Titanium
dioxide (anatase, rutile) and quasi-amorphous tin dioxide
are prepared on F-doped SnO2 in the form of dense thin
films, which can serve as electron-selective layers in perovskite
solar cells and dye-sensitized solar cells (DSSCs). The present study
brings new data about electronic and electrochemical properties of
these films at the authentic conditions occurring in a dye-sensitized
solar cell (DSSC). Hydrolysis of TiCl4 provides pure rutile
TiO2 at low temperatures, but TiO2 (anatase)
grows in these layers upon calcination. In acetonitrile medium, the
flat band potential of TiO2 (rutile) is more negative than
that of TiO2 (anatase). This is opposite ordering to that
observed in aqueous media. The energy of conduction band minimum of
TiO2 (anatase) equals −4.15 ± 0.07 eV at the
conditions mimicking the DSSC’s environment. Electrochemical
reductive doping of SnO2 provides a material with the most
negative flat band potential and the largest overpotential for the
reduction of I3
–, Co(bpy)3
3+, and Cu(tmby)2
2+. Voltammetric
screening of all the electrode materials in six different electrolyte
solutions, relevant to DSSC applications, gives salient information
about the mediator type and effects of calcination and the addition
of 4-tert-butylpyridine. These data provide novel
inputs for optimization of DSSCs and for perovskite photovoltaics,
too.