XAFS characterization of the structural site of Yb in synthetic pyrope and grossular garnets

Abstract 

The incorporation and site preference of minor amounts (about 1 wt%) of Yb³⁺ in synthetic pyrope (Mg₃Al₂Si₃O₁₂) and grossular (Ca₃Al₂Si₃O₁₂) garnet were studied by X-ray Absorption Fine-Structure (XAFS) Spectroscopy. The measurements, performed in the temperature range 77–343 K at both Yb L_I- and L_III-edges, demonstrate that Yb³⁺ enters the garnet structure and is located in the dodecahedral site in both samples. The coordination environment of Yb³⁺ in the two samples was compared to that of the X-site cation in end-member synthetic pyrope and grossular and in Yb₃Al₅O₁₂ as determined by single-crystal X-ray diffraction. The local geometry around Yb³⁺ is different from that of Mg and Ca in the bulk of the garnet, and also from that of Yb³⁺ in Yb₃Al₅O₁₂.

Τhe XAFS results indicate that, (1) structural relaxation occurs around Yb³⁺ in the garnet structure; (2) the host garnet matrix exerts a major structural control on the incorporation of Yb³⁺, and (3) minor amounts of Yb³⁺ in garnet are located in structural sites and not in ill-defined defects.