Role of structure imperfection in the formation of the magnetotransport properties of rare-earth manganites with a perovskite structure

The structure, the structure imperfection, and the magnetoresistance, magnetotransport, and microstructure properties of rare-earth perovskite La_0.3Ln_0.3Sr_0.3Mn_1.1O_3–δ manganites are studied by X-ray diffraction, thermogravimetry, electrical resistivity measurement, magnetic, ⁵⁵Mn NMR, magnetoresistance measurement, and scanning electron microscopy. It is found that the structure imperfection increases, and the symmetry of a rhombohedrally distorted R3̅c perovskite structure changes into its pseudocubic type during isovalent substitution for Ln = La³⁺, Pr³⁺, Nd³⁺, Sm³⁺, or Eu³⁺ when the ionic radius of an A cation decreases. Defect molar formulas are determined for a real perovskite structure, which contains anion and cation vacancies. The decrease in the temperatures of the metal–semiconductor (T_ms) and ferromagnet–paramagnet (T_C) phase transitions and the increase in electrical resistivity ρ and activation energy E_a with increasing serial number of Ln are caused by an increase in the concentration of vacancy point defects, which weaken the double exchange 3d⁴(Mn³⁺)–2p⁶(O^2–)–3d³(Mn⁴⁺)–V^(a)–3d⁴(Mn³⁺). The crystal structure of the compositions with Ln = La contains nanostructured planar clusters, which induce an anomalous magnetic hysteresis at T = 77 K. Broad and asymmetric ⁵⁵Mn NMR spectra support the high-frequency electronic double exchange Mn³⁺(3d⁴) ↔ O^2–(2p⁶) ↔ Mn⁴⁺(3d³) and indicate a heterogeneous surrounding of manganese by other ions and vacancies. A correlation is revealed between the tunneling magnetoresistance effect and the crystallite size. A composition–structure imperfection–property experimental phase diagram is plotted. This diagram supports the conclusion about a strong influence of structure imperfection on the formation of the magnetic, magnetotransport, and magnetoresistance properties of rare-earth perovskite manganites.