Chemical shifts of metallic and non-metallic Al–Re–Si approximant crystals studied by EELS and SXES

Abstract

Chemical shifts of approximant crystals of 1/0-Al₁₂Re (1/0-metallic), 1/1-Al₇₃Re₁₅Si₁₂ (1/1-metallic) and 1/1-Al₇₃Re₁₇Si₁₀ (1/1-non-metallic) were examined by using electron energy-loss spectroscopy (EELS) and soft-X-ray emission spectroscopy (SXES). Al L-shell excitation EELS spectra of these alloys showed an apparent chemical shift only for the 1/1-non-metallic alloy to the larger binding energy side by 0.2 eV. Al-Kα, Re-Mα and Si-Kα emission SXES spectra also showed a shift to the larger binding energy side only for 1/1-non-metallic alloy. 1/0-metallic and 1/1-metallic alloys did not show any chemical shift in EELS and SXES experiments. Chemical shifts were observed only in larger binding energy side compared with pure materials. This implies the decrease of valence charge at constituent atomic sites of 1/1-non-metallic alloy compared with 1/0-metallic, 1/1-metallic and pure materials. The decreased charges should distribute intermetallic sites, which should be related to a formation of covalent bonding among Al atomic sites reported by maximum-entropy method (MEM)/Rietveld analysis on this material. This relation between chemical shift and covalent bonding nature of this approximant alloy may support the presence of covalent bonding in Al-based quasicrystals.

Keywords:

• approximant Al–Re–Si alloy
• electronic structure
• EELS
• SXES
• chemical shift
• covalent bonding
• quasicrystal

Acknowledgements

The authors would like to acknowledge the technical assistance of Mr F. Sato and Mr M. Ageishi. The present study was partly supported by the Kazato foundation.