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All Samples of alkaline-earth silicon oxynitride glass were synthesized by conventional high-temperature melting reaction.The starting materials were MCO3(M=Ca、 Sr、 Ba), SiO2 and Si3N4, fluoride and boron oxide used as flux.Spectra of Eu2O3 doped MO-SiO2-Si3N4 (M=Sr, Ba) glasses show sharp emission peaks between 570 and 650 nm peaking at 615nm for the 4f-4f transition of Eu3+, The fluorescence emission of Eu2O3 doped CaO-SiO2-Si3N4 glass consists of a strong emission band from 400 to 580 nm and weak emission peaks between 570 and 650 nm.The sharp emission peaks assigned to the transitions of 5Do-7Fj of Eu3+ ion, while the broad band can be ascribed to the 5d-4f transition of Eu2+ ion, indicating that valence change from Eu3+ to Eu2+ was observed in CaO-SiO2-Si3N4 glasses.