The Unusual Dielectric Response of Large Area Molecular Tunnel Junctions Probed with Impedance Spectroscopy

The dielectric behavior of organic materials at molecular dimensions can be vastly different than their bulk counterparts and therefore it is important to investigate and control the dielectric response of molecular-scale materials for a large variety of applications. Large-area molecular junctions are explored to study the charge transport mechanisms with unprecedented detail and to demonstrate novel functionalities. Therefore, large-area molecular junctions are, in principle, a promising platform to study the dielectric effects at the molecular scale. This review summarizes recent progress on the measurements and understanding of the dielectric behavior of molecular systems and how they behave differently from their bulk properties. This review introduces, briefly, the concepts of impedance spectroscopy (IS) and how this technique can be applied to study the dielectric response of solid-state large-area molecular junctions. This analysis gives new insights in the factors that determine the dielectric constant of monolayers (including collective electrostatic effects and how the dielectric constant increases with monolayer thickness), how IS gives new insights into the role of defects, and the factors that contribute to the molecule–electrode contact resistance. This review ends with an outlook highlighting interesting future directions.