Molecular Orientation of -PO₃H₂ and -COOH Functionalized Dyes on TiO₂, Al₂O₃, ZrO₂, and ITO: A Comparative Study

Modification of transparent metal oxide (MO_x) surfaces with organic monolayers is widely employed to tailor the properties of interfaces in organic electronic devices, and MO_x substrates modified with light-absorbing chromophores are a key component of dye-sensitized solar cells (DSSCs). The effects of an organic modifier on the performance of a MO_x-based device are frequently assessed by performing experiments on model monolayer|MO_x interfaces, where an "inert" MO_x (e.g., Al₂O₃) is used as a control for an "active" MO_x (e.g., TiO₂). An underlying assumption in these studies is that the structure of the MO_x-monolayer complex is similar between different metal oxides. The validity of this assumption was examined in the present study. Using UV-Vis attenuated total reflection spectroscopy, we measured the mean dipole tilt angle of 4,4'-(anthracene-9,10-diyl)bis(4,1-phenylene)diphosphonic acid (A1P) adsorbed on indium tin oxide (ITO), TiO₂, ZrO₂, and Al₂O₃. When the surface roughness of the MO_x substrate and the surface coverage (𝛤) of the A1P film were constant, the molecular orientation of A1P was the same on these substrates. The study was extended to 4,4'-(anthracene-9,10-diyl)bis(4,1-phenylene)dicarboxylic acid (A1C) adsorbed on the same group of MO_x substrates. The mean tilt angle of A1C and A1P films on ITO was the same, which is likely due the intermolecular interactions resulting from the high and approximately equal 𝛤 of both films. Comparing A1C films at the same 𝛤 on TiO₂ and Al₂O₃ having the same surface roughness, there was no difference in the mean tilt angle. MD simulations of A1C and A1P on TiO₂ produced nearly identical tilt angle distributions, which supports the experimental findings. This study provides first experimental support for the assumption that the structure of the MO_x-modifer film is the same on an "active" substrate vs. a "inert" control substrate.