Donors and polaronic absorption in rutile TiO2 single crystals

Philip Michael Weiser, Christian Zimmermann, Julie Bonkerud, Lasse Vines, Eduard V. Monakhov
2020 Journal of Applied Physics  
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
more » ... bit 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 .
doi:10.1063/5.0027434 fatcat:3uijxxwakjf6thv5tausvv4gcm