Colin Van Dyck

Molecular rectifiers: a new design based on asymmetric anchoring moieties.

The quest for a molecular rectifier is among the major challenges of molecular electronics. We introduce three simple rules to design an efficient rectifying molecule and demonstrate its functioning at the theoretical level, relying on the NEGF-DFT technique. The design rules notably require both the introduction of asymmetric anchoring moieties and a decoupling bridge. They lead to a new rectification mechanism based on the compression and control of the HOMO/LUMO gap by the electrode Fermi levels, arising from a pinning effect. Significant rectification ratios up to 2 orders of magnitude are theoretically predicted as the mechanism opposes resonant to nonresonant tunneling.

Harnessing Quantum Interference in Molecular Dielectric Materials.

We investigate the relationship between dielectric response and charge transport in molecule-based materials operating in the quantum coherent regime. We find that quantum interference affects these observables differently, for instance, allowing current passing through certain materials to be reduced by orders of magnitude without affecting dielectric behavior (or band gap). As an example, we utilize ab initio electronic structure theory to calculate conductance and dielectric constants of cross-conjugated anthraquinone (AQ)-based and linearly conjugated anthracene (AC)-based materials. In spite of having nearly equal fundamental gaps, electrode bonding configurations, and molecular dimensions, we find a ∼1.7 order of magnitude (∼50-fold) reduction in the conductance of the AQ-based material relative to the AC-based material, a value in close agreement with recent measurements, while the calculated dielectric constants of both materials are nearly identical. From these findings, we propose two molecular materials in which quantum interference is used to reduce leakage currents across a ∼25 Å monolayer gap with dielectric constants larger than 4.5.

Bottom-up, Robust Graphene Ribbon Electronics in All-Carbon Molecular Junctions

Large-area molecular electronic junctions consisting of 5-carbon wide graphene ribbons (GR) with lengths of 2-12 nm between carbon electrodes were fabricated by electrochemical reduction of diazotized 1,8-diaminonaphthalene. Their conductance greatly exceeds that observed for other molecular junctions of similar thicknesses, by a factor of >1 × 104 compared to polyphenylenes and >1 × 107 compared to alkane chains. The remarkable increase of conductance of the GR nanolayer results from (i) uninterrupted planarity of fused-arene structure affording extensive π-electron delocalization and (ii) enhanced electronic coupling of molecular layer with the carbon bottom contact by two-point covalent bonding, in agreement with DFT-based simulations.

Chain Length Dependence of the Dielectric Constant and Polarizability in Conjugated Organic Thin Films

Dielectric materials are ubiquitous in optics, electronics, and materials science. Recently, there have been new efforts to characterize the dielectric performance of thin films composed of molecular assemblies. In this context, we investigate here the relationship between the polarizability of the constituent molecules and the film dielectric constant, using periodic density functional theory (DFT) calculations, for polyyne and saturated alkane chains. In particular, we explore the implication of the superlinear chain length dependence of the polarizability, a specific feature of conjugated molecules. We show and explain from DFT calculations and a simple depolarization model that this superlinearity is attenuated by the collective polarization. However, it is not completely suppressed. This confers a very high sensitivity of the dielectric constant to the thin film thickness. This latter can increase by a factor of 3-4 at reasonable coverages, by extending the molecular length. This significantly limits the decline of the thin film capacitance with the film thickness. Therefore, the conventional fit of the capacitance versus thickness is not appropriate to determine the dielectric constant of the film. Finally, we show that the failures of semilocal approximations of the exchange-correlation functional lead to a very significant overestimation of this effect.