  Properties of inorganic-organic interfaces, such as their interface dipole,
strongly depend on the structural arrangements of the organic molecules. A
prime example is tetracyanoethylene (TCNE) on Cu(111), which shows two
different phases with significantly different work functions. However, the
thermodynamically pre-ferred phase is not always the one that is best suited
for a given application. Rather, it may be desirable to selectively grow a
kinetically trapped structure. In this work, we employ density functional
theory and transi-tion state theory to discuss under which conditions such a
kinetic trapping might be possible for the model system of TCNE on Cu.
Specifically, we want to trap the molecules in the first layer in a flat-lying
orientation. This requires temperatures that are sufficiently low to suppress
the re-orientation of the molecules, which is thermodynamically more favorable
for high dosages, but still high enough to enable ordered growth through
diffusion of molecules. Based on the temperature-dependent diffusion and
re-orientation rates, we propose a temperature range at which the
re-orientation can be successfully suppressed.
