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The interface formation between copper phthalocyanine (CuPc) and tworepresentative metal substrates, i.e., Au and Co, was investigated by thecombination of ultraviolet photoelectron spectroscopy and inverse photoelectronspectroscopy. The occupied and unoccupied molecular orbitals and thus thetransport band gap of CuPc are highly influenced by film thickness, i.e.,molecule-substrate distance. Due to the image charge potential given by themetallic substrates the transport band gap of CuPc "opens" from $(1.4 \pm 0.3)$eV for 1 nm thickness to $(2.2 \pm 0.3)$ eV, and saturates at this value above10 nm CuPc thickness. The interface dipoles with values of 1.2 eV and 1.0 eVfor Au and Co substrates, respectively, predominantly depend on the metalsubstrate work functions. X-ray photoelectron spectroscopy measurements usingsynchrotron radiation provide detailed information on the interaction betweenCuPc and the two metal substrates. While charge transfer from the Au or Cosubstrate to the Cu metal center is present only at sub-monolayer coverages,the authors observe a net charge transfer from the molecule to the Co substratefor films in the nm range. Consequently, the Fermi level is shifted as in thecase of a p-type doping of the molecule. This is, however, a competingphenomenon to the energy band shifts due to the image charge potential.

Transport band gap opening at metal-organic interfaces