Electron transport in semiconducting polymers is usually inferior to hole transport, which is ascribed to charge trapping on isolated defect sites situated within the energy bandgap. However, a general understanding of the origin of these omnipresent charge traps, as well as their energetic position, distribution and concentration, is lacking. Here we investigate electron transport in a wide range of semiconducting polymers by current-voltage measurements of single-carrier devices. We observe for this materials class that electron transport is limited by traps that exhibit a gaussian energy distribution in the bandgap. Remarkably, the electron-trap distribution is identical for all polymers considered: the number of traps amounts to 3 × 10(23) traps per m(3) centred at an energy of ~3.6 eV below the vacuum level, with a typical distribution width of ~0.1 eV. This indicates that the electron traps have a common origin that, we suggest, is most likely related to hydrated oxygen complexes. A consequence of this finding is that the trap-limited electron current can be predicted for any polymer.

This article reviews the basic physical processes of charge transport and recombination in organic semiconductors. As a workhorse, LEDs based on a single layer of poly(p-phenylene vinylene) (PPV) derivatives are used. The hole transport in these PPV derivatives is governed by trap-free space-charge-limited conduction, with the mobility depending on the electric field and charge-carrier density. These dependencies are generally described in the framework of hopping transport in a Gaussian density of states distribution. The electron transport on the other hand is orders of magnitude lower than the hole transport. The reason is that electron transport is hindered by the presence of a universal electron trap, located at 3.6 eV below vacuum with a typical density of ca. 3 × 10¹⁷ cm⁻³. The trapped electrons recombine with free holes via a non-radiative trap-assisted recombination process, which is a competing loss process with respect to the emissive bimolecular Langevin recombination. The trap-assisted recombination in disordered organic semiconductors is governed by the diffusion of the free carrier (hole) towards the trapped carrier (electron), similar to the Langevin recombination of free carriers where both carriers are mobile. As a result, with the charge-carrier mobilities and amount of trapping centers known from charge-transport measurements, the radiative recombination as well as loss processes in disordered organic semiconductors can be fully predicted. Evidently, future work should focus on the identification and removing of electron traps. This will not only eliminate the non-radiative trap-assisted recombination, but, in addition, will shift the recombination zone towards the center of the device, leading to an efficiency improvement of more than a factor of two in single-layer polymer LEDs.

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Electron traps in semiconducting polymersNicolai, H. T.; Mandoc, M. M.; Blom, P. W. M. Physics, 83(19), 195204-1-195204-5. [195204]. https://doi.org/10.1103/PhysRevB. 83.195204 Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. The low electron currents in poly(dialkoxy-p-phenylene vinylene) (PPV) derivatives and their steep voltage dependence are generally explained by trap-limited conduction in the presence of an exponential trap distribution. Here we demonstrate that the electron transport of several PPV derivatives can also be well described with a trap distribution that is Gaussianly distributed within the band gap. In contrast to the exponential distribution the trap-limited electron currents can now be modeled using the same Gaussian trap distribution for the various PPV derivatives.

Characterization of the hole transport in blue-emitting polymers as poly(9,9-dioctylfluorene) (PFO) is strongly hindered by their large ionization potential of ∼6 eV. Using common anodes as poly(3,4-ethylenedioxythiophene)/poly(styrenesulphonic acid) leads to a strongly injection limited current. We demonstrate that molybdenum trioxide forms an Ohmic hole contact on PFO, enabling the observation of a space-charge-limited current(SCLC). This allows a direct determination of the hole mobility PFO of 1.3×10−9 m2/V s at room temperature, in good agreement with previously reported mobility values determined by time-of-flight measurements.