On‐surface polymerization is feasible on semiconducting surfaces. Thermally triggered covalent coupling of 10,10′‐dibromo‐9,9′‐bianthryl molecules on the TiO2(011)‐(2×1) surface is demonstrated. The result paves the way for application of the thermally driven on‐surface polymerization on semiconducting surfaces and indicates that methods based on such a reaction are more universal than previously thought.

Based on scanning tunneling microscopy experiments, we show that the covalent coupling of aryl halide monomers on the rutile TiO2(011)-(2 × 1) surface is controlled by the density of surface hydroxyl groups. The efficiency of the polymerization reaction depends on the level of surface hydroxylation, but the presence of hydroxyl groups is also essential for the reaction to occur.

Durch thermisch ausgelöste kovalente Verknüpfung werden 10,10′‐Dibrom‐9,9′‐bianthryl‐Moleküle auf einer TiO2(011)‐(2×1)‐Oberfläche polymerisiert. Dieses Resultat bereitet den Weg für thermische Polymerisationen auf Halbleiteroberflächen, die allgemeiner anwendbar sein könnten als bisher gedacht.

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SummaryIslands composed of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecules are grown on a hydrogen passivated Ge(001):H surface. The islands are studied with room temperature scanning tunneling microscopy and spectroscopy. The spontaneous and tip-induced formation of the top-most layer of the island is presented. Assistance of the scanning probe seems to be one of the factors that facilitate and speed the process of formation of the top-most layer.