Pressure Tuning the Mixture of Eu${}^{2+}$ and Eu${}^{3+}$ in Eu${}_4$Bi${}_6$Se${}_{13}$

Abstract

The investigation of crystallographic, electronic, and magnetic characteristics, especially the mixed valences of Eu${}^{2+}$ and Eu${}^{3+}$ under pressure of a novel europium-based bismuth selenide compound, Eu${}_4$Bi${}_6$Se${}_{13}$, presented. This new compound adopts a monoclinic crystal structure classified under the P$2_1$/m space group (#11). It exhibits distinctive structural features, including substantial Eu-Se coordination numbers, Bi-Se ladders, and linear chains of Eu atoms that propagate along the b-axis. Electronic resistivity assessments indicate that Eu${}_4$Bi${}_6$Se${}_{13}$ exhibits weak metallic behaviors. Magnetic characterization reveals uniaxial magnetic anisotropy, with a notable spin transition at approximately 1.2 T when the magnetic field is oriented along the b-axis. This behavior, coupled with the specific Eu-Eu interatomic distances and the magnetic saturation observed at low fields, supports the identification of metamagnetic properties attributable to the flipping of europium spins. The Curie-Weiss analysis of the magnetic susceptibility measured both perpendicular and parallel to the b-axis and high-pressure partial fluorescence yield (PFY) results detected by X-ray absorption spectroscopy (XAS) reveal the tendency of the material to enter a mixed valent state where the trivalent state becomes more prominent with the pressure increase or temperature decrease.

22 pages 8 figures