journal article·2020-02-11

Electrostatic Interactions Shape Molecular Organization and Electronic Structure of Organic Semiconductor Blends

Gabriele D’Avino, Steffen Duhm, Raffaele Guido Della Valle, Georg Heimel, Martin Oehzelt, Satoshi Kera, Nobuo Ueno, David Beljonne, Ingo Salzmann

Chemistry of Materials· Volume 32· Issue 3
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Abstract

Halogenation of conjugated molecules represents a powerful approach to tune the electronic structure of molecular thin films through inductive effects and long-range intermolecular electrostatic interactions. The mixing of halogenated molecules with their pristine counterparts has recently proven successful in altering the blend’s energy levels to adjust the open-circuit voltage of organic solar cells by the mixing ratio. Here, we show that the prevailing rationale for this effect is not equally valid for different molecular orientations. We provide a comprehensive experimental and theoretical analysis of the prototypical blend formed by pentacene and perfluoropentacene to relate structure with electronic properties. We find a mixed-stack structural motif in standing and lying orientations depending on the substrate nature. In the standing orientation, the ionization potential lies in between the values of the pure components, in line with the established picture of averaged molecular quadrupole moments. For the lying orientation, however, we experimentally observe an ionization potential lower than both pristine values, which seems at odds with this simple rationale. Electrostatic simulations based on the knowledge of the atomistic structure of the films capture the complex experimental scenario for both orientations. In particular, the ultralow ionization potential of films formed by lying molecules is identified as a signature of the monolayer structure, where quadrupolar interactions are responsible for a difference of ca. 0.4 eV in the highest occupied molecular orbital energy as compared to thicker films with the same molecular orientation.
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Research context

OpenAlex topics: Organic Electronics and Photovoltaics · Spectroscopy and Quantum Chemical Studies · Advanced Chemical Physics Studies

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Institut Néel CNRS & Grenoble Alpes University, 38042 Grenoble, France

Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices and Joint International Research Laboratory of Carbon-Based Functional Materials and Devices, Soochow University, 215123 Suzhou, People’s Republic of China

Dipartimento di Chimica Industriale Toso Montanari, Università di Bologna/INSTM-UdR, 40136 Bologna, Italy

Institut für Physik, Humboldt-Universität zu Berlin, 12489 Berlin, Germany

Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany

Institute for Molecular Science, 444-8787 Okazaki, Japan

Graduate School of Advanced Integration Science, Chiba University, 263-8522 Chiba, Japan

Laboratory for the Chemistry of Novel Materials, University of Mons, B7000 Mons, Belgium

Department of Physics, Department of Chemistry & Biochemistry, Centre for Research in Molecular Modeling (CERMM), Centre for NanoScience Research (CeNSR), Concordia University, Montreal, QC, H4B 1R6, Canada

Funding

State Administration of Foreign Experts Affairs · Collaborative Innovation Center of Suzhou Nano Science and Technology · Ministry of Education of the People's Republic of China · Fonds de Recherche du Qu?bec - Nature et Technologies · Concordia University · Natural Sciences and Engineering Research Council of Canada · Soochow University-Western University Joint Center for Synchrotron Radiation Research

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