Tunneling Probability Increases with Distance in Junctions Comprising Self-Assembled Monolayers of Oligothiophenes.

Molecular tunneling junctions should enable the tailoring of charge-transport at the quantum level through synthetic chemistry but are hindered by the dominance of the electrodes. We show that the frontier orbitals of molecules can be decoupled from the electrodes, preserving their relative energies in self-assembled monolayers even when a top-contact is applied. This decoupling leads to the remarkable observation of tunneling probabilities that increase with distance in a series of oligothiophenes, which we explain using a two-barrier tunneling model. This model is generalizable to any conjugated oligomers for which the frontier orbital gap can be determined and predicts that the molecular orbitals that dominate tunneling charge-transport can be positioned via molecular design rather than by domination of Fermi-level pinning arising from strong hybridization. The ability to preserve the electronic structure of molecules in tunneling junctions facilitates the application of well-established synthetic design rules to tailor the properties of molecular-electronic devices.

Electronic spin transport and spin precession in single graphene layers at room temperature.

Electronic transport in single or a few layers of graphene is the subject of intense interest at present. The specific band structure of graphene, with its unique valley structure and Dirac neutrality point separating hole states from electron states, has led to the observation of new electronic transport phenomena such as anomalously quantized Hall effects, absence of weak localization and the existence of a minimum conductivity. In addition to dissipative transport, supercurrent transport has also been observed. Graphene might also be a promising material for spintronics and related applications, such as the realization of spin qubits, owing to the low intrinsic spin orbit interaction, as well as the low hyperfine interaction of the electron spins with the carbon nuclei. Here we report the observation of spin transport, as well as Larmor spin precession, over micrometre-scale distances in single graphene layers. The 'non-local' spin valve geometry was used in these experiments, employing four-terminal contact geometries with ferromagnetic cobalt electrodes making contact with the graphene sheet through a thin oxide layer. We observe clear bipolar (changing from positive to negative sign) spin signals that reflect the magnetization direction of all four electrodes, indicating that spin coherence extends underneath all of the contacts. No significant changes in the spin signals occur between 4.2 K, 77 K and room temperature. We extract a spin relaxation length between 1.5 and 2 mum at room temperature, only weakly dependent on charge density. The spin polarization of the ferromagnetic contacts is calculated from the measurements to be around ten per cent.

Tailoring two-dimensional PTCDA-melamine self-assembled architectures at room temperature by tuning molecular ratio.

Engineering and tuning multi-component supramolecular self-assemblies on surfaces is one of the challenges of nanotechnology. We use scanning tunneling microscopy to investigate the influence of molecular ratio on the self-assembly of PTCDA-melamine structures on Au(111)-(22 x complex square root of 3). Our observations reveal that three different chiral supramolecular networks having a PTCDA:melamine ratio of 3:2, 1:2, 1:4 can be selectively created by tuning the ratio of molecules deposited on the surface. The 1:2 ratio network having melamine in excess has been observed previously but the 1:4 network has not yet been reported. In comparison, the multi-component 3:2 network having PTCDA in excess is a completely new structure.

Controlling destructive quantum interference in tunneling junctions comprising self-assembled monolayers via bond topology and functional groups.

Quantum interference effects (QI) are of interest in nano-scale devices based on molecular tunneling junctions because they can affect conductance exponentially through minor structural changes. However, their utilization requires the prediction and deterministic control over the position and magnitude of QI features, which remains a significant challenge. In this context, we designed and synthesized three benzodithiophenes based molecular wires; one linearly-conjugated, one cross-conjugated and one cross-conjugated quinone. Using eutectic Ga-In (EGaIn) and CP-AFM, we compared them to a well-known anthraquinone in molecular junctions comprising self-assembled monolayers (SAMs). By combining density functional theory and transition voltage spectroscopy, we show that the presence of an interference feature and its position can be controlled independently by manipulating bond topology and electronegativity. This is the first study to separate these two parameters experimentally, demonstrating that the conductance of a tunneling junction depends on the position and depth of a QI feature, both of which can be controlled synthetically.