Modification on the Unoccupied Electronic Structure of Organic Semiconductor by Alkali Metal

We have investigated the evolution of both the occupied and unoccupied states for alkali metal (Cs and Na) doped Copper-Phthalocyanine (CuPc) with photoemission and inverse photoemission spectroscopy. As the doping ratio increases, the lowest unoccupied molecular orbital (LUMO) of CuPc shifts downward, reaching the Fermi level. After the saturation, the LUMO intensity decreases monotonically, while a gap state grows in the valence spectra, which gives direct evidence for the origin of the doping-induced gap state in CuPc molecules.