Influence of gas atmosphere and temperature on the conductivity and the photoconductivity of a TiO2 single crystal in the surface region.

The electrical photoconductivity and conductivity at (and near) the surface of a TiO(2) single crystal (rutile) was studied in a range of temperatures between 300 and 573 K and under different ambient gases (oxygen and nitrogen) by means of impedance spectroscopy. The long times required (many hours) to reach steady state photoconductivity can be explained by the reduction of the material upon illumination. At about 475 K a maximum is observed in the equilibrium photoconductivity and a minimum in the rate constants of the rise and decay after switching on and off, respectively, the light. After switching off the light a fast decay takes place during the first milliseconds followed by a slow exponential decay. The first one is related to recombination through defects, while the latter is due to re-oxidation processes of the material. The results are correlated with measurements of photocatalytic activity.

Nanocrystalline versus microcrystalline Li(2)O:B(2)O3 composites: anomalous ionic conductivities and percolation theory

We study ionic transport in nano- and microcrystalline (1-x)Li(2)O:xB(2)O3 composites using standard impedance spectroscopy. In the nanocrystalline samples (average grain size of about 20 nm), the ionic conductivity sigma(dc) increases with increasing content x of B2O3 up to a maximum at x approximately 0.5. Above x approximately 0.92, sigma(dc) vanishes. By contrast, in the microcrystalline samples (grain size about 10 &mgr;m), sigma(dc) decreases monotonically with x and vanishes above x approximately 0. 55. We can explain this strikingly different behavior by a percolation model that assumes an enhanced conductivity at the interfaces between insulating and conducting phases in both materials and explicitly takes into account the different grain sizes.