Abstract
Anionic nonstoichiometry in fluorides (replacement of F1– with O2–) deteriorates the quality of optical materials. Two reviews have been devoted to the initial stage of anionic nonstoichiometry: fluorides MF2 (M = Ca, Sr, Ba) are considered in this paper, and fluorides RF3 (R are 16 rare-earth elements) will be considered in the next one. These 19 fluorides play an important role in the fluoride materials science, comprising more than 70% of 27 MFm that are used to design two-component fluoride crystalline materials. The initial stage of anionic nonstoichiometry in MF2 is the only one in which oxofluorides MF2 – 2xOx with low oxygen content are formed. Partial replacement of F1– with O2– in the fluorite structure is accompanied by thermal stabilization of the structure type when moving up the temperature scale with a maximum in the melting curves of the oxofluoride phase, which decomposes upon cooling. No other intermediate phases containing fluorine and oxygen were found in the MF2–MO systems studied.
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