressively increase and the perovskite structure becomes more regular, which is consistent with the incorporation of Mn^IV cations. The presence of Mn vacancies (as much as 13% in samples prepared under high oxygen pressure) perturbs the conduction paths for the transport of holes across Mn–O–Mn, weakening the double-exchange interaction. This structural disorder explains the observed decrease of the ferromagnetic Curie temperature (T_C) as δ increases.