Ligand-Field-Modulated Molecular Junctions: On Covalently Bonded Ethynyl–Electrode Interfaces

Abstract

Energy-level alignment (ELA) between Fermi levels of electrodes and frontier molecular orbitals (FMOs) dictates single-molecule I–V bias characteristics. Proposed herein to better achieve ELA is the drive of E FMO toward E Fermi via interactions between the anchoring group and the undercoordinated gold atom at the electrode apex, where the interactions and the shift of E FMO resemble the ligand-field-modulated orbital splitting. This concept is demonstrated by −CC–electrode and −CC–CC–electrode junctions. The junction current of the latter, with an additional ethynyl moiety, is slightly larger than that of the former for molecules with the same backbone. This finding is contradictory to the length-dependent exponential decrease in current. Simulations show that the orbital splitting creates an FMO composed of 5d xz orbitals of gold, with contributions not only from the ligated metal atom but also, intriguingly, from neighboring atoms or atoms in the underneath second layer, indicative of a distinct pinning effect. When the other terminal group is a −CN group, asymmetric I–V bias curves are observed. The degree of electric rectification is associated with the electrode configuration (e.g., pyramidal, stepped, or planar) and thus the strength of ethynyl–electrode ligand–metal orbital mixing. The scanning tunneling microscopy-based break junction technique shows a more pronounced rectification for junctions of the −CC–CC–electrode than for junctions of the −CC–electrode.

Charge transport in molecular junctions: General physical pictures, electrical measurement techniques, and their challenges

“…Since OPE3 is far longer than the Debye length, the modest gating efficiency is attributed to Fermi‐level pinning, which comes from OPE3's strong coupling to gold electrodes (especially, strong terminal ethynylene‐gold interaction). [ 91 ] At this point, it is important to address the issue that short EME systems are reported to suffer from low gating efficiency, [ 80 ] largely owing to their size being shorter or comparable to Debye lengths of common electrolytes.…”

Increased Surface Density of States at the Fermi Level for Electron Transport Across Single‐Molecule Junctions

“…Electron transport at the electrode‐molecule interfaces is important to many scientific disciplines and technological innovations. The interfacial transporting rate, formulated by the Fermi's golden rule, [1] is proportional to the surface density of states (SDOS) at the electrode Fermi level and to the square of the molecule‐electrode coupling strength which involves the molecular electronic structures and interfacial properties such as surface dipoles, [2] surface adsorption, [3, 4] charge transfer, [5] and orbital mixing [6] at the contact. For electron transport across molecular junctions, the junction conductance is typically described by a simple single‐level model [7, 8] .…”

Increased Surface Density of States at the Fermi Level for Electron Transport Across Single‐Molecule Junctions

“…Electron transport at the electrode‐molecule interfaces is important to many scientific disciplines and technological innovations. The interfacial transporting rate, formulated by the Fermi's golden rule, [1] is proportional to the surface density of states (SDOS) at the electrode Fermi level and to the square of the molecule‐electrode coupling strength which involves the molecular electronic structures and interfacial properties such as surface dipoles, [2] surface adsorption, [3, 4] charge transfer, [5] and orbital mixing [6] at the contact. For electron transport across molecular junctions, the junction conductance is typically described by a simple single‐level model [7, 8] .…”