Abstract Sm3+‐doped and Sm3+/Dy3+ codoped SiO2–SrO–MgO glasses were prepared by conventional melt quenching and Sr2MgSi2O7 based glass–ceramics from sintering and crystallization of the glass powders. The thermal, structural, and optical properties of the glasses and glass–ceramics were investigated as a function of the dopant concentration. The optical characterization includes the photoluminescence spectra and the lifetimes of the 4G5/2 (Sm3+) and 4F9/2 (Dy3+) excited states. In Sm3+ single‐doped samples, the emission intensity increases up to a concentration of 0.3 mol% Sm3+ ions and then decreases due to nonradiative energy transfer processes. The emission spectra in the glass–ceramics show a more resolved structure and higher intensity compared to the glass samples, suggesting a different and crystalline environment for the Sm3+ ions. The non‐radiative processes also influence the experimental decays of the glass samples which deviate from a single exponential with lifetimes decreasing as Sm3+ concentration increases. The emission and excitation spectra of the codoped samples do not show significant energy transfer between Sm3+ and Dy3+ ions. Different emitting colors can be obtained in the codoped glasses by changing the excitation wavelength. The studied glass–ceramics could be applied as enamels on ceramic or metallic substrates.
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