journal article·2024Open access

Polaron absorption in aligned conjugated polymer films: breakdown of adiabatic treatments and going beyond the conventional mid-gap state model

Garrett LeCroy, Raja Ghosh, Viktoriia Untilova, Lorenzo Guio, Kevin H. Stone, Martin Brinkmann, Christine Luscombe, Frank C. Spano, Alberto Salleo

Materials Horizons· Volume 11· Issue 2

Abstract

= 0.075 - 0.75 eV range and unambiguously assign intermolecular and intramolecular optical absorption components of hole polarons in rr-P3HT. This data represents the first experimental quantification of these polarized components and allowed long-standing theoretical predictions to be compared to experimental results. The experimental data is discrepant with predictions of polaron absorption based on an adiabatic framework that works under the Born-Oppenheimer approximation, but the data is entirely consistent with a more recent nonadiabatic treatment of absorption based on a modified Holstein Hamiltonian. This nonadiabatic treatment was used to show that both intermolecular and intramolecular polaron coherence break down at length scales significantly smaller than estimated structural coherence in either direction. This strongly suggests that polaron delocalization is fundamentally limited by energetic disorder in rr-P3HT.
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Research context

OpenAlex topics: Organic Electronics and Photovoltaics · Conducting polymers and applications · Organic Light-Emitting Diodes Research

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

Affiliations

Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305, USA

Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA 92037, USA

Université de Strasbourg, CNRS, ICS UPR 22, F-67000 Strasbourg, France

Department of Materials Science and Engineering, University of Washington, Seattle, WA, USA

Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA

pi-Conjugated Polymers Unit, Okinawa Institute of Science and Technology, Onna, Okinawa 904-0495, Japan

Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, USA

Funding

Agence Nationale de la Recherche · Basic Energy Sciences · National Science Foundation

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