Near-neighbour impurity effect on the spin-state transitions in LaCoO3 at low temperature (12<T<300 K)

Abstract

The low-temperature magnetic susceptibility behaviour of LaCoO3 prepared under different conditions as well as substituted samples such as LaCo0.95M0.05O3 (M=Al, Ga, Cr, Fe, Mn, Ni) and La0.98Sr0.02CoO3 have been investigated in the temperature range 12–300 K. Earlier interpretations of the magnetic susceptibility have been reexamined. In the case of LaCoO3 samples containing Al, Ga, Cr and Fe impurities spin-state transitions involving a temperature independent activation energy (∼0.01 eV) are observed atT<200 K. Analysis of the data indicates that either the excited state has an intermediate-spin (t 2g 5 e g 1 ) configuration or only half the Co ions are involved in the activated transition to the high-spin (t 2g 4 e g 2 ) configuration. Al3+, and Cr3+ increases the activation energy considerably. Substitution of L ≠ 0 ions such as Mn3+ and Ni3+ or Co4+ (low-spin) seems to introduce ferromagnetic interactions and stabilizes the paramagnetic state. LaCoO3, when Co is substituted by Mn (5%) or La is substituted by Sr (2%) show giant magnetic moments. When Co is substituted by Ni (5%) a ferromagnetic ground state is observed.