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Tunable and ultrabroadband mid-infrared (MIR) emissions in the range of 2.5–4.5 μm are firstly reported from Co2+-doped nano-chalcogenide (ChG) glass composites. The composites embedded with a variety of binary (ZnS, CdS, ZnSe) and ternary (ZnCdS, ZnSSe) ChG nanocrystals (NCs) can be readily obtained by a simple one-step thermal annealing method. They are highly transparent in the near- and mid-infrared wavelength region. Low-cost and commercially available Er3+-doped fiber lasers can be used as the excitation source. By crystal-field engineering of the embedded NCs through cation- or anion-substitution, the emission properties of Co2+ including its emission peak wavelength and bandwidth can be tailored in a broad spectral range. The phenomena can be accounted for by crystal-field theory. Such nano-ChG composites, perfectly filling the 3–4 μm spectral gap between the oscillations of Cr2+ and Fe2+ doped II VI ChG crystals, may find important MIR photonic applications (e.g., gas sensing), or can be used directly as an efficient pump source for Fe2+: II VI crystals which are suffering from lack of pump sources.

International audience; Changes in glass structure and crystallization behaviour from oxyfluoride silicate glass to oxyfluoride germanate glass were studied by modifying the ratio of Si/Ge in oxyfluoride germanosilicate glass ceramics, and transparent glass ceramic with low light scattering and efficient mid-infrared emissions were obtained. The NaYF4 nanocrystals crystallization ability of oxyfluoride glass was decreased with the increase in Ge content, which can be attributed to the weakened oxide and fluoride phase separation in GeO2-rich glass. Upconversion and down-conversion emission spectra together with Ho3+: 5I6 energy level fluorescent decay curves have been discussed for SiO2-rich glass ceramics and GeO2-rich glass ceramics, in which the fluoride crystallization induced the decrease of multi-phonon non-radiative decay rates plays the main role in the energy transfer processes. The influence of Si/Ge ratio on 2 μm and 3 μm fluorescent emissions in glasses and glass ceramics, and its link with glass network structural changes were discussed. The optimized Yb/Ho codoped oxyfluoride germanosilicate glass ceramic with low light scattering, high peak emission cross section(11.18 × 10−21cm2) and maximum gain coefficient (1.387 cm−1) at 2888 nm provides a potential application in the development of new 3 μm laser devices based on transparent oxyfluoride glass ceramic materials.