C60 chain phases on ZnPc/Ag(111) surfaces: Supramolecular organization driven by competing interactions.

Serpentine chain C60 phases were observed in scanning tunneling microscopy (STM) images of C60 layers on zinc phthalocyanine (ZnPc) or pentacene covered Ag(111) and Au(111) surfaces. This low-density, quasi-one-dimensional organization contrasts starkly with the close-packed hexagonal phases observed for C60 layers on bare metal substrates. STM was employed to perform a detailed investigation of these chain structures for C60/ZnPc/Ag(111) heterolayers. Motivated by the similarity of these chain phases, and the chain and stripe organization occurring in dipole-fluid systems, we investigated a model based on competing van der Waals attractions and electrostatic repulsions between C60 molecules as an explanation for the driving force behind these monolayer phases. Density functional theory (DFT) calculations revealed significant charge transfer to C60 from the Ag(111) substrate, through the intervening ZnPc layer, inducing electrostatic interactions between C60 molecules. Molecular dynamics simulations performed with attractive van der Waals interactions plus repulsive dipole-dipole interactions reproduced the C60 chain phases with dipole magnitudes consistent with DFT calculations.

Fermi level alignment in self-assembled molecular layers: the effect of coupling chemistry.

Photoelectron spectroscopy was used to explore changes in Fermi level alignment, within the pi-pi* gap, arising from modifications to the coupling chemistry of conjugated phenylene ethynylene oligomers to the Au surface. Self-assembled monolayers were formed employing either thiol (4,4'-ethynylphenyl-1-benzenethiol or OPE-T) or isocyanide (4,4'-ethynylphenyl-1-benzeneisocyanide or OPE-NC) coupling. The electronic density of states in the valence region of the two systems are nearly identical with the exception of a shift to higher binding energy by about 0.5 eV for OPE-NC. Corresponding shifts appear in C(1s) spectra and in the threshold near E(F). The lack of change in the optical absorption suggests that a rigid shift of the Fermi level within the pi-pi* gap is the major effect of modifying the coupling chemistry. Qualitative consideration of bonding in each case is used to suggest the influence of chemisorption-induced charge transfer as a potential explanation. Connections to other theoretical and experimental work on the effects of varying coupling chemistries are also discussed.