Characteristic Coordination Structure around Nd Ions in Sol-Gel-Derived Nd-Al-Codoped Silica Glasses

Al codoping can improve the poor solubility of rare-earth ions in silica glasses. However, the mechanism is not well understood. The coordination structure around Nd ions in sol-gel-derived Nd-Al-codoped silica glasses with different Al content was investigated by optical and pulsed electron paramagnetic resonance spectroscopies. Both tetrahedral AlO4 and octahedral AlO6 units were observed around Nd ions as ligands. The average total number of these two types of ligands for each Nd3+ ion was similar to 2 irrespective of Al content and was larger by 1-2 orders of magnitude than that calculated for a uniform distribution of codopant ions (similar to 0.08-0.25). With increasing Al content, AlO4 units disappeared and AlO6 units became dominant. The preferential coordination of AlOx (x = 4, 6) units to Nd ions enabled the amount of Al necessary to dissolve Nd ions uniformly in silica glass at a relatively low temperature of 1150-1200 degrees C to be minimized, and the conversion of AlO4 units to AlO6 units around Nd ions caused the asymmetry of the crystal field at the Nd sites to increase and the site-to-site distribution to decrease.