Long-Range Activationless Photostimulated Charge Transport in Symmetric Molecular Junctions

Molecular electronic junctions consisting of nitroazobenzene oligomers covalently bonded to a conducting carbon surface using an established “all-carbon” device design were illuminated with UV–vis light through a partially transparent top electrode. Monitoring junction conductance with a DC bias imposed permitted observation of photocurrents while varying the incident wavelength, light intensity, molecular layer thickness, and temperature. The photocurrent spectrum tracked the in situ absorption spectrum of nitroazobenzene, increased linearly with light intensity, and depended exponentially on applied bias. The electronic characteristics of the photocurrent differed dramatically from those of the same device in the dark, with orders of magnitude higher conductance and very weak attenuation with molecular layer thickness (β = 0.14 nm–1 for thickness above 5 nm). The temperature dependence of the photocurrent was opposite that of the dark current, with a 35% decrease in conductance between 80 and 450 K, while the dark current increased by a factor of 4.5 over the same range. The photocurrent was similar to the dark current for thin molecular layers but greatly exceeded the dark current for low bias and thick molecular layers. We conclude that the light and dark mechanisms are additive, with photoexcited carriers transported without thermal activation for a thickness range of 5–10 nm. The inverse temperature dependence is likely due to scattering or recombination events, both of which increase with temperature and in turn decrease the photocurrent. Photostimulated resonant transport potentially widens the breadth of conceivable molecular electronic devices and may have immediate value for wavelength-specific photodetection.