Atomic force microscopy is capable of resolving the chemical structure of a single molecule on a surface. In previous research, such high resolution has only been obtained at low temperatures. Here we demonstrate that the chemical structure of a single molecule can be clearly revealed even at room temperature. 3,4,9,10-perylene tetracarboxylic dianhydride, which is strongly adsorbed onto a corner-hole site of a Si(111)–(7 × 7) surface in a bridge-like configuration is used for demonstration. Force spectroscopy combined with first-principle calculations clarifies that chemical structures can be resolved independent of tip reactivity. We show that the submolecular contrast over a central part of the molecule is achieved in the repulsive regime due to differences in the attractive van der Waals interaction and the Pauli repulsive interaction between different sites of the molecule.
Controlling the structural deformation of organic molecules can drive unique reactions that cannot be induced only by thermal, optical or electrochemical procedures. However, in conventional organic synthesis, including mechanochemical procedures, it is difficult to control skeletal rearrangement in polycyclic aromatic hydrocarbons (PAHs). Here, we demonstrate a reaction scheme for the skeletal rearrangement of PAHs on a metal surface using high-resolution noncontact atomic force microscopy. By a combination of organic synthesis and on-surface cyclodehydrogenation, we produce a well-designed PAH—diazuleno[1,2,3-cd:1′,2′,3′-fg]pyrene—adsorbed flatly onto Cu(001), in which two azuleno moieties are highly strained by their mutual proximity. This local strain drives the rearrangement of one of the azuleno moieties into a fulvaleno moiety, which has never been reported so far. Our proposed thermally driven, strain-induced synthesis on surfaces will pave the way for the production of a new class of nanocarbon materials that conventional synthetic techniques cannot attain.
In/Si(111) surfaces have a variety of phases, among which 4×1 and √7×√3 show intriguing one-/two-dimensional (1D/2D) electronic properties. Here, we carry out extensive experiments to investigate the mechanical properties of various phases on the surfaces by atomic force microscopy at room temperature. Energy dissipation associated with flexibility is measured at the atomic scale. In the 4×1 phase, dissipation locally increases at the inner parts of couples of In chains, which correspond to mobile In atoms in a dynamical fluctuation model for the phase transition. An extremely large dissipation signal is obtained on the √7×√3 phase, indicating that a single atomic layer of In is weakly attached to the Si substrate, which is consistent with the 2D electronic properties.
Twisted bilayer graphene (TBG), in which two monolayer graphene are stacked with an in-plane rotation angle, has recently become a hot topic due to unique electronic structures. TBG is normally produced in air by the tear-and-stack method of mechanical exfoliation and transferring graphene flakes, by which a sizable, millimeter-order area, and importantly clean interface between layers are hard to obtain. In this study, we resolved these problems by directly transferring the easy-to-exfoliate CVD-grown graphene on SiC substrate to graphene in a high vacuum without using any transfer assisting medium and observed electronic band modulations due to the strong interlayer coupling.
Understanding the precise atomic structure of ice surfaces is critical for revealing the mechanisms of physical and chemical phenomena at the surfaces, such as ice growth, melting, and chemical reactions. Nevertheless, no conclusive structure has been established. In this study, noncontact atomic force microscopy was used to address the characterization of the atomic structures of ice Ih(0001) and Ic(111) surfaces. The topmost hydrogen atoms are arranged with a short-range (2 × 2) order, independent of the ice thickness and growth substrates used. The electrostatic repulsion between non–hydrogen-bonded water molecules at the surface causes a reduction in the number of the topmost hydrogen atoms together with a distortion of the ideal honeycomb arrangement of water molecules, leading to a short-range–ordered surface reconstruction.
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