Effects of water in the Surface Adsorption of Dye molecules at Nanostructured TiO2

• The dye-sensitized solar cell is a promising new alternative to conventional solar cells. However these molecular solar cells may suffer from long term stability problems. Some of these problems are believed to be linked to the presence of water. Recently, dyes possessing long hydrophobic chains have been introduced, as an effort to come to terms with problems related to water [1]. In this study the Ru-dyes N3, N719 and 520DN (an analog containing hydrophobic chains) bound to TiO2, have after being exposed to water, been investigated by photoelectron spectroscopy (PES). PES was used to understand on a molecular level, how the introduction of water influences the molecular and electronic structure of these dye sensitized surfaces.In general, the surface sensitized with 520DN does not give signs of any major changes after being subjected to water. The investigation therefore found that the hydrophobic chains in the dye surface with 520DN effectively protect the molecular structure of the surface. However the surfaces of N3 and N719 do show large changes after exposing the surface to water. More specifically, it has been found that the outermost molecular orbitals (HOMO), which are vital for the function of the solar cell, are affected by water by shifting towards higher binding energies.Also, changes in the thiocyanate group can be found in the N3 and N719 dyes after being exposed to water. Specifically, the sulphur S2p energy levels have a substantially larger amount of a second spin-orbit split peak after being exposed to water. The nitrogen N1s peak relating to the thiocyanate group also changes shape. Moreover, in the case of N719, the counter ion TBA+ is not present on the dye sensitized surface after being subjected to water.Finally, the amount of dye on the TiO2 surfaces is also important for the efficiency of the solar cell. It was found that the coverage of N3 and N719 dye decreases when exposed to water, but the coverage of the 520DN dye remains the same.

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