A Review of the Structure and Physical Properties of Fluorozirconate and Rare-Earth-Doped ZBLAN Glasses

Heavy metal fluoride glasses (HMFGs), particularly fluorozirconate glass systems such as ZBLAN have attracted considerable attention due to their unique physical properties, including low phonon energies, wide transparency from the UV to the mid-IR, and high rare-earth ion doping solubility, making them promising materials for photonic applications. This review provides an overview of fluoride glass synthesis methods, structural characteristics, and physical properties of fluorozirconate glasses, with emphasis on glass processing conditions, thermal, mechanical, and optical properties. The structural characteristics are discussed in terms of zirconium–fluorine polyhedral networks and their compositional dependence, while physical properties are analyzed, including glass transition behavior, crystallization tendency, elastic moduli, and infrared transmission. Rare-earth doped Er3+, Ho3+, and Tm3+ ZBLAN glasses are also discussed, which exhibit efficient emissions in the near and mid-IR spectral regions. Although significant progress has been achieved, limitations related to thermal stability, mechanical strength, and incomplete understanding of structure–property relationships persist. Future research should therefore focus on compositional optimization and predictive structural modeling to enable the design of improved fluoride glasses for various applications.