Preferential site ordering alters the magnetic structure of Sm$_3$Ru$_4$Sn$_{13-x}$Ge$_x$ ($x = 0$-2)

Abstract

An important aspect of materials research is the ability to tune different physical properties through controlled alloying. The Ln$_3$M$_4$X$_{13}$ (Ln = Lanthanide, M = Transition Metal, X = Tetrel) filled skutterudite family is of interest due to the tunability of its constituent components and their effects on physical properties, such as superconductivity and complex magnetism. In this work, Sm$_3$Ru$_4$Sn$_{13-x}$Ge$_x$ (x = 0 -- 2) was synthesized via excess Sn-flux and characterized using powder and single-crystal X-ray diffraction, magnetometry, X-ray photoelectron spectroscopy, and heat capacity. Sm$_3$Ru$_4$Sn$_{13}$ and its Ge-solid-solution members crystallize in the Pm-3n space group, which has two unique Wyckoff positions for the tetrel (X) site. In the solid solution members, Ge shows preferential occupancy for one of the two Wyckoff sites, reaching $\sim$60$\%$ and 100$\%$ occupancy when x = 1 and 2, respectively. Magnetometry and heat capacity measurements of Sm$_3$Ru$_4$Sn$_{13}$ indicated antiferromagnetic ordering at $T_N$ = 7.3 K. However, Sm$_3$Ru$_4$Sn$_{12}$Ge and Sm$_3$Ru$_4$Sn$_{11}$Ge$_2$ showed notably lower-temperature antiferromagnetic phase transitions with substantial peak-broadening at $T_N$ = 5.5 K and 4.1 K, respectively. These data suggest that alloying Ge into Sm$_3$Ru$_4$Sn$_{13}$ causes magnetic frustration within the structure, likely attributable to a change in the density of states from additional Ge $p$ states at the Fermi level. This work demonstrates that preferentially alloying Ge in Sm$_3$Ru$_4$Sn$_{13-x}$Ge$_x$ allows for more precise tunability of its magnetic structure, elucidating design principles for different quantum phases in intermetallic materials.