Real-time decay of fluorinated fullerene molecules on Cu(001) surface controlled by initial coverage

Surface specificity and mechanistic pathway of de-fluorination of C60F48 on coinage metals

“…4 and 5 indicate a partial de-uorination of C 60 F 48 at the time scales of some nanoseconds analyzed in the simulations. However, as suggested above, it is possible that mechanisms operating at longer time scales, such as rotation of the molecule over the surface, 26,27 contribute to the complete de-uorination of the molecule as implied by our experimental results (Fig. 3).…”

“…Among them, for the present study it is worth noting the supramolecular order reported for unperturbed C 60 F 36 on Au(111) 25 or the gradual and long lasting loss of halogen atoms taking place for C 60 F 18 , a tortoise-shaped molecule with far fewer uorine atoms than the allotrope studied here, on Cu(100). [26][27][28] In this work, different C 60 F 48 coverages are deposited onto diverse transition metal surfaces to unveil the role that the organic-metal interactions have on the chemical stability of this molecule at room temperature (RT) and give insight into the pathway of surface-induced de-uorination of the molecules. By combining scanning tunneling microscopy (STM), frequency modulation atomic force microscopy (FM-AFM) X-ray photoelectron spectroscopy (XPS) and ultra-violet photoelectron spectroscopy (UPS), we demonstrate that whereas on Au(111) the molecule preserves its chemical structure, the C-F bonds of C 60 F 48 are cleaved when approaching more reactive surfaces such as Cu(111) or Ni(111) transforming into C 60 at room temperature.…”

Fluorination of Cu(001) Surface by C60F48 Molecule Adsorption

“…16,17 In contrast to the gold surface, a decomposition of C 60 F 18 molecules with the F-induced superstructure on the Cu(001) surface was observed by STM. 18,19 In the present work, we use the molecule with a high fluorine content C 60 F 48 and perform a systematic XPS study of fluorine, carbon, and copper chemical states depending on coverage and time. The XPS spectra analysis allows us to detail fluorine−carbon and fluorine−copper interactions and make a quantitative estimation of the compounds on the Cu(001) surface.…”

On-surface products from de-fluorination of C60F48 on Ag(111): C60, C60Fx and silver fluoride formation

“…A much less studied case of on-surface dehalogenation is the reactive adsorption of fluorinated fullerenes (C 60 F x ) on some metals. [10][11][12][13][14][15] Because the increase in fluorine content of C 60 F x enhances the acceptor character of the molecule, C 60 F 48 is an excellent molecular p-dopant in organic electronics devices, [16][17][18] such as organic field effect transistors (OFETs), 19,20 where the molecular species are in contact with metallic electrodes. Any deviation of the stoichiometry of the molecule at its interface with the metal will cause an imbalance of the energy level alignment at the contact with undesired consequences in the device performance.…”