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Type-I clathrates possess extremely low thermal conductivities, a property that makes them promising materials for thermoelectric applications. The incorporation of cerium into one such clathrate has recently been shown to lead to a drastic enhancement of the thermopower, another property determining the thermoelectric efficiency. Here we explore the mechanism of the incorporation of rare earth elements into type-I clathrates. Our investigation of the crystal growth and the composition of the phase Ba 8- x  RE  x  TM  y  Si 46- y  (RE = rare earth element; TM = Au, Pd, Pt) reveals that the RE content x is mainly governed by two factors, the free cage space and the electron balance.

Mechanism of Rare Earth Incorporation and Crystal Growth of Rare Earth Containing Type-I Clathrates