Thermoelectric power of mixed electronic-ionic conductors II. Case of titanium dioxide

The purpose of the present work is the determination of the thermopower components corresponding to different charge carriers (electrons, electron holes and ions) for TiO₂ and the use of these data for evaluation of the effect of symmetry between these two properties. The procedure of the determination of these components was based on the following two approximations:

The first approximation is based on a symmetrical model assuming a consistency between thermopower and electrical conductivity within the n-p transition (minimum of electronic component of the electrical conductivity corresponds to zero value of the electronic component of thermopower).

The second approximation is based on the apparent asymmetry between thermopower and electrical conductivity within the n-p transition as determined from the first approximation.

The analysis, based on the data of the electronic components of thermopower and electrical conductivity for TiO₂ single crystal, results in the band gap (using the Jonker formalism). The determined band gap is equal to 2.77 eV and 2.57 eV at the first and the second approximations, respectively, while the band gap determined from the experimentally measured data is equal 3.35 eV. These values are consistent with the band gap determined from the data of electrical conductivity corresponding to the n-p transition point (E_g=3.16 eV) and for the data measured experimentally and those free of the ionic conductivity component (E_g=2.79 eV). The obtained results indicate that thermopower and electrical conductivity most likely exhibit the effect of symmetry.