Transition to electron doping in La1−xCaxMnO3 manganite system: Size-induced effects on magnetic order, probed by electron resonance technique

The XX-band electron magnetic resonance was measured on nano-sized half-doped La0.5Ca0.5MnO3 and electron-doped La0.4Ca0.6MnO3 manganite compounds at 5–600 K temperature range. The electron paramagnetic resonance parameters were fitted with known theoretical models. The low temperature ferromagnetic resonance data were analyzed together with the results of neutron diffraction and magnetic measurements. The size effects in half-doped and electron-doped nano-powders are strongly different. A suppression of bulk-like antiferromagnetic/charge ordered component and stabilization of frustrated ferromagnetic-like (FM) order were found for Ca0.5 series, in which the core–shell interaction and a spin disorder at the surfaces weaken upon increase in grain size. However, well pronounced FM spin correlations in the paramagnetic state of Ca0.6 nano-crystals have not induced the FM long-range ordering. The local nature of double exchange coupling and the resulting localization of carriers in electron-doped compounds seem to be responsible for this effect.

► Temperature dependent XX-band EMR of nano-sized La0.5Ca0.5MnO3 and La0.4Ca0.6MnO3.
► Size effects in half-doped and electron-doped nano-powders are strongly different.
► Ca0.5: suppression of the bulk-like AFM/CO component and stabilization of FM order.
► Ca0.5: core–shell interaction and shell spin disorder weaken upon increase in grain size.
► Ca0.6: evident FM spin correlations in PM state do not induce long-range FM ordering.