Magnesium-based melts such as Mg/Al or Mg/Zn mixtures are excellent reaction media for the growth of complex metal silicides which may be of potential interest as thermoelectric compounds. Silicon reacts with divalent metals (A = Ca, Sr, Ba, Eu, Yb) in Mg-rich fluxes to form a variety of (A/Mg)2Si compounds with a charge-balanced 2:1 ratio of metal to silicon. Reactions with calcium yield well-formed crystals of CaMgSi with the orthorhombic TiNiSi structure type. Exploration of europium substitution yields Ca1-xEuxMgSi (TiNiSi type) for x&lt;0.4; magnetic susceptibility studies indicate a change in Eu valence as the substitution decreases. More Eu-rich reaction ratios result in Eu8-xCaxMg16Si12 compounds (hexagonal Ho5Ni19P12 type). Similar exploration of ytterbium substitution in Ca1-xYbxMgSi indicates a switch to the Yb3Si5 structure (hexagonal Th3Pt5 type) occurs above x = 0.5.

Metal flux growth of Ca1-xAxMgSi (A = Eu or Yb) compounds

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