Correlation of rare earth coordination and spectral properties in Er3+ doped Na2O–Al2O3–SiO2 glasses with different Al2O3 concentrations by molecular dynamics simulations

Abstract

The molecular structure of Er2O3 doped Na2O–Al2O3–SiO2 glasses with varying Na2O/Al2O3 ratios is explored via molecular dynamics (MD) simulations using the so-called inherent structure sampling method, which allows the calculation of a large number of local structures of low concentration, as needed to determine the surrounding of low concentration dopants. General structural parameters, including radial distribution functions, coordination numbers and interatomic distances of all network forming and network modifying ions are reported. However, in this work, special attention is devoted to the effect of Al2O3 concentration on the local surrounding of the doped Er3+ ions. It is shown that the Er atoms coordinate 5-6 oxygen ions in their first coordination sphere in the investigated glasses. The Er-O coordination number increases monotonically with increasing Al2O3 concentration and decreasing Na2O/Al2O3 ratio. It is found that the Er atoms are preferably connected to non-bridging oxygen atoms (NBO) in all glasses, even in the peraluminous composition. Additionally, the MD simulation results are compared to the glasses spectral properties that were already investigated in detail by Tanabe and Hanada. The increasing Er-NBO coordination number derived by MD simulations could be correlated with the increased peak splitting of the Er3+ absorption peaks reported by Tanabe and Hanada. Furthermore, a correlation between the Judd-Ofelt parameters published by Tanabe and Hanada and the Er3+ coordination in the glass structure is discussed. It is shown that the Er-O coordination increases with increasing Ω2 parameter as the Al2O3 concentration increases in the glass composition. A correlation of the average overall Er-O coordination number with the symmetry of the local Er site is proposed.