CO-tip manipulation using repulsive interactions

Understanding the interactions between a tip apex and a target atom or molecule is crucial for the manipulation of individual molecules with precise control by using scanning tunnelling microscopy (STM) and atomic force microscopy. Herein, we demonstrate the manipulation of target CO molecules on a Cu(111) substrate using a CO-functionalized W tip with atomic-scale accuracy. All experiments were performed in a home-built ultra-high vacuum STM system at 5 K. The CO-tip was fabricated by picking up a single CO molecule from a Cu(111) surface. In contrast to a metal tip, repulsive interactions occur between the CO-tip and the target CO molecule. This repulsive interaction promises perfect lateral hopping without any vertical hopping. Hopping events were directly monitored as sudden current drops in the simultaneously measured I-z curves. A larger barrier height between the CO-tip and the target CO (∼9.5 eV) was found from the slope of the I-z curve, which decreases the electron tunnelling probability between the tip and sample. Therefore, electron-driven manipulation cannot be a major trigger for the CO-CO repulsive manipulation. The CO-tip is able to manipulate only the target CO molecule, even when another CO molecule was located ∼0.5 nm away. Statistical measurements revealed that the nearest neighbour atop site is the energetically stable position after hopping. However, if the CO target has another CO molecule in a neighbouring position (denoted as a 'pair'), the target CO hops more than twice as far. This means that the CO-tip experiences a larger repulsive interaction from the pair. These observations of CO-tip manipulation are useful for the design of two-dimensional artificial molecular networks as well as for developing a better understanding of catalytic oxidation processes.