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The current–voltage (J–V) curves of Al/TiO2/n‐Si structures present an anomalous behavior where the current becomes constant for a reverse bias higher than ≈0.65 V. Here we analyze devices fabricated by spin‐coating of an organometallic precursor and subsequent annealing in an O2 atmosphere. The details of the current saturation phenomenon are interpreted as a consequence of the formation of a depletion...