A study on Electronic Properties of Passive Film Formed on Ti

Electronic properties of passive films formed on Ti at film formation potentials $(E_f)V_{SCE}$ in pH 8.5 buffer solution and in an artificial seawater were examined through the photocurrent measurement and Mott-Schottky analysis. The passive films formed on Ti in pH 8.5 buffer solution exhibited a n-type semiconductor with a band gap energys $(E_g);E_g^{n=2}=3.4$ eV for nondirect electron transition, and $E_g^{n=0.5}=3.7$ eV for direct electron transition. These band gap values were almost same as those for the passive films formed in artificial seawater, indicating that chloride ion ($Cl^-$ in solution did not affect the electronic structure of the passive film on Ti. $E_g$ for passive films formed on Ti were found to be greater than those ($E_g^{n=0.5}=3.1$ eV, $E_g^{n=2}=3.4$) for a thermal oxide film formed on Ti in air at $400^{\circ}C$. The disorder energy of passive film, determined from the absorption tail of photocurrent spectrum, was much greater than that for the thermal oxide film farmed on Ti in air at $400^{\circ}C$. The greater $E_g$ and the higher disorder energy for the passive film compared with those for the thermal oxide fIlm suggest that the passive film on Ti exhibited more disorded structure than the thermal oxide film. The donor density (about $2.4{\times}10^{20}cm^{-3}$) for the passive film formed in artificial seawater was greater than that (about $20{\times}10^{20}cm^{-3}$) formed in pH 8.5 buffer solution, indicating that $Cl^-$ increased the donor density for the passive film on Ti.