ABSTRACT
The self-assembly of organic molecules on surfaces is a promising approach for the development of nanoelectronic devices. Although a variety of strategies have been used to establish stable links between molecules, little is known about the electrical conductance of these links. Extended electronic states, a prerequisite for good conductance, have been observed for molecules adsorbed on metal surfaces. However, direct conductance measurements through a single layer of molecules are only possible if the molecules are adsorbed on a poorly conducting substrate. Here we use a nanoscale four-point probe to measure the conductivity of a self-assembled layer of cobalt phthalocyanine on a silver-terminated silicon surface as a function of thickness. For low thicknesses, the cobalt phthalocyanine molecules lie flat on the substrate, and their main effect is to reduce the conductivity of the substrate. At higher thicknesses, the cobalt phthalocyanine molecules stand up to form stacks and begin to conduct. These results connect the electronic structure and orientation of molecular monolayer and few-layer systems to their transport properties, and should aid in the rational design of future devices.
ABSTRACT
A stable hydrogen-bonding junction is formed between 3,4,9,10-perylene-3,4,9,10-tetracarboxylic-dianhydride (PTCDA) and 1,3,5-triazine-2,4,6-triamine (melamine). This bimolecular system was studied on the Ag-Si(111) square root 3 x square root R 30 degrees surface at sub-monolayer coverage, and two distinct phases are observed. A hexagonal lattice is formed that is stabilized by hydrogen bonding between PTCDA and melamine. This phase, in which melamine acts as a 3-fold vertex, is a close analogue to the 3,4,9,10-perylene-3,4,9,10-tetracarboxylic-diimide-melamine network reported recently. To our knowledge this hydrogen-bonding junction has not been previously observed and might not be expected due to lone pair repulsion. However we confirm that this combination is stable using ab initio methods. In the second intermixed phase parallel rows of PTCDA molecules coexist with an array of melamine molecules, and we propose a model for this structure.
ABSTRACT
We have investigated the ordered phases of the perylene derivatives perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride (PTCDA) and the imide analogue PTCDI on the Ag-Si(111)square root(3) x square root(3)R30 degrees surface using scanning tunneling microscopy. We find that PTCDA forms square, hexagonal, and herringbone phases, which coexist on the surface. The existence of a square phase on a hexagonal surface is of particular interest and is a result of a near commensurability between the molecular dimensions and the surface lattice. Contrast variations across the square islands arise from PTCDA molecules binding to different sites on the surface. PTCDI on Ag-Si(111)square root(3) x square root(3)R30 degrees forms extended rows, as well as two-dimensional islands, both of which are stabilized by hydrogen bonding mediated by the presence of imide groups. We present models for the molecular arrangements in all these phases and highlight the role of hydrogen bonding in controlling this order.
