A-Site Cation Size Effect on Structure and Magnetic Properties of Sm(Eu,Gd)Cr0.2Mn0.2Fe0.2Co0.2Ni0.2O3 High-Entropy Solid Solutions

Nanomaterials (Basel). 2021 Dec 23;12(1):36. doi: 10.3390/nano12010036.

Abstract

Three high-entropy Sm(Eu,Gd)Cr0.2Mn0.2Fe0.2Co0.2Ni0.2O3 perovskite solid solutions were synthesized using the usual ceramic technology. The XRD investigation at room temperature established a single-phase perovskite product. The Rietveld refinement with the FullProf computer program in the frame of the orthorhombic Pnma (No 62) space group was realized. Along with a decrease in the V unit cell volume from ~224.33 Å3 for the Sm-based sample down to ~221.52 Å3 for the Gd-based sample, an opposite tendency was observed for the unit cell parameters as the ordinal number of the rare-earth cation increased. The average grain size was in the range of 5-8 μm. Field magnetization was measured up to 30 kOe at 50 K and 300 K. The law of approach to saturation was used to determine the Ms spontaneous magnetization that nonlinearly increased from ~1.89 emu/g (Sm) up to ~17.49 emu/g (Gd) and from ~0.59 emu/g (Sm) up to ~3.16 emu/g (Gd) at 50 K and 300 K, respectively. The Mr residual magnetization and Hc coercive force were also determined, while the SQR loop squareness, k magnetic crystallographic anisotropy coefficient, and Ha anisotropy field were calculated. Temperature magnetization was measured in a field of 30 kOe. ZFC and FC magnetization curves were fixed in a field of 100 Oe. It was discovered that the Tmo magnetic ordering temperature downward-curve decreased from ~137.98 K (Sm) down to ~133.99 K (Gd). The spin glass state with ferromagnetic nanoinclusions for all the samples was observed. The <D> average and Dmax maximum diameter of ferromagnetic nanoinclusions were calculated and they were in the range of 40-50 nm and 160-180 nm, respectively. The mechanism of magnetic state formation is discussed in terms of the effects of the A-site cation size and B-site poly-substitution on the indirect superexchange interactions.

Keywords: crystal structure; high entropy perovskites; indirect superexchange interactions; magnetic properties; transition metals.