Redox Control of Charge Transport in Vertical Ferrocene Molecular Tunnel Junctions

Abstract

Controlling charge transport through molecular-scale devices is of crucial importance. This article reports an effective route to tailor cross-plane charge transport in a vertical molecular tunneling junction through controlled chemical or electrochemical redox reaction in the self-assembled molecular monolayers buried under graphene. This redox control of the cross-plane charge transport is important for exploring fundamental mechanisms and realizing new functionalities in molecular electronics.

Van der Waals Heterostructures by Design: From 1D and 2D to 3D

“…35 The flexible assembly of diverse 2D/2D heterostructures with widely variable electronic structures and twisting angles while retaining atomically clean interfaces has provided a rich playground for exploring exotic properties, such as unconventional ll superconductivity, 17 Moire ´excitons, 36 and 2D magnetic order. 37 Such 2D/2D heterostructures are further extended to hybrid 2D/self-assembled monolayers (SAMs), 38,39 extended VDW superlattices, 40 and 3D VDW frameworks. 41 Finally, considering VDW interactions represent a universal force between any two given materials, the VDW-integration approach can be broadly expanded to virtually any material systems as long as the interface is flat enough or at least one component is compliant enough to allow the interface to naturally relax to VDW distance to activate the VDW interaction.…”

Functional Redox‐Active Molecular Tunnel Junctions

“…Large area molecular junctions typically lack a gate electrode, but recently a large-area junction of the form of AuÀ SAM//graphene/electrolyte with a derivative of compound 13 has been reported where the redox-state of Fc could be controlled. [62] Here, the oxidation state of the Fc units can be controlled via electrochemical gating through the graphene top electrode. In this device configuration, the rectification of the junction could be turned on and off by controlling the redox state Fc moieties (Figure 11c).…”

“…The Fermi‐levels of the source and drain electrode with respect to the molecular levels were controlled by the gating electrode, resulting in the crossing of the Fermi‐levels with the molecular orbitals as indicated by the white arrows where the oxidation state of the molecule changes. Large area molecular junctions typically lack a gate electrode, but recently a large‐area junction of the form of Au−SAM//graphene/electrolyte with a derivative of compound 13 has been reported where the redox‐state of Fc could be controlled [62] . Here, the oxidation state of the Fc units can be controlled via electrochemical gating through the graphene top electrode.…”

π‐Conjugation Induced Anchoring of Ferrocene on Graphdiyne Enable Shuttle‐Free Redox Mediation in Lithium‐Oxygen Batteries

“…In fact, given that the π – π interaction between the layered GDY and ferrocene, more Fc in electrolyte may be absorbed on GDY with increase of Fc concentration. [ 21 ] We hold the opinion that the electronic interaction in RM‐support is crucial to the synergistic enhancement of electrocatalytic performance. To demonstrate the OER behavior, we conducted chronopotentiometry (CP) in advance to deposit equal amounts of Li 2 O 2 (Figure S6 , Supporting Information), and then sweeping in an OER involved potential.…”