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A compositional and crystallographic study was carried out on the Smy(FexNi1−x)4Sb11.5Sn0.5 filled skutterudite system (0.40 ≤ x ≤ 0.80) with the aim to determine the equilibrium Sm filling fraction (y) within the considered x range. The relevance of the material lies in its potential thermoelectric properties: in analogy with similar skutterudites systems, these features should in fact result as being improved with respect to the ones of the corresponding Sn-free system thanks to the partial substitution of Sn for Sb, which is expected to lower the phonon thermal conductivity. The results of Rietveld refinements allowed us to study the skutterudite structural properties and to discuss them, adopting a comparative approach with respect to the ones of the Sn-free system Smy(FexNi1−x)4Sb12. Relying on the refined Sm occupancy factors, the p/n crossover is shown to be located at x ~ 0.53, meaning that the introduction of Sn induces an enlargement of the p-region; moreover, at variance with the Sn-free system, the coefficient of thermal expansion does not show any significant mismatch between n- and p-compositions, which should ensure a prolonged lifetime of a device made of n- and p-legs that both derive from the studied system.

Compositional Optimization and Structural Properties of the Filled Skutterudite Smy(FexNi1−x)4Sb11.5Sn0.5