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Ionic redistribution at solid interfaces in ionic materials is the keystone of nanoionics. An experimental master piece has been provided by CaF 2 -BaF 2  heterolayers. Meanwhile this system and the involved heterojunctions are extraordinarily well-understood. The present paper gives an account of this model system by reviewing not only transport experiments and defect-chemical modeling as a function of temperature and spacing of the individual layers, but also transition from semi-infinite to mesoscopic conditions, transition from Mott–Schottky to Gouy–Chapman behavior as well as the impact of ionic redistribution on the electronic minority carriers. Owing to the availability of bulk transport data, the analysis works well for in-plane and out-of-plane measurements with only the space charge potential as fit parameter. Space charge effects are able to provide an interpretation of the annealing behavior, too. The experiments are corroborated by molecular dynamics simulations. Extrapolating the ionic redistribution effects down to the atomic level may even explain homovalent doping effects in non-equilibrium mixtures of the two fluorides.

On the CaF 2 -BaF 2 interface