Phase separation in potassium-doped ZnPc thin films.

In this study synchrotron radiation was used to investigate the electronic properties of a thin film of zinc-phthalocyanine (ZnPc) deposited on Si(001)-2x1 and progressively doped with K atoms. The molecular orientation was probed by angular-dependent x-ray absorption spectroscopy and the molecules were found to lie with the macrocycle plane roughly perpendicular to the surface. The evolution of the electronic properties of the film was then followed by measuring the photoemission spectra upon in situ evaporation of K atoms on the pristine ZnPc film. The results show that doping proceeds through charge donation from the K atoms to the molecular units whose lowest unoccupied molecular orbital (LUMO) becomes progressively filled. Despite the fact that the LUMO spectral weight increases as the stoichiometry x in the K(x)ZnPc compound varies from about 1 to 4 (as determined by core level photoemission), no detectable density of states was observed at the Fermi level, showing that the film remains insulating for all the investigated stoichiometries. On the other hand the C 1s spectra, which appear merely broadened at the earliest stages of doping (x approximately 1), clearly develop two distinct components when x exceeds 2, suggesting that the charge state is not the same for all the molecules. At the same time, the modification of the valence band points towards the coexistence of two distinct phases with x=2 and x=4.