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The main objective of the present research work is to identify efficient glasses and glass ceramics as gain media for the development of lasers and optical amplifiers. Therefore, it is more important to select a host material having the lowest phonon energy. Oxyfluorosilicate glasses containing metal fluorides received much attention as they can exhibit combined properties of oxides and fluorides as well as to minimize the phonon energy of the host glasses. These glasses present the lowest phonon energy among oxide glasses, which increases the quantum efficiency from excited states of rare-earth ions in these matrices and make them promising materials for developing more efficient lasers and fibre optic amplifiers. In this book, we also presents the McCumber's and Judd-Ofelt theory. From the Judd-Ofelt theory, we can evaluate the Judd-Ofelt (JO) intensity parameters ( ), effective bandwidths (Delta eff), radiative transition probabilities (AR), stimulated emission cross-sections (semi ) and branching ratios (betaR) for the luminescence levels of Oxyfluorosilicate glasses.