Photostimulated Near-Resonant Charge Transport over 60 nm in Carbon-Based Molecular Junctions.

The bias and temperature dependence of both dark and photoinduced currents in carbon-based molecular junctions were examined over a wide range of oligomeric layer thickness (d) values from 4 to 60 nm. The dark current density versus bias (JV) response of nitroazobenzene molecular junctions exhibits the exponential thickness dependence consistent with coherent tunneling when d < 5 nm, but becomes weakly dependent on d and temperature (T) for d = 15-60 nm. The photocurrent (PC) response is orders of magnitude higher than the dark current for the same d and bias, with very different curve shape and much earlier onset with bias. Although the dark and PC differed greatly in magnitude for d > 14 nm, they both exhibit near zero attenuation coefficients (β < 0.05 nm-1) and are activationless (Eact < 5 meV) below ∼200 K. For d > 14 nm, both dark and PC become electric field (E) dependent and exhibit approximate overlap of J versus E response for d = 14-60 nm. The value of ln J versus E1/2 is linear for both PC and dark current, with very different magnitudes and slopes. We propose an orbital mediated transport for PC, which involves sequential tunneling of photogenerated electrons and holes between frontier orbitals of adjacent, weakly interacting oligomeric subunits. Such transport is "bulk-limited", E dependent, and nearly activationless due to small tunneling barriers and short distances between adjacent molecular orbitals. In contrast, the dark current is activated and injection limited due to an interfacial energy barrier much larger than that for bulk transport in the junction interior. Rapid, low-barrier transport between orbitals in adjacent molecules should significantly extend the "range" of molecular electronics to >50 nm and avoid the usually strong temperature dependence observed in thicker organic films.