This paper reports the electron transport characteristics of carbon/molecule/Cu molecular junctions, where aromatic molecules (azobenzene or AB and nitroazobenzene or NAB) are employed as the molecular component. It is shown that these devices can be made with high yield (>90%), display excellent reproducibility, and can withstand at least 1.5 × 10 9 potential cycles and temperatures of at least 180°C. Transport mechanisms are investigated by analysis of current density/voltage (J-V) curves as a function of the molecular layer thickness and temperature. Results show that J decreases exponentially with thickness, giving a measured value for the low-bias attenuation factor ( ) of 2.5 ( 0.1 nm -1 for AB and NAB. In addition, it is shown that transport is not thermally activated over a wide range of temperatures (5-450 K) and that the appearance of a thermally "activated" region at higher temperatures can be accounted for by the effect of temperature on the distribution of electrons around the Fermi level of the contact(s). These results indicate that quantum mechanical tunneling is likely the mechanism for charge transport in these junctions. Although application of the Simmons tunneling model leads to transport parameters consistent with nonresonant tunneling, the parameters obtained from fitting experimental data indicate that the barrier height and/or shape, effective mass, and dielectric constant (ε) can all change with thickness. Experimental measurements of ε and density functional theory (DFT) calculations of molecular energy levels and polarizability support these conclusions. Finally, the implications of the transport mechanisms are discussed from the viewpoint of designing functional molecular electronic devices
