The aim of this work is to further the understanding of the important parameters in the
formation process of 2D nanostructures and therewith pioneer for novel applications. Such 2D
nanostructures can be composed of specially designed organic molecules, which are adsorbed
on various surfaces. In order to study true 2D structures, monolayers were deposited. Their
properties have been investigated by scanning tunneling microscopy (STM) under ultra-high
vacuum (UHV) conditions as well as under ambient conditions. The latter is a highly
dynamic environment, where several parameters come into play. Complementary surface
analysis techniques such as low-energy electron diffraction (LEED), X-Ray photo-emission
spectroscopy (XPS), and Raman spectroscopy were used when necessary to characterize
these novel molecular networks.
In order to conduct this type of experiments, high technical requirements have to be
fulfilled, in particular for UHV experiments. Thus, the focus is on a drift-stable STM, which
lays the foundation for high resolution STM topographs. Under ambient conditions, the
liquid-solid STM can be easily upgraded by an injection add-on due to the highly flexible
design. This special extension allows for adding extra solvent without impairing the high
resolution of the STM data. Besides the device, also the quality of the tip is of pivotal
importance. In order to meet the high requirements for STM tips, an in vacuo ion-sputtering
and electron-beam annealing device was realized for the post-preparation of scanning probes
within one device. This two-step cleaning process consists of an ion-sputtering step and
subsequent thermal annealing of the probe.
One study using this STM setup concerned the incorporation dynamics of coronene (COR)
guest molecules into pre-existent pores of a rigid 2D supramolecular host networks of trimesic
acid (TMA) as well as the larger analogous benzenetribenzoic acid (BTB) at the liquid-solid
interface. By means of the injection add-on the additional solution containing the guest
molecules was applied to the surface. At the same time the incorporation process was
monitored by the STM. The incorporation dynamics into geometrically perfectly matched
pores of trimesic acid as well as into the substantially larger pores of benzentribenzoic acid
exhibit a clearly different behavior. For the BTB network instantaneous incorporation within
the temporal resolution of the experiment was observed; for the TMA network, however,
intermediate adsorption states of COR could be visualized before the final adsorption state
was reached.
A further issue addressed in this work is the generation of metal-organic frameworks (MOFs)
under ultra-high vacuum conditions. A suitable building block therefore is an aromatic
trithiol, i.e. 1,3,5-tris(4-mercaptophenyl)benzene (TMB). To understand the specific role
of the substrate, the surface-mediated reaction has been studied on Cu(111) as well as on
Ag(111). Room temperature deposition on both substrates results in densely packed trigonal
structures. Yet, heating the Cu(111) with the TMB molecules to moderate temperature
(150 °C) yields two different porous metal coordinated networks, depending on the initial
surface coverage. For Ag(111) the first structural change occurs after annealing the sample
at 300 °C. Here, several disordered structures with partially covalent disulfur bridges were
identified.
Proceeding further in the scope of increasing interaction strength between the building
blocks, covalent organic frameworks (COFs) were studied under ultra-high vacuum conditions
as well as under ambient conditions. For this purpose, a promising strategy is covalent
coupling through radical addition reactions of appropriate monomers, i.e. halogenated
aromatic molecules such as 1,3,5-tris(4-bromophenyl)benzene (TBPB) and 1,3,5-tris(4-
iodophenyl)benzene (TIPB). Besides the correct choice of a catalytic surface, the activation
energy for