Thermally‐Induced Reentrant Order‐Disorder‐Order Transitions in ALa₉(GeO₄)₆O₂ Apatites

Abstract

Oxyapatites A10(GeO4)6O2 (A – alkaline, rare‐earth elements) are considered promising materials for applications in solid‐state lighting and non‐contact thermometry. The temperature dynamics of the oxygen sublattice have a crucial influence on the luminescent properties of these optical hosts. Here, the structural evolution with temperature of germanates with the general formula ALa9(GeO4)6O2 (A – Li, Na, K, Rb) is investigated, using X‐ray and neutron powder diffraction methods. These compounds crystallize in space‐group P63/m. NPD experiments helped to determine the oxygen and alkaline metal positions. Thermally‐induced reentrant structural transitions relating to the oxygen in the apatite channel are discovered for the first time. In the example of Eu‐doped RbLa9(GeO4)6O2 and KLa9(GeO4)6O2, it is demonstrated that the luminescence of the Eu3+ ion is influenced by small changes in the crystal structure.