Engineering the line up of electronic energy levels at inorganic–organic semiconductor interfaces by variation of surface termination and by substitution

In the Anderson model the alignment of electronic energy levels follows from the assumption that the vacuum‐levels of the contacting phases are at equal height. Engineering of the line up may be attempted by changing the ionization energy of the substrate and/or of the adsorbate. We report on the variation of the Si(111) ionization energy by induced surface dipoles of –CH 3 , –H, and –GaSe terminations and the induced variation of the HOMO line up of PTCDA and ZnPc layers. In addition the variation of the line up by changing the organic molecule ionization energy is exemplified by F substitution in ZnPc. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)