Site-Specific Substitution Preferences in the Solid Solutions Li12Si7–xGex, Li12–yNaySi7, Na7LiSi8–zGez, and Li3NaSi6–vGev

Lavinia M. Scherf, Nathalie Riphaus, Thomas F. Fässler

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

The mixed silicide-germanides Li12Si7–xGex, Na7LiSi8–zGez, and Li3NaSi6–vGevwhich could serve as potential precursors for Si1–xGexmaterials were synthesized and characterized by X-ray diffraction methods. The full solid solution series Li12Si7–xGex(0 ≤ x ≤ 7) is easily accessible from the elements and features preferential occupation of the more negatively charged crystallographic tetrel positions by Ge, which is the more electronegative element. In case of Na7LiSi8–zGeza broad solid solution range of 1.3 ≤ x ≤ 8 is available but the ternary silicide Na7LiSi8could not be obtained by the tested methods of synthesis. The solubility of Ge in Li3NaSi6–vGevis highly limited to a maximum of v ≈ 0.5, and again the formally more negatively charged tetrel positions are preferred by Ge. Additionally, the two crystallographic Li positions in Li12Si7with unusually large displacement parameters can be partially substituted by Na in Li12–yNaySi7with 0 ≤ y ≤ 0.6. The statistical mixing of Li and Na in this solid solution contrasts the typical ordering of Li and Na in most ternary tetrelides.

Original languageEnglish
Pages (from-to)1143-1151
Number of pages9
JournalZeitschrift fur Anorganische und Allgemeine Chemie
Volume2016
Issue number20
DOIs
StatePublished - 2016

Keywords

  • Electronegativity
  • Germanium
  • Lithium
  • Silicon
  • Solid solution

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