The formation and crystal chemistry of ternary clathrates in the Ba-Cu-Si system were investigated on a series of compounds Ba8Cu x Si46−x (3 ≤ x ≤ 8). The phase diagram around the clathrate phase was constructed at 800°C, revealing a homogeneity range from Ba8Cu3.4Si42.6 to Ba8Cu4.8Si41.2. Structural investigations confirmed that the clathrates in this system crystallize with cubic primitive symmetry, in the type I clathrate structure (space group Pm \( \bar{3} \) n). Single-crystal x-ray diffraction indicates that the Cu atoms partially substitute for Si atoms on the 6d site; no vacancies are observed.
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Acknowledgements
We thank M. Waas for assistance in the SEM/EDX investigation, and A. Prokofiev, A. Grytsiv, and S. Laumann for assistance with several experiments and fruitful discussions. This work was supported by FFG Project THECLA (815648).
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Yan, X., Giester, G., Bauer, E. et al. Ba-Cu-Si Clathrates: Phase Equilibria and Crystal Chemistry. J. Electron. Mater. 39, 1634–1639 (2010). https://doi.org/10.1007/s11664-010-1253-x
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DOI: https://doi.org/10.1007/s11664-010-1253-x