Donors and polaronic absorption in rutile TiO2 single crystals

Abstract

We have used a combination of optical absorption and electrical conductivity measurements to study the effect of the main donor on small polarons in rutile TiO 2 single crystals rendered n-type conductive by hydrogenation or doping with Nb. The electrical conductivity measured at 295 K for hydrogenated samples shows a clear correlation with the interstitial hydrogen (H i ) concentration, which is consistent with reports that H i is the main shallow donor in rutile TiO 2 . Conductive samples exhibit two distinct optical absorption bands in the IR spectral region, at ω 1 = 6500 cm −1 (∼0.8 eV) and ω 2 = 3100 cm −1 (∼0.4 eV), which are present in both hydrogen-rich and Nb-doped samples. The intensities of the absorption bands are proportional to the electrical conductivity, and they exhibit an Arrhenius-like temperature dependence for temperatures between 25-50 K and 50-100 K for H-doped and Nb-doped samples, respectively. The thermal activation energies (E A s) for the absorption bands depend strongly on the main donor: ω 2 exhibits E A (H) and E A (Nb) of ∼4 and ∼10 meV, respectively, whereas ω 1 shows E A (H) and E A (Nb) of ∼1 and ∼2 meV, respectively. The combination of temperature-dependent data for the optical absorption bands and interstitial deuterium (D i )-small polaron vibrational lines support a model where the thermal activation is associated with the reconfiguration of small polarons involving Ti sites far away from the donor. The thermal activation of the optical absorption bands gives us insight into the dynamics of donor-dependent small polaron reconfiguration in rutile TiO 2 .

On the permittivity of titanium dioxide

“…Besides, H i can interact with acceptors and passivate them, increasing the net n-type conductivity. We have demonstrated previously 14 , 15 that annealing of single-crystalline TiO 2 wafers in N 2 at 1100–1200 °C or in forming gas (FG), 10%at. H 2 and 90%at.…”

Niobium K-Edge X-ray Absorption Spectroscopy of Doped TiO2 Produced from Ilmenite Digested in Hydrochloric Acid

“…The electrical conductivity of Nb-doped TiO 2 depends on both the level of Nb doping with the conductivity increasing approximately linearly with Nb content over the range 0.003–0.03 atom % Nb. 47 The electrical conductivity is also dependent on the number of oxygen vacancies. The Nb(V) substituting for Ti(IV) requires a charge balance which is met by oxygen deficiency.…”

On the dielectric constant of titanium dioxide

“…Besides, Hi can interact with acceptors and passivate them, increasing the net n-type conductivity. We have demonstrated previously [13,14] that annealing of TiO2 in N2 at 1100-1200 o C or in forming gas (FG),…”