Structure–composition sensitivity in “Metallic” Zintl phases: A study of Eu(Ga1−xTtx)2 (Tt=Si, Ge, 0≤x≤1)

Two isoelectronic series, Eu(Ga1−xTtx )2 (Tt =Si, Ge, 0≤x ≤1), have been synthesized and characterized by powder and single-crystal X-ray diffraction, physical property measurements, and electronic structure calculations. In Eu(Ga1−x Six )2, crystal structures vary from the KHg2-type to the AlB2-type, and, finally, the ThSi2-type structure as x increases. The hexagonal AlB2-type structure is identified for compositions 0.18(2)≤x <0.70(2) with Ga and Si atoms statistically distributed in the polyanionic 63 nets. As smaller Si atoms replace Ga atoms while the number of valence electrons increases, the lattice parameters, unit cell volumes, and Ga–Si distances in this phase region decrease significantly. Although aspects of X-ray diffraction results suggest puckering of the 63 nets for the Si-richest example of the AlB2-type Eu(Ga1−x Six )2, the complete experimental evidence remains inconclusive. On the other hand, in Eu(Ga1−x Gex )2, six different structural types were observed as x varies. In addition to EuGa2 (KHg2-type; space group Imma ) and EuGe2 (own structure type, space group P 3¯m 1), the ternary phases studied show four different structures: the AlB2-type for Ga-rich compositions; the YPtAs-type structure for EuGaGe; and two new structures, which are intergrowths of the YPtAs-type EuGaGe and EuGe2, for Ge-rich compositions. These two Ge-rich phases include: (1) Eu(Ga0.45(2)Ge0.55(2))2 containing two YPtAs-type motifs of EuGaGe plus one EuGe2 motif; and (2) Eu(Ga0.40(2)Ge0.60(2))2 containing one YPtAs-type motif alternating with a split site at View the MathML source