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Identification of Ultrafast Relaxation Processes As a Major Reason for Inefficient Exciton Diffusion in Perylene-Based Organic Semiconductors

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† Institut für Physikalische und Theoretische Chemie, Universität Würzburg, Emil-Fischer-Str. 42, 97074 Würzburg, Germany
‡ Lehrstuhl für Experimentelle Physik VI, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany
§ ZAE Bayern e.V., Am Galgenberg 87, 97074 Würzburg, Germany
[email protected]
Cite this: J. Am. Chem. Soc. 2014, 136, 26, 9327–9337
Publication Date (Web):June 9, 2014
https://doi.org/10.1021/ja413115h
Copyright © 2014 American Chemical Society
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Abstract

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The exciton diffusion length (LD) is a key parameter for the efficiency of organic optoelectronic devices. Its limitation to the nm length scale causes the need of complex bulk-heterojunction solar cells incorporating difficulties in long-term stability and reproducibility. A comprehensive model providing an atomistic understanding of processes that limit exciton trasport is therefore highly desirable and will be proposed here for perylene-based materials. Our model is based on simulations with a hybrid approach which combines high-level ab initio computations for the part of the system directly involved in the described processes with a force field to include environmental effects. The adequacy of the model is shown by detailed comparison with available experimental results. The model indicates that the short exciton diffusion lengths of α-perylene tetracarboxylicdianhydride (PTCDA) are due to ultrafast relaxation processes of the optical excitation via intermolecular motions leading to a state from which further exciton diffusion is hampered. As the efficiency of this mechanism depends strongly on molecular arrangement and environment, the model explains the strong dependence of LD on the morphology of the materials, for example, the differences between α-PTCDA and diindenoperylene. Our findings indicate how relaxation processes can be diminished in perylene-based materials. This model can be generalized to other organic compounds.

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Details of the quantum dynamical simulation together with the potential energy surface of the SD1 state and the Cartesian coordinates of relevant DIP and PTCDA dimers are given. This material is available free of charge via the Internet at http://pubs.acs.org/.

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