The microstructure of erbium–ytterbium co-doped oxyfluoride glass–ceramic optical fibers

Oxyfluoride transparent glass–ceramics combine some features of glasses (easier shaping or lower than single crystals cost of fabrication) and some advantages of rare-earth doped single crystals (narrow absorption/emission lines and longer lifetimes of luminescent levels). Since the material seems to be promising candidate for efficient fiber amplifiers, the manufacturing as well as structural and optical examination of the oxyfluoride glass–ceramic fibers doped with rare-earth ions seems to be a serious challenge. In the first stage oxyfluoride glasses of the following compositions 48SiO2–11Al2O3–7Na2CO3–10CaO–10PbO–11PbF2–3ErF3 and 48SiO2–11Al2O3–7Na2CO3–10CaO–10PbO–10PbF2–3YbF3–1ErF3 (in molar%) were fabricated from high purity commercial chemicals (Sigma–Aldrich). The fabricated glass preforms were drawn into glass fibers using the mini-tower. Finally, the transparent Er3+ doped and Er3+/Yb3+ co-doped oxyfluoride glass–ceramic fibers were obtained by controlled heat treatment of glass fibers. The preceding differential thermal analysis (DTA) studies allowed estimating both the fiber drawing temperature and the controlled crystallization temperature of glass fibers. X-ray diffraction examination (XRD) at each stage of the glass–ceramic fibers fabrication confirmed the undesirable crystallization of preforms and glass fibers has been avoided. The fibers shown their mixed amorphous–crystalline microstructure with nano-crystals of size even below 10 nm distributed in the glassy host. The crystal structure of the grown nano-crystals has been determined by XRD and confirmed by electron diffraction (SAED). Results obtained by both techniques seem to be compatible: Er3FO10Si3 (monoclinic; ICSD 92512), Pb5Al3F19 (triclinic; ICSD 91325) and Er4F2O11Si3 (triclinic; ICSD 51510) against to initially expected PbF2 crystals.

► Er–Yb co-doped oxyfluoride glass drawn into fiber.
► Heat treatment above Tg enables growth of fluoride/oxyfluoride nano-crystals.
► Desired glass–ceramics microstructure was confirmed by X-ray/electron diffraction.