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The current–voltage characteristics (IVCs) of anodic TiO2 films in a thin-film structure (Carbon paste/TiO2/Ti/Al) were investigated in the temperature range of T = 80–300 K with bias voltages from −0.5 V to +0.5 V. Anodic oxide film, with a thickness of 14 nm, was obtained by electrochemical oxidation of Ti at a voltage of 10 V. The obtained data for various temperatures showed that the IVCs in the forward (negative on the Ti electrode) and reverse (positive on the Ti electrode) bias of the thin film structure are not symmetrical. Based on the analysis, three temperature ranges (sections) were identified in which the IVCs differ in their behavior. Examination of the IVCs revealed that the conductivity mechanism in Section I (temperature range from 298 to 263 K) is determined by the Space Charge Limited Current (SCLC). Section II, in the temperature range from 243 to 203 K, is characterized by the onset of conductivity involving donor centers, in the case where the concentration of electrons on traps is significantly higher than the concentration of electrons in the conduction band. In Section III, within the temperature range from 183 to 90 K, the conduction mechanism is the Poole–Frenkel process involving donor centers. These donor centers are located below the level of traps in the forbidden band. The results obtained indicate that anodic TiO2 is an n-type semiconductor, in the bandgap of which there are both electron traps and donor centers formed by anionic (oxygen) vacancies. The different behavior of the characteristic energy with different sample biasing in the case of the Poole–Frenkel mechanism indicates a two-layer structure of anodic TiO2.
Мошников et al. (Sat,) studied this question.