Probing the incoherent admixture of low and high-spin states of Co in (LaPr)CoO3 perovskite: focus on structural phase transitions

Abstract

We report the mixed valence and intermediate spin-state (IS) transitions in Pr substituted LaCoO3 perovskites in the form of bulk and nanostructures. Various compositions (x) of La1−x Pr x CoO3 (0 ⩽ x⩽ 0.9) were synthesized using the sol–gel process under moderate heat treatment conditions (600 °C). The structural analysis of these compounds reveals a phase crossover from the monoclinic phase (space group, s.g.: I2/a) to an orthorhombic one (s.g.: Pbnm), and a rhombohedral phase (s.g.: R-3c) to an orthorhombic one (s.g.: Pnma) in the bulk and nanostructures, respectively, for the composition range 0 ⩽ x⩽ 0.6. Such a structural transformation remarkably reduces the Jahn–Teller distortion factor ΔJT: 0.374 → 0.0016 signifying the dominant role of the IS state (S Avg = 1) of trivalent Co ions in the investigated system. Magnetization measurements reveal the ferromagnetic (FM) nature of bulk LaCoO3 along with a weak antiferromagnetic (AFM) component coexisting with an FM component. This coexistence results in a weak loop-asymmetry (zero-field exchange-bias effect ∼134 Oe) at low temperatures. Here the FM ordering occurs due to the double-exchange interaction (J EX /k B∼ 11.25 K) between the tetravalent and trivalent Co ions. Significant decrease in the ordering temperatures was noticed in the nanostructures (T C ∼ 50 K) as compared to the bulk counterpart (∼90 K) due to the finite size/surface effects in the pristine compound. However, the incorporation of Pr leads to the development of a strong AFM component (J EX/k B ∼ 18.2 K) and enhances the ordering temperatures (∼145 K for x = 0.9) with negligible FM correlations in both bulk and nanostructures of LaPrCoO3 due to the dominant super-exchange interaction: Co3+/4+‒O‒Co3+/4+. Further evidence of the incoherent mixture of low-spin (LS) and high-spin (HS) states comes from the M–H measurements which yields a saturation magnetization of M S ∼ 275 emu mol−1 (under the limit of 1/H → 0) consistent with the theoretical value of 279 emu mol−1 corresponding to the spin admixture: 65% LS + 10% IS of trivalent Co along with 25% of LS Co4+ in the bulk pristine compound. A similar analysis yields: Co3+ [30% LS + 20% IS] + Co4+ [50% of LS] for the nanostructures of LaCoO3, yet the Pr substitution decreases the spin admixture configuration. The Kubelka–Munk analysis of the optical absorbance results in a significant decrease in the optical energy band gap (E g:1.86 → 1.80 eV) with the incorporation of Pr in LaCoO3 which corroborates the above results.