Molecular Dynamics Simulations of the Structures of Europium Containing Silicate and Cerium Containing Aluminophosphate Glasses

Rare earth ion doped glasses find applications in optical and photonic devices such as optical windows, laser, and optical amplifiers, and as model systems for immobilization of nuclear waste. Macroscopic properties of these materials, such as luminescence efficiency and phase stability, depend strongly on the atomic structure of these glasses. In this thesis, I have studied the atomic level structure of rare earth doped silicate and aluminophosphate glasses by using molecular dynamics simulations. Extensive comparisons with experimental diffraction and NMR data were made to validate the structure models. Insights on the local environments of rare earth ions and their clustering behaviors and their dependence on glass compositions have been obtained. In this thesis, MD simulations have been used to investigate the structure of Eu2O3-doped silica and sodium silicate glasses to understand the glass composition effect on the rare earth ions local environment and their clustering behaviors in the glass matrix, for compositions with low rare earth oxide concentration (~1mol%). It was found that Eu–O distances and coordination numbers were different in silica (2.19-2.22 Å and 4.6-4.8) from those in sodium silicate (2.32 Å and 5.8). High tendencies of Eu clustering and short Eu-Eu distances in the range 3.40-3.90 Å were observed in pure silica glasses as compared to those of silicate glasses with much better dispersed Eu3+ ions and lower probability to form clusters. The results show Eu3+ clustering behavior dependence on the system size and suggest for low doping levels, over 12,000 atoms to obtain statistical meaningful results on the local environment and clustering for rigid silica-based glasses. The structures of four cerium aluminophosphate glasses have also been studied using MD simulations for systems of about 13,000 atoms to investigate aluminum and cerium ion environment and their distribution. P5+ and Al3+ local structures were found stable while those of Ce3+ and Ce4+ ions, through their coordination numbers and bond lengths, are glass composition-dependence. Cerium clusters were found in the high cerium glasses.P5+ coordination numbers around cerium revealed the preference of phosphorus ions in the second coordination shell. Total structure factors from MD simulations and experimental diffraction results show a general agreement from comparison for all the cerium aluminophosphate glasses and with compositional changes up to 25 Å-1. Aluminum enters the phosphate glass network mainly as AlO4 and AlO5 polyhedra only connected through corner sharing to PO4 tetrahedra identified by Q11(1 AlOx), Q12(2 AlOx), Q21(1 AlOx), and Q22(2 AlOx) species.