Electronic states of titanyl phthalocyanine films on alkanethiolate self-assembled monolayers probed by two-photon photoemission

We studied both occupied and unoccupied states of titanyl phthalocyanine (TiOPc) films formed on an octanethiolate self-assembled monolayer (SAM) on an Au(1 1 1) surface fabricated in a wet chemical process using two-photon photoemission (2PPE) spectroscopy. A 1.90-nm-thick layer of TiOPc formed an unoccupied state at 2.9 eV above the Fermi level. This state was resonantly enhanced at 4.3-4.4 eV photon energy, suggesting that electrons were excited from the highest occupied molecular orbital of TiOPc. The 2PPE measurements of photon energy dependence and light polarization selectivity revealed that the unoccupied state originates from a charge transfer exciton not observed in organic thin films deposited on bare metallic substrates. The formation of a charge transfer exciton implies that the SAM strongly insulates the molecular monolayer.