Elementary steps in electrical doping of organic semiconductors

Max L. Tietze (), Johannes Benduhn, Paul Pahner, Bernhard Nell, Martin Schwarze, Hans Kleemann, Markus Krammer, Karin Zojer, Koen Vandewal and Karl Leo ()
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Max L. Tietze: Technische Universität Dresden
Johannes Benduhn: Technische Universität Dresden
Paul Pahner: Technische Universität Dresden
Bernhard Nell: Technische Universität Dresden
Martin Schwarze: Technische Universität Dresden
Hans Kleemann: Technische Universität Dresden
Markus Krammer: Graz University of Technology
Karin Zojer: Graz University of Technology
Koen Vandewal: Technische Universität Dresden
Karl Leo: Technische Universität Dresden

Nature Communications, 2018, vol. 9, issue 1, 1-9

Abstract: Abstract Fermi level control by doping is established since decades in inorganic semiconductors and has been successfully introduced in organic semiconductors. Despite its commercial success in the multi-billion OLED display business, molecular doping is little understood, with its elementary steps controversially discussed and mostly-empirical-materials design. Particularly puzzling is the efficient carrier release, despite a presumably large Coulomb barrier. Here we quantitatively investigate doping as a two-step process, involving single-electron transfer from donor to acceptor molecules and subsequent dissociation of the ground-state integer-charge transfer complex (ICTC). We show that carrier release by ICTC dissociation has an activation energy of only a few tens of meV, despite a Coulomb binding of several 100 meV. We resolve this discrepancy by taking energetic disorder into account. The overall doping process is explained by an extended semiconductor model in which occupation of ICTCs causes the classically known reserve regime at device-relevant doping concentrations.

Date: 2018
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DOI: 10.1038/s41467-018-03302-z

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