  The energy level alignment at organic/inorganic (o/i) semiconductor
interfaces is crucial for any light-emitting or -harvesting functionality.
Essential is the access to both occupied and unoccupied electronic states
directly at the interface, which is often deeply buried underneath thick
organic films and challenging to characterize. We use several complementary
experimental techniques to determine the electronic structure of
p-quinquephenyl pyridine (5P-Py) adsorbed on ZnO(10-10). The parent anchoring
group, pyridine, significantly lowers the work function by up to 2.9 eV and
causes an occupied in-gap state (IGS) directly below the Fermi level
$E_\text{F}$. Adsorption of upright-standing 5P-Py also leads to a strong work
function reduction of up to 2.1 eV and to a similar IGS. The latter is then
used as an initial state for the transient population of three normally
unoccupied molecular levels through optical excitation and, due to its
localization right at the o/i interface, provides interfacial sensitivity, even
for thick 5P-Py films. We observe two final states above the vacuum level and
one bound state at around 2 eV above $E_\text{F}$, which we attribute to the
5P-Py LUMO. By the separate study of anchoring group and organic dye combined
with the exploitation of the occupied IGS for selective interfacial
photoexcitation this work provides a new pathway for characterizing the
electronic structure at buried o/i interfaces.
