Abstract

The temperature dependence of the DC conductivity in the semiconducting phase of undoped and Al, Cr, and Ti-doped VO2 has been interpreted with the aid of AC conductivity and thermopower measurements down to 77 K. A hopping conductivity is shown to be dominant for T < 180 K and to make up about 10% of the total conductivity at the metal–semiconductor transition temperature. The frequency dependence of the AC conductivity, σ~fs, is shown to be sensitive to crystalline disorder through the parameter s; s ~0.5 for 'good' crystals and 0.7–0.9 for highly doped or nonstoichiometric material. For the best crystals, a phonon drag contribution is found to exist in the thermopower. The hopping component of the DC conductivity is analyzed in terms of variable range hopping within a nonuniform density of states. For a total density of states between 1018–1020 this leads to a localization radius of 3–11 Å and the conclusion that the position of the Fermi level within the gap strongly influences the relative contributions of hopping and band conduction. A model for the density of states within the energy gap for both pure and doped VO2 is presented on the basis of localized correlations between electrons on pairs of vanadium or vanadium–impurity sites.

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