We demonstrate that well prepared and characterized Cr tips can provide atomic resolution on the bulk NaCl(001) surface with dynamic atomic force microscopy in the noncontact regime at relatively large tip-sample separations. At these conditions, the surface chemical structure can be resolved yet tipsurface instabilities are absent. Our calculations demonstrate that chemical identification is unambiguous, because the interaction is always largest above the anions. This conclusion is generally valid for other polar surfaces, and can thus provide a new practical route for straightforward interpretation of atomically resolved images.
Individual molecules of Co-Salen, a small chiral paramagnetic metal--organic Schiff base complex, were deposited on NaCl(001) and subsequently imaged with noncontact atomic force microscopy employing Cr coated tips in a cryogenic ultrahigh vacuum environment. Images were obtained in which both the position and orientation of the adsorbed molecules and the atomic structure of the surface are resolved simultaneously, enabling the determination of the exact adsorption site. Density functional theory calculations were used to identify the ionic sublattice resolved with the Cr tip and also to confirm the adsorption site and orientation of the molecule on the surface. These calculations show that the central Co atom of the molecule physisorbs on top of a Cl ion and is aligned along 110-directions in its lowest energy configuration. In addition, a local energy minimum exists along 100-directions. Due to the chirality of the molecule, two mirror symmetric configurations rotated by approximately +/-5 degrees away from these directions are energetically equivalent. The resulting 16 low energy configurations are observed in the experimental images.
Individual molecules of Co-Salen, a small chiral paramagnetic
metal–organic
complex, deposited on NiO(001) were imaged with noncontact atomic
force microscopy (NC-AFM) using metallic Cr coated tips. Experimentally,
we simultaneously resolve both the molecule and the individual surface
ions. Images recorded at low temperatures show that the Co-Salen molecules
are aligned slightly away from the ⟨110⟩ directions
of the surface and that the Co center of the molecule is located above
a bright spot in atomically resolved images of the surface. Density
functional theory calculations predict that the molecule adsorbs with
the central Co atom on top of an oxygen ion and is in its lowest energy
configuration aligned either + or −4° away from the ⟨110⟩
directions, dependent on the chirality of the molecule. Combining
theoretical predictions and experimental data allows us to identify
bright spots in NC-AFM images as oxygen sites on NiO(001) and hence
determine the exact adsorption geometry and position of the molecule.
Additionally, we observed tip-induced translations of the Co-Salen
molecules along ⟨110⟩ directions on the substrate, which
corresponds to the lowest energy pathway for diffusion. A comparison
of these results with theoretical calculations and previously published
experimental data for Co-Salen on the (001) surface of bulk NaCl highlights
differences in the character of adsorption of individual molecules
and the ensuing growth of Co-Salen thin films on these substrates.
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.
Here, we present a very small evaporator unit suitable to deposit molecules onto a sample in a cryogenic environment. It can be transported in an ultrahigh vacuum system and loaded into Omicron-type cantilever stages. Thus, molecule deposition inside a low temperature force microscope is possible. The design features an insulating base plate with two embedded electrical contacts and a crucible with low power consumption, which is thermally well isolated from the surrounding. The current is supplied via a removable power clip. Details of the manufacturing process as well as the used material are described. Finally, the performance of the whole setup is demonstrated.
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