The effects of radiation damage at the surfaces of CaF2 films grown on Si(111) substrates have been studied and the electronic transitions responsible for the formation of surface F centers have been identified by photon‐stimulated desorption and soft x‐ray photoelectron spectroscopy. The dominant desorption channel for F+ ions is a direct Auger‐stimulated process following an electronic transition from Ca 3p to 3d‐derived states above the CaF2 conduction band minimum. At the Si 2p edge, there is an indirect x‐ray induced electron‐stimulated desorption process that contributes only slightly to the desorption of F+. The changes in the kinetic energy distributions of the desorbing F+ ions as a function of film thickness are also discussed.

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