Molecular ensemble junctions with inter-molecular quantum interference

We report of a high yield method to form nanopore molecular ensembles junctions containing ~40,000 molecules, in which the semimetal bismuth (Bi) is a top contact. Conductance histograms of these junctions are double-peaked (bi-modal), a behavior that is typical for single molecule junctions but not expected for junctions with thousands of molecules. This unique observation is shown to result from a new form of quantum interference that is inter-molecular in nature, which occurs in these junctions since the very long coherence length of the electrons in Bi enables them to probe large ensembles of molecules while tunneling through the junctions. Under such conditions, each molecule within the ensembles becomes an interference path that modifies via its tunneling phase the electronic structure of the entire junction. This new form of quantum interference holds a great promise for robust novel conductance effects in practical molecular junctions.