Control of Oxidation State of Eu Ions in Na2O–Al2O3–SiO2 Glasses

Glasses doped with well-controlled Eu3+ and Eu2+ ions have attracted considerable interest due to the possibility of tuning the wavelength range of the emitted light from violet to red by using their 5D0→7Fj and 5d–4f electron transitions. Glasses were prepared to dope Eu3+ ions in a Na2O–Al2O3–SiO2 system, and the changes in the valence state of Eu3+ ions and the glass structure surrounding the Eu atoms during heating under H2 atmosphere were investigated using fluorescence spectroscopy, X-ray absorption fine-structure spectroscopy, and 27Al magic-angle spinning solid-state nuclear magnetic resonance spectroscopy. The reduction behavior of Eu3+ ions was dependent on the Al/Na molar ratio of the glass. For Al/Na < 1, the Al3+ ions formed the AlO4 network structure accompanied by the Na+ ions as charge compensators; the Eu3+ ions occupied the interstitial positions in the SiO4 network structure and were not reduced even under heating in H2 gas. On the other hand, in the glasses containing Al2O3 with the Al/Na ratio exceeding unity, the Eu3+ ions commenced to be coordinated by the AlO4 units in addition to the SiO4 network structure. When heated in H2 gas, H2 gas molecules reacted with the AlO4 units surrounding Eu3+ ions to form AlO6 units terminated with OH bonds, and reduced Eu3+ ions to Eu2+ via the extracted electrons.