Beschreibung:
<jats:title>Abstract</jats:title><jats:p>Lithium fluoride thin films with various thicknesses have been grown on <jats:italic>c</jats:italic>‐plane sapphire substrates by radio‐frequency sputtering. The thin films are granular with a preferential [111] orientation of the grains. Thickness‐dependent measurements allow the separation of bulk and interface conductions. The normalized conductance decreases linearly with decreasing LiF layer thickness with a negative extrapolated intercept. DC polarization, AC impedance spectroscopy and electromotive force measurement indicate depletion of lithium ion vacancies as majority charge carriers and hence a negative space‐charge potential. A generalized Mott–Schottky approach within the model of heterogeneous doping fully explains the entire boundary defect chemistry.</jats:p>