Oxygen adatom, charge state, noncontact atomic force microscopy (nc-AFM), Kelvin probe force microscopy (KPFM), tipsample distance, tip-induced electric field, density functional theory (DFT).

Structural superlubricity describes the state of virtually frictionless sliding if two atomically flat interfaces are incommensurate, that is, they share no common periodicity. Despite the exciting prospects of this low friction phenomenon, there are physical limitations to the existence of this state. Theory predicts that the contact size is one fundamental limit, where the critical size threshold mainly depends on the interplay between lateral contact compliance and interface interaction energies. Here we provide experimental evidence for this size threshold by measuring the sliding friction force of differently sized antimony particles on MoS. We find that superlubric sliding with the characteristic linear decrease of shear stress with contact size prevails for small particles with contact areas below 15 000 nm. Larger particles, however, show a transition toward constant shear stress behavior. In contrast, Sb particles on graphite show superlubricity over the whole size range. Ab initio simulations reveal that the chemical interaction energies for Sb/MoS are much stronger than for Sb/HOPG and can therefore explain the different friction properties as well as the critical size thresholds. These limitations must be considered when designing low friction contacts based on structural superlubricity concepts.

We study a low-temperature on-surface reversible chemical reaction of oxygen atoms to molecules in ultrahigh vacuum on the semiconducting rutile TiO2(110)-(1 × 1) surface. The reaction is activated by charge transfer from two sources, natural surface/subsurface polarons and experimental Kelvin probe force spectroscopy as a tool for electronic charge manipulation with single electron precision. We demonstrate a complete control over the oxygen species not attainable previously, allowing us to deliberately discriminate in favor of charge or bond manipulation, using either direct charge injection/removal through the tip-oxygen adatom junction or indirectly via polarons. Comparing our ab initio calculations with experiment, we speculate that we may have also manipulated the spin on the oxygens, allowing us to deal with the singlet/triplet complexities associated with the oxygen molecule formation. We show that the manipulation outcome is fully governed by three experimental parameters, vertical and lateral tip positions and the bias voltage.