The novel organic semiconductor dinaphthothienothiophene (DNTT) has gained considerable interest because its large charge carrier mobility and distinct chemical robustness enable the fabrication of organic field effect transistors with remarkable long-term stability under ambient conditions. Structural aspects of DNTT films and their control, however, remain so far largely unexplored. Interestingly, the crystalline structure of DNTT is rather similar to that of the prototypical pentacene, for which the molecular orientation in crystalline thin films can be controlled by means of interface-mediated growth. Combining atomic force microscopy, near-edge X-ray absorption fine structure, photoelectron emission microscopy, and X-ray diffraction, we compare substrate-mediated control of molecular orientation, morphology, and wetting behavior of DNTT films on the prototypical substrates SiO and graphene as well as technologically relevant dielectric surfaces (SiO and metal oxides that were pretreated with self-assembled monolayers (SAMs)). We found an immediate three-dimensional growth on graphene substrates, while an interfacial wetting layer is formed on the other substrates. Rather surprisingly, we observe distinct temporal changes of DNTT thin films on SiO and the SAM-treated dielectric substrates, which exhibit a pronounced dewetting and island formation on time scales of minutes to hours, even under ambient conditions, leading to a breakup of the initially closed wetting layer. These findings are unexpected in view of the reported long-time stability of DNTT-based devices. Therefore, their future consideration is expected to enable the further improvement of such applications, especially since these structural modifications are equivalently observed also on the SAM-treated dielectric surfaces, which are commonly used in device processing.

We present a new polymorph of the two-dimensional (2D) silica film with a characteristic ‘zigzag’ line structure and a rectangular unit cell which forms on a Ru(0001) metal substrate. This new silica polymorph may allow for important insights into growth modes and transformations of 2D silica films as a model system for the study of glass transitions. Based on scanning tunneling microscopy, low energy electron diffraction, infrared reflection absorption spectroscopy, and X-ray photoelectron spectroscopy measurements on the one hand, and density functional theory calculations on the other, a structural model for the ‘zigzag’ polymorph is proposed. In comparison to established monolayer and bilayer silica, this ‘zigzag’ structure system has intermediate characteristics in terms of coupling to the substrate and stoichiometry. The silica ‘zigzag’ phase is transformed upon reoxidation at higher annealing temperature into a SiO2 silica bilayer film which is chemically decoupled from the substrate.

We use an aberration corrected spectro-microscope, the low energy electron microscope/photoelectron emission microscope (LEEM/PEEM) SMART, to follow the preparation and structure of a bilayer silica film on Ru(0001) as a function of temperature and oxidation conditions. This allows us to analyze the growth process at different length scales in order to judge on the overall quality and the morphology of the film. It is found that the film growth occurs in a crystalline and a vitreous phase as previously discovered using scanning tunneling microscopy. However, the present experiment allows an analysis on the sub-micron level to gain insight into the growth process at a mesoscopic scale. We find that the fully oxidized film can be prepared but that this film contains holes. These are unavoidable and are important to consider, if one wants to use the films for ensemble averaging experiments to investigate migration and reaction of molecules between the silica film and the Ru(0001) substrate

We investigate the scattering of electrons belonging to Shockley states of (111)-oriented noble metal surfaces using angle resolved photoemission (ARPES) and scanning tunneling microscopy (STM). Both ARPES and STM indicate that monatomic steps on a noble metal surface may act either as strongly repulsive or highly transmissive barriers for surface electrons, depending on the coherence of the step lattice, and irrespectively of the average step spacing. By measuring curved crystal surfaces with terrace length ranging from 30 to 180Å, we show that vicinal surfaces of Au and Ag with periodic step arrays exhibit a remarkable wave function coherence beyond 100Å step spacings, well beyond the Fermi wavelength limit and independently of the projection of the bulk band gap on the vicinal plane. In contrast, the analysis of transmission resonances investigated by STM shows that a pair of isolated parallel steps defining a 58Å wide terrace confines and decouples the surface state of the small terrace from that of the (111) surface. We conclude that the formation of laterally confined quantum well states in vicinal surfaces as opposed to propagating superlattice states depends on the loss of coherence driven by imperfection in the superlattice order.