Journal
SOLID STATE SCIENCES
Volume 4, Issue 5, Pages 723-729Publisher
ELSEVIER
DOI: 10.1016/S1293-2558(02)01319-5
Keywords
silicon; clathrates; fullerenes; intercalation compounds; Zintl-type phases
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Low sodium content silicides discovered by some of us in the sixties are compared to some analogous fan-Lilies of materials. As endofullerenes constituted by the smallest Si-20, Si-24 and Si-28 clusters, they are polymerized in 3D-structures of face sharing polyhedra, giving rise to clathrate-like structures (similar to those of the gas and liquid hydrates). Several physical properties (conductivity, Na-23 and Si-29 NMR, EPR) show that the electronic transfer from sodium to the silicon host is rather low and appears only gradually with rising Na-content as a consequence of Na 3s and Si 3s-3p orbital mixing which gives rise to an antibonding band. Silicon clathrates differ from the homologous germanium and tin compounds characterized by a large number of defects in the host structure which leads to stronger ionization of the alkali atoms and to the formation of some Ge- anions within Zintl-Klenim-type phases. (C) 2002 editions scientifiques et medicales Elsevier SAS. All rights reserved.
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