Structural modulations in the rare-earth metal digermanides REAl1-xGe2 (RE = Gd-Tm, Lu, Y; 0.8 < x < 0.9). Correlations between long- and short-range vacancy ordering.

Abstract

Rare-earth metal aluminum germanides with the general formula REAl(1-x)Ge(2) (RE = Gd, Tb, Dy, Ho, Er, Tm, Lu, and Y) have been synthesized by direct fusion of the corresponding elements. The structures have been studied by single-crystal X-ray diffraction and selected-area electron diffraction (SAED). The average structure represents a randomly "stuffed" variant of the orthorhombic ZrSi(2) structure type, also known as the CeNi(1-x)Si(2) type (Pearson symbol oC16; space group Cmcm). The SAED patterns for selected members of the family suggest the coexistence of commensurate and incommensurate structural modulations. The most prominent model for long-range vacancy ordering is the Tb(4)FeGe(8) type (Pearson symbol mP26; space group P21/n), which is the commensurate 4-fold superstructure of CeNi(1-x)Si(2) (x = (3)/4). Short-range correlations cause additional deviations in the 4-fold superlattice. These results shed more light on the structural complexity as a function of the aluminum vacancies and size of the rare-earth metal. Magnetic susceptibility measurements are presented and discussed. The measured ordering temperatures and calculated ones based on empirical rules and Ruderman-Kittel-Kasuya-Yosida interactions are shown to be in close agreement.