The N3/TiO 2 interfacial structure is dependent on the pH conditions during sensitization.

The electronic structure of the N3/TiO interface can directly influence the performance of a dye sensitized solar cell (DSSC). Therefore, it is crucial to understand the parameters that control the dye's orientation on the semiconductor's surface. A typical step in DSSC fabrication is to submerge the nanoparticulate semiconductor film in a solution containing the dye, the sensitizing solution. The pH of the N3 sensitizing solution determines the distribution of the N3 protonation states that exist in solution. Altering the pH of the sensitizing solution changes the N3 protonation states that exist in solution and, subsequently, the N3 protonation states that anchor to the TiO substrate. We utilize the surface specific technique of heterodyne detected vibrational sum frequency generation spectroscopy to determine the binding geometry of N3 on a TiO surface as a function of the sensitizing solution pH conditions. It is determined that significant reorientation of the dye occurs in pH ≤2.0 conditions due to the lack of N3-dye carboxylate anchoring groups participating in adsorption to the TiO substrate. Consequently, the change in molecular geometry is met with a change in the interfacial electronic structure that can hinder electron transfer in DSSC architectures.