Electron transport and redox reactions in carbon-based molecular electronic junctions

Abstract

A unique molecular junction design is described, consisting of a molecular mono- or multilayer oriented between a conducting carbon substrate and a metallic top contact. The sp² hybridized graphitic carbon substrate (pyrolyzed photoresist film, PPF) is flat on the scale of the molecular dimensions, and the molecular layer is bonded to the substrate via diazonium ion reduction to yield a strong, conjugated C–C bond. Molecular junctions were completed by electron-beam deposition of copper, titanium oxide, or aluminium oxide followed by a final conducting layer of gold. Vibrational spectroscopy and XPS of completed junctions showed minimal damage to the molecular layer by metal deposition, although some electron transfer to the molecular layer resulted in partial reduction in some cases. Device yield was high (>80%), and the standard deviations of junction electronic properties such as low voltage resistance were typically in the range of 10–20%. The resistance of PPF/molecule/Cu/Au junctions exhibited a strong dependence on the structure and thickness of the molecular layer, ranging from 0.13 Ω cm² for a nitrobiphenyl monolayer, to 4.46 Ω cm² for a biphenyl monolayer, and 160 Ω cm² for a 4.3 nm thick nitrobiphenyl multilayer. Junctions containing titanium or aluminium oxide had dramatically lower conductance than their PPF/molecule/Cu counterparts, with aluminium oxide junctions exhibiting essentially insulating behavior. However, in situ Raman spectroscopy of PPF/nitroazobenzene/AlO_x/Au junctions with partially transparent metal contacts revealed that redox reactions occurred under bias, with nitroazobenzene (NAB) reduction occurring when the PPF was biased negative relative to the Au. Similar redox reactions were observed in PPF/NAB/TiO_x/Au molecular junctions, but they were accompanied by major effects on electronic behavior, such as rectification and persistent conductance switching. Such switching was evident following polarization of PPF/molecule/TiO₂/Au junctions by positive or negative potential pulses, and the resulting conductance changes persisted for several minutes at room temperature. The “memory” effect implied by these observations is attributed to a combination of the molecular layer and the TiO₂ properties, namely metastable “trapping” of electrons in the TiO₂ when the Au is negatively biased.