The surface electric conduction in amorphous and crystallized molybdenum oxide films was studied as a function of electronic structure by current-voltage and simultaneous spectroscopic ellipsometry measurements on structures of the kind Al/Molybdenum oxide (MoOx)/Al, at temperatures up to 400 °C and in ambient air. At room temperature, both amorphous and crystalline MoOx samples were found to be sub-stoichiometric in oxygen. The random distribution of oxygen vacancies and the imperfect atomic ordering induced the creation of an intermediate band (IB) located near the valence band and of individual electronic gap states. At temperatures below 300 °C, the conduction was found to exhibit ambipolar character in which electrons and holes participated, the former moving in the conduction band and the latter in the IB and though gap states. Above 300 °C, due to samples gradual oxidation and improvement of atomic ordering (samples crystallization), the density of states in the IB and the gap gradually decreased. The above in their turn resulted in the gradual suppression of the ambipolar character of the conduction, which at 400 °C was completely suppressed and became similar to that of ordinary n-type semiconductor. The above phenomena were found to be reversible, so as the semiconducting MoOx samples were returning to room temperature the ambipolarity of the conduction was gradually re-appearing giving rise to an unusual phenomenon of "metallic" temperature variation of electrical resistance when electrons were injected.
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