Influence of Substrate Bonding and Surface Morphology on Dynamic Organic Layer Growth: Perylenetetracarboxylic Dianhydride on Au(111).

We investigated the dynamics of the initial growth of the first epitaxial layers of perylenetetracarboxylic dianhydride (PTCDA) on the Au(111) surface with high lateral resolution using the aberration-corrected spectro-microscope SMART. With this instrument, we could simultaneously study the different adsorption behaviors and layer growth on various surface areas consisting of either a distribution of flat (111) terraces, separated by single atomic steps ("ideal surface"), or on areas with a high density of step bunches and defects ("realistic surface"). The combined use of photoemission electron microscopy, low-energy electron microscopy, and µ-spot X-ray absorption provided a wealth of new information, showing that the growth of the archetype molecule PTCDA not only has similarities but also has significant differences when comparing Au(111) and Ag(111) substrate surfaces. For instance, under otherwise identical preparation conditions, we observed different growth mechanisms on different surface regions, depending on the density of step bunches. In addition, we studied the spatially resolved desorption behavior which also depends on the substrate morphology.

Direct observation of epitaxial organic film growth: temperature-dependent growth mechanisms and metastability.

The growth of the first ten layers of organic thin films on a smooth metallic substrate has been investigated in real-time using the model system PTCDA on Ag(111). The complex behaviour is comprehensively studied by electron microscopy, spectroscopy and diffraction in a combined PEEM/LEEM instrument revealing several new phenomena and yielding a consistent picture of this layer growth. PTCDA grows above room temperature in a Stranski-Krastanov mode, forming three-dimensional islands on a stable bi-layer, in competition with metastable 3rd and 4th layers. Around room temperature this growth mode changes into a quasi layer-by-layer growth, while at temperatures below about 250 K a Vollmer-Weber-like behaviour is observed. By means of laterally resolved soft X-ray absorption spectroscopy the orientation of all adsorbed molecules is found to be homogeneously flat lying on the surface, even during the growth process. The films grow epitaxially, showing long-range order with rotational domains. For the monolayer these domains could be directly analysed, showing an average size of several micrometers extending over substrate steps.