No abstract

We have studied the diffusion of the two organic molecules DC and HtBDC on the Cu(110) surface by scanning tunneling microscopy. Surprisingly, we find that long jumps, spanning multiple lattice spacings, play a dominating role in the diffusion of these molecules--the root-mean-square jump lengths are as large as 3.9 and 6.8 lattice spacings, respectively. The presence of long jumps is revealed by a new and simple method of analysis, which is tested by kinetic Monte Carlo simulations.

The electronic connection of single molecules to nanoelectrodes on a surface is a basic, unsolved problem in the emerging field of molecular nanoelectronics. By means of variable temperature scanning tunneling microscopy, we show that an organic molecule (C90H98), known as the Lander, can cause the rearrangement of atoms on a Cu(110) surface. These molecules act as templates accommodating metal atoms at the step edges of the copper substrate, forming metallic nanostructures (0.75 nanometers wide and 1.85 nanometers long) that are adapted to the dimensions of the molecule.

The interaction of largish molecules with metal surfaces has been studied by combining the imaging and manipulation capabilities of the scanning tunneling microscope (STM). At the atomic scale, the STM results directly reveal that the adsorption of a largish organic molecule can induce a restructuring of a metal surface underneath. This restructuring anchors the molecules on the substrate and is the driving force for a self-assembly process of the molecules into characteristic molecular double rows.

Adsorption structures formed upon vapor deposition of the natural amino acid L-cysteine onto the (111) surface of gold have been investigated by scanning tunneling microscopy under ultrahigh vacuum conditions. Following deposition at room temperature and at cysteine coverages well below saturation of the first monolayer, we found coexistence of unordered molecular islands and extended domains of a highly ordered molecular overlayer of quadratic symmetry. As the coverage was increased, a number of other structures with local hexagonal order emerged and became dominant. Neither of the room temperature, as-deposited, ordered structures showed any fixed rotational relationship to the underlying gold substrate, suggesting a comparatively weak and nonspecific molecule-substrate interaction. Annealing of the cysteine-covered substrate to 380 K lead to marked changes in the observed adsorption structures. At low coverages, the unordered islands developed internal order and their presence started to perturb the appearance of the surrounding Au(111) herringbone reconstruction. At coverages beyond saturation of the first monolayer, annealing led to development of a ( radical3 x radical3)R30 degrees superstructure accompanied by the formation of characteristic monatomically deep etch pits, i.e., the behavior typically observed for alkanethiol self-assembled monolayers on Au(111). The data thus show that as-deposited and thermally annealed cysteine adsorption structures are quite different and suggest that thermal activation is required before vacuum deposited cysteine becomes covalently bound to single crystalline Au(111).

Pronounced surface restructuring leads to the formation of chiral kink sites (see scanning tunneling microscopy image) when a chiral molecular overlayer (2,5,8,11,14,17‐hexa‐(tert‐butyl)decacyclene) is adsorbed onto an extended, flat metal surface (Cu{110}). The process is proposed to happen as a result of the adsorbed molecule inducing chirality in the achiral surface.

The adsorption of a large organic molecule, named Lander, has been studied on a Cu͑110͒ substrate by scanning tunneling microscopy ͑STM͒. At low temperatures three different conformations of the molecule are observed on the flat surface terraces. At room temperature the Lander molecules are highly mobile and anchor preferentially to step edges. There the molecules cause a rearrangement of the Cu step atoms leading to the formation of Cu nanostructures that are adapted to the dimension of the molecule, as revealed directly by STM manipulation experiments. Upon annealing to 500 K the molecules order at higher coverages partially into small domains. In all cases the exact adsorption conformation of the molecules was identified through an interplay with elastic scattering quantum chemistry calculations.

The design and performance of a fast-scanning, low- and variable-temperature, scanning tunneling microscope (STM) incorporated in an ultrahigh vacuum system is described. The sample temperature can be varied from 25 to 350 K by cooling the sample using a continuous flow He cryostat and counter heating by a W filament. The sample temperature can be changed tens of degrees on a time scale of minutes, and scanning is possible within minutes after a temperature change. By means of a software implemented active drift compensation the drift rate can be as low as 1 nm/day. The STM is rigid, very compact, and of low weight, and is attached firmly to the sample holder using a bayonet-type socket. Atomic resolution on clean metal surfaces can be achieved in the entire temperature range. The performance of the instrument is further demonstrated by images of adsorbed hexa-tert-butyl-decacyclene molecules on Cu(110), by STM movies, i.e., sequential STM images with a time resolution down to 1 s/image (100×100 Å2 with 256×256 pixels), of the mobility of these molecules, and finally by constant current images of standing waves in the electronic local density of states on Cu(110).