Abstract
AbstractThe clathrate Cs8–xGa8–ySi38+y was obtained from a stoichiometric reaction of the elements in an alkali metal halide flux, whereas K8Zn3.5Si42.5 and Rb7.9Zn3.6Si42.4 were synthesized using a combined alkali metal halide/zinc flux. These methods allow to get virtually single‐phase materials with good crystallinity. The compounds were analyzed and characterized by means of powder and single‐crystal X‐ray diffraction methods. Rather unexpectedly, the substitution of Si by Zn in K8Zn3.5Si42.5 and Rb7.9Zn3.6Si42.4 also occurs at the atomic site 24k beside the usually observed 6c site, which has not been found before for intermetallic clathrates with alkali metal guest atoms and substitution of the host atom by group 12 elements. The size effect of the guest atoms Rb and Cs on the alkali metal content of Ga‐Si and Zn‐Si clathrates is established. Furthermore, magnetic and transport measurements (electrical resistivity, Seebeck coefficient and thermal conductivity) are reported.
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