The upconversion (UC) of the rare earth doped glass-ceramics has been extensively investigated due to their potential ap-plications in many fields, such as color display, high density memories, optical data storage, sensor and energy solar cell, etc. Many series of them, especially the oxyfluorides glasses containing Ba2LaF7 nanocrystals were studied in this review work, due to the ther-mal and mechanical toughness, high optical transmittance from the ultraviolet to the infrared regions, and a low nonlinear refractive index compared to the other commercial laser glasses. Moreover, the energy transfer (ET) between the rare earth ions and transition metals plays an important role in the upconversion process. The cooperative ET has been researched very activly in UC glasses due to applications in the fields of solar cells, such as in the Er/Yb, Tm/Yb, Tb/Yb, Tb/Er/Yb and Tm/Er/Yb couples. The present article re-views on the recent progress made on: (i) upconversion materials with fluoride microcrystals in glasses and the mechanisms involved, including the UC in double and tri-dopant RE ions activated fluoride microcrystal, energy transfer process; and (ii) the effect of the metal Mn and nanoparticles of Au, Ag, Cu on the enhancement of UC emissions. Discussions have also been made on materials, ma-terial synthesis, the structural and emission properties of glass-ceramics. Additionally, the conversion efficiency is still a challenge for the spectra conversion materials and application; challenge and future advances have also been demonstrated.
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