Electrochemical Characterization of TiO2 Blocking Layers for Dye-Sensitized Solar Cells

Thin compact layers of TiO2 are grown by thermal oxidation of Ti, by spray pyrolysis, by electrochemical deposition, and by atomic layer deposition. These layers are used in dye-sensitized solar cells to prevent recombination of electrons from the substrate (FTO or Ti) with the hole-conducting medium at this interface. The quality of blocking is evaluated electrochemically by methylviologen, ferro/ferricyanide, and spiro-OMeTAD as the model redox probes. Two types of pinholes in the blocking layers are classified, and their effective area is quantified. Frequency-independent Mott–Schottky plots are fitted from electrochemical impedance spectroscopy. Certain films of the thicknesses of several nanometers allow distinguishing the depletion layer formation both in the TiO2 film and in the FTO substrate underneath the titania film. The excellent blocking function of thermally oxidized Ti, electrodeposited film (60 nm), and atomic-layer-deposited films (>6 nm) is documented by the relative pinhole area of less...