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The invention concerns a crystalline lithium fluoride doped with at least 0.018 moles per kg of a bivalent positive ion M present in fluorinated state, in particular of the single crystal type. The ion may be Mg2+, Zn2+, Co2+. Said fluoride exhibits a strong reflectivity and the intense radiation capable of being derived therefrom can be efficiently received by a luminous and fast scintillator, in particular of the rare-earth halide type. The invention is particularly applicable as monochromator of an X-ray fluorescence for elementary analysis.