Comprehensive analysis on the effect of ionic size and size disorder parameter in high entropy stabilized ferromagnetic manganite perovskite

Abstract

A series of high entropy manganites, $(5{A}_{0.2}){\mathrm{MnO}}_{3}$, were prepared with varying the average ionic radius, $\ensuremath{\langle}{r}_{A}\ensuremath{\rangle}$, and cationic size disorder, ${\ensuremath{\sigma}}^{2}$, on the $A$ site. All the samples were synthesized using the citrate sol-gel method. In all the compounds, the manganese valence was kept unaltered with reference to the conventional manganite ${\mathrm{La}}_{0.6}{\mathrm{Sr}}_{0.4}{\mathrm{MnO}}_{3}$, which is ferromagnetic with ${T}_{C}\ensuremath{\sim}365$ K. The ratio of manganese valance is found to be unaltered as confirmed using x-ray photoelectron studies. The samples were characterized by powder x-ray diffraction, field-emission scanning electron microscopy (FE-SEM), energy dispersive x-ray analysis, elemental mapping, and magnetization measurements. These high entropy oxides show the variation in Curie temperature over a wide range from 85 to 273 K depending on the average $A$-site ionic radius, $\ensuremath{\langle}{r}_{A}\ensuremath{\rangle}$. A drastic drop down in the ferromagnetic transition temperature of ${T}_{C}=365$ K for ${\mathrm{La}}_{0.6}{\mathrm{Sr}}_{0.4}{\mathrm{MnO}}_{3}$ with $\ensuremath{\langle}{r}_{A}\ensuremath{\rangle}=1.2536\phantom{\rule{0.16em}{0ex}}\AA{}$ to ${T}_{C}=137\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ for (${\mathrm{La}}_{0.2}{\mathrm{Nd}}_{0.2}{\mathrm{Gd}}_{0.2}{\mathrm{Sr}}_{0.2}{\mathrm{Ba}}_{0.2}$)${\mathrm{MnO}}_{3}$ of comparable $\ensuremath{\langle}{r}_{A}\ensuremath{\rangle}=1.2532\phantom{\rule{0.16em}{0ex}}\AA{}$ can be attributed to the high entropy and/or cationic size disorder effect. The variation of ${T}_{C}$ with $\ensuremath{\langle}{r}_{A}\ensuremath{\rangle}$ for the whole series of high entropy manganites does not follow the expected linear behavior; rather, it follows opposite traces of the variation in ${\ensuremath{\sigma}}^{2}$ with $\ensuremath{\langle}{r}_{A}\ensuremath{\rangle}$. However, ${T}_{C}$ shows almost linear behavior with ${\ensuremath{\sigma}}^{2}$ except for the sample with lowest $\ensuremath{\langle}{r}_{A}\ensuremath{\rangle}$. This result suggests that the local cationic disordering is more important than the average cationic size in ferromagnetic high entropy manganites. Unlike the conventional system in these high entropy oxides, the ferromagnetic state is not suppressed; only the length scale of the double exchange mediated long-range ferromagnetic interaction is transformed to localized ferromagnetic clusters without losing the ferromagnetic identity. The presence of multiple $A$-site cations in high entropy oxides results in a local deformation of the ${\mathrm{MnO}}_{6}$ octahedra. This possibly increases the carrier localization followed by reducing the length scale of the double exchange interaction.