Grażyna Antczak

Complex Surface Diffusion Mechanisms of Cobalt Phthalocyanine Molecules on Ag(100)

We used time-lapsed scanning tunneling microscopy between 43 and 50 K and density functional theory (DFT) to explore the basic surface diffusion steps of cobalt phthalocyanine (CoPc) molecules on the Ag(100) surface. We show that the CoPc molecules translate and rotate on the surface in the same temperature range. Both processes are associated with similar activation energies; however, the translation is more frequently observed. Our DFT calculations provide the activation energies for the translation of the CoPc molecule between the nearest hollow sites and the rotation at both the hollow and the bridge sites. The activation energies are only consistent with the experimental findings, if the surface diffusion mechanism involves a combined translational and rotational molecular motion. Additionally, two channels of motion are identified: the first provides only a channel for translation, while the second provides a channel for both the translation and the rotation. The existence of the two channels explains a higher rate for the translation determined in experiment.

Note: Work function change measurement via improved Anderson method

We propose the modification to the Anderson method of work function change (Δϕ) measurements. In this technique, the kinetic energy of the probing electrons is already low enough for non-destructive investigation of delicate molecular systems. However, in our implementation, all electrodes including filament of the electron gun are polarized positively. As a consequence, electron bombardment of any elements of experimental system is eliminated. Our modification improves cleanliness of the ultra-high vacuum system. As an illustration of the solution capabilities, we present Δϕ of the Ag(100) surface induced by cobalt phthalocyanine layers.

Phthalocyanine arrangements on Ag(100): From pure overlayers of CoPc and F16CuPc to bimolecular heterostructure

We have utilized scanning tunneling microscopy (STM) and low energy electron diffraction to determine the structural properties of two types of metal-phthalocyanines (MPcs), i.e., cobalt-phthalocyanine (CoPc) and hexadecafluorinated copper-phthalocyanine (F16CuPc) on the Ag(100) surface. For coverage close to one monolayer, both systems form long-range ordered structures with square unit cells. The size and rotation of the unit cell with respect to the silver lattice depend on the chemical composition of MPc. Both types of molecules prefer adsorption with around a 30° angle between the molecular axis and the [011] silver direction. The CoPcs mainly arrange in a (5 × 5)R0 phase; however, two additional local arrangements, a 26 × 26 R 1 1 ○ and a (7 × 7)R0, were detected by STM. The F16CuPcs form a 29 × 29 R 2 2 ○ structure. The co-adsorption of CoPc and F16CuPc on the Ag(100) surface in a 1:1 ratio leads to the formation of a compositionally ordered chessboard-like 5 2 × 5 2 R 4 5 ○ structure. During filled states imaging, the different appearance of the central part of each MPc allows us to distinguish CoPcs from F16CuPcs. Regardless of the applied voltage polarity, the ligands of F16CuPcs appear brighter than the ligands of CoPcs.