Probing the interaction between 2,2'-bithiophene-5-carboxylic acid and TiO 2 by photoelectron spectroscopy: A joint experimental and theoretical study

The interaction between 2,2'-bithiophene-5-carboxylic acid (PT2) sublimed under ultra-high vacuum conditions and anatase (101) and rutile (110) TiO single crystal surfaces is investigated by studying the electronic spectral density near the Fermi level with synchrotron-based spectroscopy. The experimental results are compared to density functional theory calculations of the isolated PT2 molecule and of the molecule adsorbed on an anatase TiO (101) cluster. The relative concentrations of Ti, C, and S atoms indicate that the adsorbed molecule remains intact upon deposition, which is typical of a Stranski-Krastanov growth mode. The analysis of the O1s spectrum suggests a predominant bidentate geometry of the adsorption with both rutile and anatase surfaces, as supported by previous theoretical simulations. It is also theoretically and experimentally demonstrated that the PT2 adsorption causes the appearance of new electronic states in the gap near the TiO valence band. A pinning effect of the LUMO level of the dye is also theoretically predicted.