Sub-50 nm positioning of organic compounds onto silicon oxide patterns fabricated by local oxidation nanolithography.

We present a process to fabricate molecule-based nanostructures by merging a bottom-up interaction and a top-down nanolithography. Direct nanoscale positioning arises from the attractive electrostatic interactions between the molecules and silicon dioxide nanopatterns. Local oxidation nanolithography is used to fabricate silicon oxide domains with variable gap separations ranging from 40 nm to several microns in length. We demonstrate that an ionic tetrathiafulvalene (TTF) semiconductor can be directed from a macroscopic liquid solution (1 µM) and selectively deposited onto predefined nanoscale regions of a 1 cm(2) silicon chip with an accuracy of 40 nm.

Growth induced reordering of fullerene clusters trapped in a two-dimensional supramolecular network.

We have investigated the growth of molecular clusters in confined geometries defined by a bimolecular supramolecular network. This framework provides a regular array of identical nanoscale traps in which further deposited molecules nucleate cluster growth. For the higher fullerene, C84, molecules aggregate into close packed assemblies with an orientation which switches when the cluster size increases by one molecule. This change is controlled by the interactions between the molecules and the confining boundaries of the network pore. We show that, following nucleation of small clusters, further growth requires a reconfiguration of previously captured molecules resulting in a transition between nanoscale phases with different ordering.

Square, hexagonal, and row phases of PTCDA and PTCDI on Ag-Si(111)square root(3) x square root(3)R30 degrees.

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.