CP-AFM Molecular Tunnel Junctions with Alkyl Backbones Anchored Using Alkynyl and Thiol Groups: Microscopically Different Despite Phenomenological Similarity.

Abstract

In this paper, we report results on the electronic structure and transport properties of molecular junctions fabricated via conducting probe atomic force microscopy (CP-AFM) using self-assembled monolayers (SAMs) of n-alkyl chains anchored with acetylene groups (CnA; n = 8, 9, 10, and 12) on Ag, Au, and Pt electrodes. We found that the current-voltage (I-V) characteristics of CnA CP-AFM junctions can be very accurately reproduced by the same off-resonant single-level model (orSLM) successfully utilized previously for many other junctions. We demonstrate that important insight into the energy-level alignment can be gained from experimental data of transport (processed via the orSLM) and ultraviolet photoelectron spectroscopy combined with ab initio quantum chemical information based on the many-body outer valence Green's function method. Measured conductance GAg < GAu < GPt is found to follow the same ordering as the metal work function ΦAu < ΦAu < ΦPt, a fact that points toward a transport mediated by an occupied molecular orbital (MO). Still, careful data analysis surprisingly revealed that transport is not dominated by the ubiquitous HOMO but rather by the HOMO-1. This is an important difference from other molecular tunnel junctions with p-type HOMO-mediated conduction investigated in the past, including the alkyl thiols (CnT) to which we refer in view of some similarities. Furthermore, unlike in CnT and other junctions anchored with thiol groups investigated in the past, the AFM tip causes in CnA an additional MO shift, whose independence of size (n) rules out significant image charge effects. Along with the prevalence of the HOMO-1 over the HOMO, the impact of the "second" (tip) electrode on the energy level alignment is another important finding that makes the CnA and CnT junctions different. What ultimately makes CnA unique at the microscopic level is a salient difference never reported previously, namely, that CnA's alkyne functional group gives rise to two energetically close (HOMO and HOMO-1) orbitals. This distinguishes the present CnA from the CnT, whose HOMO stemming from its thiol group is well separated energetically from the other MOs.