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Visualisation of individual dopants in a conjugated polymer: sub-nanometre 3D spatial distribution and correlation with electrical properties
Chalmers University of Technology, Sweden.
Chalmers University of Technology, Sweden.
RISE Research Institutes of Sweden, Bioeconomy and Health, Agriculture and Food. Chalmers University of Technology, Sweden.ORCID iD: 0000-0002-5956-9934
Chalmers University of Technology, Sweden; Linköping University, Sweden.
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2022 (English)In: Nanoscale, ISSN 2040-3364, E-ISSN 2040-3372, Vol. 14, p. 15404-15413Article in journal (Refereed) Published
Abstract [en]

While molecular doping is ubiquitous in all branches of organic electronics, little is known about the spatial distribution of dopants, especially at molecular length scales. Moreover, a homogeneous distribution is often assumed when simulating transport properties of these materials, even though the distribution is expected to be inhomogeneous. In this study, electron tomography is used to determine the position of individual molybdenum dithiolene complexes and their three-dimensional distribution in a semiconducting polymer at the sub-nanometre scale. A heterogeneous distribution is observed, the characteristics of which depend on the dopant concentration. At 5 mol% of the molybdenum dithiolene complex, the majority of the dopant species are present as isolated molecules or small clusters up to five molecules. At 20 mol% dopant concentration and higher, the dopant species form larger nanoclusters with elongated shapes. Even in case of these larger clusters, each individual dopant species is still in contact with the surrounding polymer. The electrical conductivity first strongly increases with dopant concentration and then slightly decreases for the most highly doped samples, even though no large aggregates can be observed. The decreased conductivity is instead attributed to the increased energetic disorder and lower probability of electron transfer that originates from the increased size and size variation in dopant clusters. This study highlights the importance of detailed information concerning the dopant spatial distribution at the sub-nanometre scale in three dimensions within the organic semiconductor host. The information acquired using electron tomography may facilitate more accurate simulations of charge transport in doped organic semiconductors. 

Place, publisher, year, edition, pages
Royal Society of Chemistry , 2022. Vol. 14, p. 15404-15413
Keywords [en]
Conjugated polymers, Electric impedance tomography, Probes, Semiconductor doping, Spatial distribution, Dithiolene, Dopant concentrations, Dopant species, Electron tomography, Homogeneous distribution, Length scale, Molecular doping, Molecular length, Nanometres, Organic electronics, Molecules
National Category
Materials Chemistry
Identifiers
URN: urn:nbn:se:ri:diva-61233DOI: 10.1039/d2nr03554eScopus ID: 2-s2.0-85140743377OAI: oai:DiVA.org:ri-61233DiVA, id: diva2:1715501
Note

Funding details: National Science Foundation, NSF, DMR-1729737; Funding details: Vetenskapsrådet, VR, 2016-06146, 2018-03824; Funding text 1: We thank the Chalmers Material Analysis Laboratory for their support of the electron microscopes. We gratefully acknowledge financial support from the Swedish Research Council through grants 2016-06146 and 2018-03824 and from the National Science Foundation through the DMREF program (DMR-1729737).

Available from: 2022-12-02 Created: 2022-12-02 Last updated: 2023-07-06Bibliographically approved

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Röding, Magnus

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