The supramolecular structure and van der Waals interactions affect the electronic structure of ferrocenyl-alkanethiolate SAMs on gold and silver electrodes.

Understanding the influence of structural properties on the electronic structure will pave the way for optimization of charge transport properties of SAM devices. In this study, we systematically investigate the supramolecular and electronic structures of ferrocene (Fc) terminated alkanethiolate (SC Fc) SAMs on both Au and Ag substrates with = 1-15 by using a combination of synchrotron based near edge X-ray absorption spectroscopy (NEXAFS), photoemission spectroscopy (PES), and density functional theory (DFT) calculations. Odd-even effects in the supramolecular structure persist over the entire range of = 1-15, which, in turn, explain the odd-even effects in the onset energy of the highest occupied molecular (HOMO) orbital.

Orbital dependent ultrafast charge transfer dynamics of ferrocenyl-functionalized SAMs on gold studied by core-hole clock spectroscopy.

Understanding the charge transport properties in general of different molecular components in a self-assembled monolayer (SAM) is of importance for the rational design of SAM molecular structures for molecular electronics. In this study, we study an important aspect of the charge transport properties, i.e.

Controlling the direction of rectification in a molecular diode.

A challenge in molecular electronics is to control the strength of the molecule-electrode coupling to optimize device performance. Here we show that non-covalent contacts between the active molecular component (in this case, ferrocenyl of a ferrocenyl-alkanethiol self-assembled monolayer (SAM)) and the electrodes allow for robust coupling with minimal energy broadening of the molecular level, precisely what is required to maximize the rectification ratio of a molecular diode. In contrast, strong chemisorbed contacts through the ferrocenyl result in large energy broadening, leakage currents and poor device performance.

Giant enhancement in vertical conductivity of stacked CVD graphene sheets by self-assembled molecular layers.

Layer-by-layer-stacked chemical vapour deposition (CVD) graphene films find applications as transparent and conductive electrodes in solar cells, organic light-emitting diodes and touch panels. Common to lamellar-type systems with anisotropic electron delocalization, the plane-to-plane (vertical) conductivity in such systems is several orders lower than its in-plane conductivity. The poor electronic coupling between the planes is due to the presence of transfer process organic residues and trapped air pocket in wrinkles.

Supramolecular structure of self-assembled monolayers of ferrocenyl terminated n-alkanethiolates on gold surfaces.

It is important to understand the structure of redox-active self-assembled monolayers (SAMs) down to the atomic scale, since these SAMS are widely used as model systems in studies of mechanisms of charge transport or to realize electronic functionality in molecular electronic devices. We studied the supramolecular structure of SAMs of n-alkanethiolates with ferrocenyl (Fc) end groups (S(CH2)nFc, n = 3 or 4) on Au(111) by scanning tunneling microscopy (STM). In this system, the tilt angle of the Fc units with respect to the surface normal (α) depends on the value of n because the Au-S-C bond angle is fixed.

The role of van der Waals forces in the performance of molecular diodes.

One of the main goals of organic and molecular electronics is to relate the performance and electronic function of devices to the chemical structure and intermolecular interactions of the organic component inside them, which can take the form of an organic thin film, a self-assembled monolayer or a single molecule. This goal is difficult to achieve because organic and molecular electronic devices are complex physical-organic systems that consist of at least two electrodes, an organic component and two (different) organic/inorganic interfaces. Singling out the contribution of each of these components remains challenging.