In this work, the mechanical properties of C(60) molecules adsorbed on Cu(111) are measured by tuning-fork-based noncontact atomic force microscopy (nc-AFM) and spectroscopy at cryogenic conditions. Site-specific tip-sample force variations are detected above the buckyball structure. Moreover, high-resolution images obtained by nc-AFM show the chemical structure of this molecule and describes unambiguously its orientations on the surface.
Directed molecular repositioning is a key step toward the build up of molecular machines. To artificially generate and control the motion of molecules on a surface, excitations by light, chemical, or electrical energy have been demonstrated. Here, the application of local mechanical forces is implemented to achieve directed rotations of molecules. Three-dimensional force spectroscopy with sub-Ångström precision is used to characterize porphyrin derivatives with peripheral carbonitrile groups. Extremely small areas on these molecules (≈ 100 × 100 pm(2)) are revealed which can be used to control rotations. In response to the local mechanical forces, the molecular structure elastically deforms and then changes its conformation, which leads to its rotation. Depending on the selection of one of four submolecular areas, the molecule is either rotated clockwise or counterclockwise.
Three-dimensional dynamic force spectroscopy measurements were carried out above KBr(001) at low temperature in order to investigate the distance dependence of the tip-sample interactions. In particular, the recorded 3D frequency shift data as well as the extracted interaction force and potential energy fields were analysed with respect to influences of tip and/or sample deformations. We found that a postprocessing correction of the observed deformations significantly modifies the magnitude of the extracted interaction forces and also the image contrast.
Recent advances in non-contact atomic force microscopy (nc-AFM) have led to the possibility of achieving unprecedented resolution within molecular structures, accomplished by probing short-range repulsive interaction forces. Here we investigate C(60) molecules adsorbed on KBr(111) and Cu(111) by tuning-fork-based nc-AFM. First, measurements of C(60) deposited on KBr(001) were conducted in cryogenic conditions revealing highly resolved nc-AFM images of the self-assembly. Using constant-frequency shift mode as well as three-dimensional spectroscopic measurements, we observe that the relatively weak molecule-substrate interaction generally leads to the disruption of molecular assembled structures when the tip is probing the short-range force regime. This particular issue hindered us in resolving the chemical structure of this molecule on the KBr surface. To obtain a better anchoring of C(60) molecules, nc-AFM measurements were performed on Cu(111). Sub-molecular resolutions within the molecules was achieved which allowed a direct and unambiguous visualization of their orientations on the supporting substrate. Furthermore, three-dimensional spectroscopic measurements of simultaneous force and current have been performed above the single molecules giving information of the C(60) molecular orientation as well as its local conductivity. We further discuss the different imaging modes in nc-AFM such as constant-frequency shift nc-AFM, constant-height nc-AFM and constant-current nc-AFM as well as three-dimensional spectroscopic measurement (3D-DFS) employed to achieve such resolution at the sub-molecular scale.
Molecules of Co-salen, a paramagnetic metal-organic Schiff base complex, self-assemble into two different well ordered morphologies on a NaCl(001) substrate: nanowires, which form networks, and compact nanocrystallites. Their growth can be controlled by adjusting the deposition parameters. It turns out that the nanowires are metastable. Molecular resolution images suggest that the packing in both morphologies is the same as in bulk Co-salen single crystals. Only the orientation of the c-axis with respect to the substrate is different. The origin of this intriguing bimodal growth is associated with a monomer-to-dimer transition, which probably takes place during initial nucleation at step edges.
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