Rectification and negative differential resistance via orbital level pinning.

A donor-acceptor system, 4-thiophenyl-azafulleroid (4TPA-C60), is investigated at the point of HOMO/LUMO resonance and beyond to understand how negative differential resistance (NDR) features may be observed in such systems. Our previous investigation showed that charge transfer between the occupied and unoccupied states at resonance hindered crossing of the HOMO and LUMO levels, thus preventing the formation of an NDR feature. In this work, it is shown that the negative differential resistance feature of 4TPA-C60 can be tailored based on the couplings at the metal/molecule interface. Ab initio calculations show that limited charge extraction from atomically sharp contacts results in a HOMO-LUMO pinning effect which delays the onset of the NDR feature. Subsequent unpinning of the states can only occur when additional charge extraction channels enter the bias window, highlighting an important role which non-frontier states play in charge transport. The proposed charge transfer mechanism is then exploited by introducing a fluorine atom into the C60 cage to tune the energies of the acceptor, and narrow the width of the current peak. These findings not only demonstrate the importance of the metal/molecule interface in the design of molecular electronic architectures but also serve to inform future design of molecular diodes and RTDs.

HOMO-LUMO coupling: the fourth rule for highly effective molecular rectifiers.

Three rules for creating highly effective unimolecular rectifiers that utilize asymmetric anchoring groups have been proposed by Van Dyck and Ratner [Ratner et al., Nano Lett., 2015, 15, 1577-1584]. This study investigates their proposed rectification mechanism in a functionalised azafullerene system (4TPA-C60) and identifies a fourth rule. NEGF-DFT shows that 4TPA-C60 fulfills the three design rules and finds that a saturated bridge is not required to fulfil the third rule, contrary to previous belief. Instead a twisted-π bridge decouples the donor and acceptor states whilst still providing a high conductance pathway. The molecular junction has a calculated rectification ratio of 145 at a bias of ±1 V and the U-type rectification mechanism is driven by the pinning of the HOMO to the LUMO when the device is forward biased, but not when reverse biased. The switching behaviour is a result of a charge dipole forming at different interfaces for different bias directions. An additional design rule is thus proposed: charge transport should allow bias dependent coupling of filled to unfilled states. The findings in this work not only help in understanding charge transport in molecular rectifiers, but also have wider implications for the design of molecular resonant tunneling devices.

Non-Close-Packed Breath Figures via Ion-Partitioning-Mediated Self-Assembly.

We report a one-step method of forming non-close-packed (NCP) pore arrays of micro- and sub-micropores using chloroform-based solutions of polystyrene acidified with hydrogen bromide for breath figure (BF) patterning. As BF patterning takes place, water vapor condenses onto the polystyrene solution, forming water droplets on the solution surface. Concurrently, preferential ion partitioning of hydrogen bromide leads to positively charged water droplets, which experience interdroplet electrostatic repulsion. Self-organization of charged water droplets because of surface flow and subsequent evaporation of the droplet templates result in ordered BF arrays with pore separation/diameter (L/D) ratios of up to 16.5. Evidence from surface potential scans show proof for preferential ion partitioning of HBr. Radial distribution functions and Voronoi polygon analysis of pore arrays show that they possess a high degree of conformational order. Past fabrication methods of NCP structures typically require multi-step processes. In contrast, we have established a new route for facile self-assembly of previously inaccessible patterns, which comprises of only a single operational step.