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The spectral-kinetic characteristics of BaF2 crystals and ceramics doped with Cd, Sc, and Tm have been investigated. Some increase in intensity of an ultrafast component (I1) of radioluminescence compared to I1 of the BaF2 crystal has been recorded in BaF2:Sc (2.0 mol.%) ceramics annealed in an atmosphere of CF 4. Significantly greater increase in I1 was obtained in a BaF 2:Tm (1.0 mol.%) crystal. A new mechanism explaining the growth of I1 has been proposed; the transfer of energy from the excited (Tm3+)* ion to a nearby pair of Ba2+ ion-interstitial ion of fluorine.