Electrons in the Band Gap: Spectroscopic Characterization of Anatase TiO2 Nanocrystal Electrodes under Fermi Level Control

Macroscopic properties of semiconductor nanoparticle networks in functional devices strongly depend on the electronic structure of the material. Analytical methods allowing for the characterization of the electronic structure in situ, i.e., in the presence of an application-relevant medium, are therefore highly desirable. Here, we present the first spectral data obtained under Fermi level control of electrons accumulated in anatase TiO2 electrodes in the energy range from the MIR to the UV (0.1-3.3 eV). Band gap states were electrochemically populated in mesoporous TiO2 films in contact with an aqueous electrolyte. The combination of electrochemical and spectroscopic measurements allows us for the first time to determine both the energetic location of the electronic ground states as well as the energies of the associated optical transitions in the energetic range between the fundamental absorption threshold and the onset of lattice absorption. On the basis of our observations, we attribute spectral contributions in the vis/NIR to d-d transitions of Ti3+ species and a broad MIR absorption, monotonically increasing toward lower wavenumbers, to a quasi-delocalization of electrons. Importantly, signal intensities in the vis/NIR and MIR. are linearly correlated. Absorbance and extractable charge show the same exponential dependence on electrode potential. Our results demonstrate that signals in the vis/NIR and MIR are associated with an exponential distribution of band gap states.