A chromophore-bridge-anchor molecular architecture is used to manipulate the molecular level energy position, with respect to the band edges of the substrate, of a chromophore bound to a surface via an anchor group. An energy shift of the chromophore's frontier orbitals is induced by the addition of an oriented molecular dipole into the bridge part of the compound. This principle has been tested using three Zinc Tetraphenylporphyrin derivatives of comparable structure: two of which possess a dipole, but pointing in opposite directions and, for comparison, a compound without a dipole. UV-vis absorption and emission spectroscopies have been used to probe the electronic structure of the compounds in solution, while UV photoemission spectroscopy has been used to measure the relative position of the molecular levels of the chromophore with respect to the band edges of a ZnO(11-20) single crystal substrate. It is shown that the introduction of a molecular dipole does not alter the chromophore's HOMO-LUMO gap, and that the molecular level alignment of the compounds bound to the ZnO surface follows the behavior predicted by a simple parallel-plate capacitor model.
All Science Journal Classification (ASJC) codes
- Electronic, Optical and Magnetic Materials
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films