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Eder, Georg (2013): From building blocks to 2D networks: an STM study on the interactions at the nanoscale. Dissertation, LMU München: Fakultät für Geowissenschaften



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 the scission of the carbon-halogen bonds is an essential parameter. In the case of ultra-high vacuum experiments, the influence of substrate temperature, material, and crystallographic orientation on the coupling reaction was studied. For reactive Cu(111) and Ag(110) surfaces room temperature deposition of TBPB already leads to a homolysis of the C-Br bond and subsequent formation of proto-polymers. Applying additional heat facilitates the transformation of proto-polymers into 2D covalent networks. In contrast, for Ag(111) just a variety of self-assembled and rather poorly ordered structures composed of intact molecules has emerged. The deposition onto substrates held at 80 K has never resulted in proto-polymers. For ambient conditions, the polymerization reaction of 1,3,5-tri(4-iodophenyl)benzene (TIPB) on Au(111) was studied by STM after drop-casting the monomer onto the substrate held either at room temperature or at 100 °C. For room temperature deposition only poorly ordered non-covalent arrangements were observed. In accordance with the established UHV protocol for halogenated coupling reaction, a covalent aryl-aryl coupling was accomplished for high temperature deposition. Interestingly, these covalent aggregates were not directly adsorbed on the Au(111) surface, but attached on top of a chemisorbed monolayer comprised of iodine and partially dehalogenated TIPB molecules. For a detailed analysis of the processes, the temperature dependent dehalogenation reaction was monitored by X-ray photoelectron spectroscopy under ultra-high vacuum conditions.