Surface Modification of ZnO(0001)–Zn with Phosphonate-Based Self-Assembled Monolayers: Binding Modes, Orientation, and Work Function

We used partially fluorinated alkyl and aromatic
phosphonates as model systems with similar molecular dipole
moments to form self-assembled monolayers (SAMs) on the
Zn-terminated ZnO(0001) surface. The introduced surface
dipole moment allows tailoring the ZnO work function to tune
the energy levels at the inorganic−organic interface to organic
semiconductors, which should improve the efficiency of charge
injection/extraction or exciton dissociation in hybrid electronic
devices. By employing a wide range of surface characterization
techniques supported by theoretical calculations, we present a
detailed picture of the phosphonates’ binding to ZnO, the
molecular orientation in the SAM, their packing density, as
well as the concomitant work function changes. We show that
for the aromatic SAM the interaction between neighboring molecules is strong enough to drive the formation of a more densely packed monolayer with a higher fraction of bidentate binding to ZnO, whereas for the alkyl SAM a lower packing density was found with a higher fraction of tridentate binding.