Rational design, crystal structure, and frustrated magnetism of the Ge-containing YbFe2O4-type layered oxides In2Zn3−xCoxGeO8 (0 ≤ x ≤ 3)

Abstract

YbFe₂O₄-type layered oxides have attracted tremendous interest because the unique crystal comprises two distinct geometrically frustrated triangular cation-sublattices. Herein, a series of YbFe₂O₄-type materials In₂Zn_3−xCo_xGeO₈ (0 ≤ x ≤ 3) were rationally designed and experimentally synthesized for the first time. The crystal structures of In₂Zn_3−xCo_xGeO₈ were investigated comprehensively by Rietveld refinements against high-resolution monochromatic Cu K_α1 XRD data. Zn²⁺, Co²⁺, and Ge⁴⁺ cations are distributed randomly on the [MO]₂ bilayer and possess a trigonal bipyramid (TBP) coordination geometry. Because Co²⁺ has an unpaired electron in the d_z2 orbital and a larger electronegativity than Zn²⁺, Co²⁺-to-Zn²⁺ equivalent substitution in In₂Zn_3−xCo_xGeO₈ results in more compact MO₅-TBPs, which is the origin of anisotropic lattice expansion and contraction along the a and c axes, respectively. The Co²⁺ moments in the [MO]₂ bilayer are strongly AFM coupled and geometrically frustrated, therefore resulting in a spin-glass magnetic transition at around T_g = 20 K for In₂ZnCo₂GeO₈, while a long-range AFM ordering is established for In₂Co₃GeO₈ with a Néel temperature of 53 K, attributed to the significantly enhanced AFM interactions and increased In³⁺/Co²⁺ anti-site disordering, as compared to those in In₂ZnCo₂GeO₈.