A molecular overlayer with the Fibonacci square grid structure.

Quasicrystals differ from conventional crystals and amorphous materials in that they possess long-range order without periodicity. They exhibit orders of rotational symmetry which are forbidden in periodic crystals, such as five-, ten-, and twelve-fold, and their structures can be described with complex aperiodic tilings such as Penrose tilings and Stampfli-Gaehler tilings. Previous theoretical work explored the structure and properties of a hypothetical four-fold symmetric quasicrystal-the so-called Fibonacci square grid. Here, we show an experimental realisation of the Fibonacci square grid structure in a molecular overlayer. Scanning tunnelling microscopy reveals that fullerenes (C60) deposited on the two-fold surface of an icosahedral Al-Pd-Mn quasicrystal selectively adsorb atop Mn atoms, forming a Fibonacci square grid. The site-specific adsorption behaviour offers the potential to generate relatively simple quasicrystalline overlayer structures with tunable physical properties and demonstrates the use of molecules as a surface chemical probe to identify atomic species on similar metallic alloy surfaces.

Large Spatially Resolved Rectification in a Donor-Acceptor Molecular Heterojunction.

We demonstrate that rectification ratios (RR) of ≳250 (≳1000) at biases of 0.5 V (1.2 V) are achievable at the two-molecule limit for donor-acceptor bilayers of pentacene on C60 on Cu using scanning tunneling spectroscopy and microscopy. Using first-principles calculations, we show that the system behaves as a molecular Schottky diode with a tunneling transport mechanism from semiconducting pentacene to Cu-hybridized metallic C60. Low-bias RRs vary by two orders-of-magnitude at the edge of these molecular heterojunctions due to increased Stark shifts and confinement effects.

Chiral "pinwheel" heterojunctions self-assembled from C60 and pentacene.

We demonstrate the self-assembly of C60 and pentacene (Pn) molecules into acceptor-donor heterostructures which are well-ordered and--despite the high degree of symmetry of the constituent molecules--chiral. Pn was deposited on Cu(111) to monolayer coverage, producing the random-tiling (R) phase as previously described. Atop R-phase Pn, postdeposited C60 molecules cause rearrangement of the Pn molecules into domains based on chiral supramolecular "pinwheels". These two molecules are the highest-symmetry achiral molecules so far observed to coalesce into chiral heterostructures. Also, the chiral pinwheels (composed of 1 C60 and 6 Pn each) may share Pn molecules in different ways to produce structures with different lattice parameters and degree of chirality. High-resolution scanning tunneling microscopy results and knowledge of adsorption sites allow the determination of these structures to a high degree of confidence. The measurement of chiral angles identical to those predicted is a further demonstration of the accuracy of the models. van der Waals density functional theory calculations reveal that the Pn molecules around each C60 are torsionally flexed around their long molecular axes and that there is charge transfer from C60 to Pn in each pinwheel.