Hopping transport

Keywords Electron transfer Hole transport Hopping Superexchange Couphng to the molecular surroundings... 

In solid state materials, single-step electron transport between dopant species is well known. For example, electron-hole recombination accounts for luminescence in some materials [H]. Multistep hopping is also well known. Models for single and multistep transport are enjoying renewed interest in tlie context of DNA electron transfer [12, 13, 14 and 15]. Indeed, tliere are strong links between tire ET literature and tire literature of hopping conductivity in polymers [16]. 

Henderson P T, Jones D, Hampikian G, Kan Y Z and Schuster G B 1999 Long-distance charge transport in dupiex DNA the phonon-assisted poiaron-iike hopping mechanism Proc. Natl Acad. Sc/., USA 96 8353-8... 

In the above consideration it has been tacitly assumed that the charge carrier mobility docs not depend on the electric field. This is a good approximation for molecular crystals yet not for disordered systems in which transport occurs via hopping. Abkowitz et al. [37] have solved that problem for a field dependence of ft of the form p-po (FIFU) and trap-free SCL conduction. Their treatment predicts... 

Recently the effect of intrinsic traps on hopping transport in random organic systems was studied both in simulation and experiment [72]. In the computation it has been assumed that the eneigy distribution of the traps features the same Gaussian profile as that of bulk states. 

Because polarons are localized species, their natural transport mechanism is hopping. We shall now briefly describe the small polaron model, as developed by Holstein and Emin [26, 29, 46]. 

At very low temperatures, Holstein predicted that the small polaron would move in delocalized levels, the so-called small polaron band. In that case, mobility is expected to increase when temperature decreases. The transition between the hopping and band regimes would occur at a critical temperature T, 0.40. We note, however, that the polaron bandwidth is predicted to be very narrow ( IO Viojo, or lO 4 eV for a typical phonon frequency of 1000 cm-1). It is therefore expected that this band transport mechanism would be easily disturbed by crystal defects. 

Electron-hopping is the main charge-transport mechanism in ECHB materials. There is precedence in the photoconductivity Held for improved charge transport by incorporating a number of redox sites into the same molecule. A number of attempts to adapt this approach for ECHB materials have been documented. Many use the oxadiazole core as the electron-transport moiety and examples include radialene 40 and dendrimer 41. However, these newer systems do not offer significant improvements in electron injection over the parent PBD. 

Besides its temperature dependence, hopping transport is also characterized by an electric field-dependent mobility. This dependence becomes measurable at high field (namely, for a field in excess of ca. 10d V/cm). Such a behavior was first reported in 1970 in polyvinylcarbazole (PVK) [48. The phenomenon was explained through a Poole-ITenkel mechanism [49], in which the Coulomb potential near a charged localized level is modified by the applied field in such a way that the tunnel transfer rale between sites increases. The general dependence of the mobility is then given by Eq. (14.69)... 

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