Break junction

Abstract: Since it was first suggested1 that a single molecule might function as an active electronic component, a number of techniques have been developed to measure the charge transport properties of single molecules2,3,4,5,6,7,8,9,10,11,12. Although scanning tunnelling microscopy observations under high vacuum conditions can allow stable measurements of electron transport, most measurements of a single molecule bonded in a metal–molecule–metal junction exhibit relatively large variations in conductance. As a result, even simple predictions about how molecules behave in such junctions have still not been rigorously tested. For instance, it is well known13,14 that the tunnelling current passing through a molecule depends on its conformation; but although some experiments have verified this effect15,16,17,18, a comprehensive mapping of how junction conductance changes with molecular conformation is not yet available. In the simple case of a biphenyl—a molecule with two phenyl rings linked by a single C–C bond—conductance is expected to change with the relative twist angle between the two rings, with the planar conformation having the highest conductance. Here we use amine link groups to form single-molecule junctions with more reproducible current–voltage characteristics19. This allows us to extract average conductance values from thousands of individual measurements on a series of seven biphenyl molecules with different ring substitutions that alter the twist angle of the molecules. We find that the conductance for the series decreases with increasing twist angle, consistent with a cosine-squared relation predicted for transport through π-conjugated biphenyl systems13.

Abstract: The continuing miniaturization of microelectronics raises the prospect of nanometre-scale devices with mechanical and electrical properties that are qualitatively different from those at larger dimensions. The investigation of these properties, and particularly the increasing influence of quantum effects on electron transport, has therefore attracted much interest. Quantum properties of the conductance can be observed when ‘breaking’ a metallic contact: as two metal electrodes in contact with each other are slowly retracted, the contact area undergoes structural rearrangements until it consists in its final stages of only a few bridging atoms1,2,3. Just before the abrupt transition to tunnelling occurs, the electrical conductance through a monovalent metal contact is always close to a value of 2e2/h (≈12.9 Ω−1), where e is the charge on an electron and h is Planck's constant4,5,6. This value corresponds to one quantum unit of conductance, thus indicating that the ‘neck’ of the contact consists of a single atom7. In contrast to previous observations of only single-atom necks, here we describe the breaking of atomic-scale gold contacts, which leads to the formation of gold chains one atom thick and at least four atoms long. Once we start to pull out a chain, the conductance never exceeds 2e2/h, confirming that it acts as a one-dimensional quantized nanowire. Given their high stability and the ability to support ballistic electron transport, these structures seem well suited for the investigation of atomic-scale electronics.

Abstract: We measure the conductance of amine-terminated molecules by breaking Au point contacts in a molecular solution at room temperature. We find that the variability of the observed conductance for the diamine molecule−Au junctions is much less than the variability for diisonitrile− and dithiol−Au junctions. This narrow distribution enables unambiguous conductance measurements of single molecules. For an alkane diamine series with 2−8 carbon atoms in the hydrocarbon chain, our results show a systematic trend in the conductance from which we extract a tunneling decay constant of 0.91 ± 0.03 per methylene group. We hypothesize that the diamine link binds preferentially to undercoordinated Au atoms in the junction. This is supported by density functional theory-based calculations that show the amine binding to a gold adatom with sufficient angular flexibility for easy junction formation but well-defined electronic coupling of the N lone pair to the Au. Therefore, the amine linkage leads to well-defined conductanc...