Excitons in polycrystalline and disordered films of organic semiconductors have been shown to diffuse over distances of 10-50 nm. Here, using polarization- and wavelength-dependent photoconductivity in the highly ordered organic semiconductor rubrene, we show that the diffusion of triplet excitons in this material occurs over macroscopic distances (2-8 μm), comparable to the light absorption length. Dissociation of these excitons at the surface of the crystal is found to be the main source of photoconductivity in rubrene. In addition, we observe strong photoluminescence quenching and a simultaneous enhancement of photoconductivity when the crystal surface is functionalized with exciton splitters. In combination with time-resolved measurements, these observations strongly suggest that long-lived triplet excitons are indeed generated in molecular crystals by fission of singlets, and these triplets provide a significant contribution to the surface photocurrent generated in organic materials. Our findings indicate that the exciton diffusion bottleneck is not an intrinsic limitation of organic semiconductors.

We report a systematic study of the bias stress effect at semiconductor-dielectric interfaces using singlecrystal organic field-effect transistors as a test bed. A combination of electrical transport and ultraviolet photoelectron spectroscopy suggests that this instability is due to a ground-state ͑i.e., occurring in the dark͒ charge transfer of holes from the accumulation channel of the semiconductor to localized states of a disordered insulator. The proposed model is not semiconductor specific and therefore provides a general analytical description of this instability in a variety of organic and inorganic band semiconductors interfaced with amorphous insulators.

Fundamental studies of intrinsic charge transport properties of organic semiconductors are often hindered by charge traps associated with static disorder present even in optimized single-crystal devices. Here, we report a method of surface functionalization using an inert non-conjugated polymer, perfluoropolyether (PFPE), deposited at the surface of organic molecular crystals, which results in accumulation of mobile holes and a 'trap healing' effect at the crystal/PFPE interface. As a consequence, a remarkable ultralow-noise, trp-free conduction regime characterized by intrinsic mobility and transport anisotropy emerges in organic single crystals, and Hall effect measurements with an unprecedented signal-to-noise ratio are demonstrated. This general method to convert trap-dominated organic semiconductors to intrinsic systems may enable the determination of intrinsic transport parameters with high accuracy and make Hall effect measurements in molecular crystals ubiquitous.

In this perspective article, we discuss the dynamic instability of charge carrier transport in a range of popular organic semiconductors. We observe that in many cases field-effect mobility, an important parameter used to characterize the performance of organic field-effect transistors (OFETs), strongly depends on the rate of the gate voltage sweep during the measurement. Some molecular systems are so dynamic that their nominal mobility can vary by more than one order of magnitude, depending on how fast the measurements are performed, making an assignment of a single mobility value to devices meaningless. It appears that dispersive transport in OFETs based on disordered semiconductors, those with a high density of localized trap states distributed over a wide energy range, is responsible for the gate voltage sweep rate dependence of nominal mobility. We compare such rate dependence in different materials and across different device architectures, including pristine and trap-dominated single-crystal OFETs, as well as solution-processed polycrystalline thin-film OFETs. The paramount significance given to a single mobility value in the organic electronics community and the practical importance of OFETs for applications thus suggest that such an issue, previously either overlooked or ignored, is in fact a very important point to consider when engaging in fundamental studies of charge carrier mobility in organic semiconductors or designing applied circuits with organic semiconductors.

We report a novel method for stable doping of carbon nanotubes (CNT) based on methods of molecular self assembly. A conformal growth of a self-assembled monolayer of fluoroalkyl trichloro-silane (FTS) at CNT surfaces results in a strong increase of the sheet conductivity of CNT electrodes by 60–300%, depending on the CNT chirality and composition. The charge carrier mobility of undoped partially aligned CNT films was independently estimated in a field-effect transistor geometry (∼100 cm2V−1s−1). The hole density induced by the FTS monolayer in CNT sheets is estimated to be ∼1.8 × 1014 cm−2. We also show that FTS doping of CNT anodes greatly improves the performance of organic solar cells. This large and stable doping effect, easily achieved in large-area samples, makes this approach very attractive for applications of CNTs in transparent and flexible electronics.

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