Microscopic Insight into the Electronic Structure of BCF-Doped Oligothiophenes from Ab Initio Many-Body TheoryClick to copy article linkArticle link copied!
- Richard SchierRichard SchierPhysics Department and IRIS Adlershof, Humboldt-Universität zu Berlin, 12489 Berlin, GermanyMore by Richard Schier
- Ana M. ValenciaAna M. ValenciaPhysics Department and IRIS Adlershof, Humboldt-Universität zu Berlin, 12489 Berlin, GermanyInstitute of Physics, Carl von Ossietzky Universität Oldenburg, 26129 Oldenburg, GermanyMore by Ana M. Valencia
- Caterina Cocchi*Caterina Cocchi*Email: [email protected]Physics Department and IRIS Adlershof, Humboldt-Universität zu Berlin, 12489 Berlin, GermanyInstitute of Physics, Carl von Ossietzky Universität Oldenburg, 26129 Oldenburg, GermanyMore by Caterina Cocchi
Abstract
Lewis acids like tris(pentafluorophenyl)borane (BCF) offer promising routes for efficient p-doping of organic semiconductors. The intriguing experimental results achieved so far call for a deeper understanding of the underlying doping mechanisms. In a first-principles work, based on state-of-the-art density-functional theory and many-body perturbation theory, we investigate the electronic and optical properties of donor/acceptor complexes formed by quarterthiophene (4T) doped by BCF. For reference, hexafluorobenzene (C6F6) and BF3 are also investigated as dopants for 4T. Modeling the adducts as bimolecules in vacuo, we find negligible charge transfer in the ground state and frontier orbitals either segregated on opposite sides of the interface (4T:BCF) or localized on the donor (4T:BF3, 4T:C6F6). In the optical spectrum of 4T:BCF, a charge-transfer excitation appears at the lowest energy, corresponding to the transition between the frontier states, which exhibit very small but nonvanishing wave function overlap. In the other two adducts, the absorption is given by a superposition of the features of the constituents. Our results clarify that the intrinsic electronic interactions between donor and acceptor are not responsible for the doping mechanisms induced by BCF and related Lewis acids. Extrinsic factors, such as solvent–solute interactions, intermolecular couplings, and thermodynamic effects, have to be systematically analyzed for this purpose.
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This article is cited by 7 publications.
- Nadine Rußegger, Ana M. Valencia, Lena Merten, Matthias Zwadlo, Giuliano Duva, Linus Pithan, Alexander Gerlach, Alexander Hinderhofer, Caterina Cocchi, Frank Schreiber. Molecular Charge Transfer Effects on Perylene Diimide Acceptor and Dinaphthothienothiophene Donor Systems. The Journal of Physical Chemistry C 2022, 126
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- Christoph P. Theurer, Ana M. Valencia, Julian Hausch, Clemens Zeiser, Vipilan Sivanesan, Caterina Cocchi, Petra Tegeder, Katharina Broch. Photophysics of Charge Transfer Complexes Formed by Tetracene and Strong Acceptors. The Journal of Physical Chemistry C 2021, 125
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, 6313-6323. https://doi.org/10.1021/acs.jpcc.0c10815
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, 27801-27810. https://doi.org/10.1021/acs.jpcc.0c08812
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, 8192-8201. https://doi.org/10.1039/D3TA00231D
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- Pablo Simón Marqués, Giacomo Londi, Brett Yurash, Thuc-Quyen Nguyen, Stephen Barlow, Seth R. Marder, David Beljonne. Understanding how Lewis acids dope organic semiconductors: a “complex” story. Chemical Science 2021, 12
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, 7012-7022. https://doi.org/10.1039/D1SC01268A
- Jannis Krumland, Ana Maria Valencia, Caterina Cocchi. Exploring organic semiconductors in solution: the effects of solvation, alkylization, and doping. Physical Chemistry Chemical Physics 2021, 23
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, 4841-4855. https://doi.org/10.1039/D0CP06085B
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