Temperature dependence of the electron diffusion coefficient in electrolyte-filled TiO2 nanoparticle films: Evidence against multiple trapping in exponential conduction-band tails

The temperature and photoexcitation density dependences of the electron transport dynamics in electrolyte-filled mesoporous TiO2 nanoparticle films were investigated by transient photocurrent measurements. The thermal activation energy of the diffusion coefficient of photogenerated electrons ranged from 0.19-0.27 eV, depending on the specific sample studied. The diffusion coefficient also depends strongly on the photoexcitation density; however, the activation energy has little, if any, dependence on the photoexcitation density. The light intensity dependence can be used to infer temperature-independent dispersion parameters in the range 0.3-0.5. These results are inconsistent with the widely used transport model that assumes multiple trapping of electrons in an exponential conduction-band tail. We can also exclude a model allowing for widening of a band tail with increased temperature. Our results suggest that structural, not energetic, disorder limits electron transport in mesoporous TiO2. The analogy between this material and others in which charge transport is limited by structural disorder is discussed.