The electronic structure of porphyrin/metal interfaces studied by ultraviolet photoelectron spectroscopy

Electronic structure of interfaces between 5,10,15,20-tetraphenylporphynatozinc (ZnTPP) and four metals (Mg, Al, Ag, and Au) were studied by ultraviolet photoelectron spectroscopy (UPS). The energy levels of ZnTPP relative to the Fermi level of substrate metals could be expressed as linear functions of the work function of metals with the shift of the vacuum level at interface (Δ). The slope of the linear functions was about unity. This indicates that the energy levels of ZnTPP are fixed to the vacuum level of substrate metal with constant interfacial dipole. 5,10,15,20-Tetra(4-pyridyl)porphyrin (H₂T(4-Py)P)/metal and 5,10,15,20-tetraphenylporphyrin (H₂TPP)/metal interfaces were also investigated, and similar linearity was observed between the energy levels of porphyrin and the work function of metal with the slope of much smaller than unity. This deviation of the slope from unity might be explained by the existence of interface state.