The electronic structure of Ni-phthalocyanine/metal interfaces studied by X-ray and ultraviolet photoelectron spectroscopy

Nickel phthalocyanine (NiPc) thin films were grown stepwise on polycrystalline gold and silver substrates and the formed interfaces were characterized by X-ray and ultraviolet photoelectron spectroscopies (XPS, UPS). The variation of the XPS core level binding energy with NiPc film thickness yields information about band bending and interface dipoles. The valence band structure of the NiPc thin films was determined by UPS and exhibits four main features at binding energies 1.50 eV, 3.80 eV, 6.60 eV and 8.85 eV, respectively. The NiPc highest occupied molecular orbital (HOMO) cut-off was measured at ∼1.00 eV from the analyzer Fermi level and from the measured work function change of the growing NiPc film a final work function value for NiPc was estimated at 3.90 ± 0.10 eV. The main C1s peak of the NiPc film (∼5.0 nm) consists of two components at 284.8 eV (C–C bonds), 286.2 eV (C–N bonds) reflecting photoemission from multiple carbon sites within the molecule and a satellite at 287.9 eV, whereas the Ni2p and N1s peaks appear at ∼855.9 eV and ∼399.3 eV, respectively and are due to Ni–N bonds. The energy level diagrams of the NiPc/Au and NiPc/Ag interfaces were determined from a combination of the XPS and UPS results, yielding a hole injection barrier of 0.90 ± 0.10 eV for both substrates.