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theses

Tetraphenylporphyrin (TPP)-derived molecules have been studied extensively as efficient photosensitizers when chemisorbed on the metal oxide substrates in dye-sensitized solar cells. Still, many fundamental electronic properties of the dye/oxide interface are not understood and need careful consideration. In this thesis we present a comprehensive study of the electronic structure, energy level alignment and the adsorption geometry of the TPP-derived dye molecules adsorbed on TiO$_2$(110), ZnO(11$overline{2}$0) and Ag(100) single crystal surfaces using ultra-high vacuum (UHV) based surface sensitive techniques. The alignment of the molecular energy levels with respect to the TiO$_2$ and ZnO band edges for all TPP-derived molecules we studied was found to be insensitive to either the nature of the functional groups located on the phenyl rings, presence of zinc as a central metal ion and different binding geometry of the molecules. Binding geometry, molecule-molecule interaction and the aggregation effects in the adsorbed layer, that were observed in the UV-visible spectra of the molecules adsorbed on ZnO substrate were not observed in the ultraviolet photoemission (UPS) and inverse photoemission (IPS) spectra of the occupied and unoccupied molecular states. Using near edge X-ray absorption fine structure (NEXAFS) and scanning tunneling microscopy (STM), binding geometry of the two representative TPP-derivatives was directly determined to be upright, with the porphyrin ring under large angle with respect to the surface for the emph{p}-ZnTCPP molecules and with the porphyrin ring parallel to the surface for the emph{m}-ZnTCPP molecules. We observe that the energies and the energy level alignment of the ZnTPP molecular levels measured in UPS and IPS depend on the substrate on which the molecules are adsorbed (Ag(100) or TiO$_2$(110) single crystal surfaces). The differences are attributed to different charge screening properties of these two materials. Image charges created in the substrates during the measurement affect both the ground state electronic structure and the electronic excitations in the molecules causing the transport gap, the optical gap and the exciton binding energy of the molecules to decrease as the thickness of the film decreases. As measured in STM, the molecules in the first layer adsorb with the porphyrin rings parallel to the surface, while the phenyl rings are essentially upright on both surfaces.

ETD_4354

Ph.D.

Includes bibliographical references

Includes vita

by Senia Coh

http://hdl.rutgers.edu/1782.1/rucore10001600001.ETD.000066661

doi:10.7282/T3NC5ZZT

ETD doctoral

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