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Chemical doping is widely used to manipulate the electrical and thermoelectric properties of organic semiconductors, yet intelligent design of polymer–dopant systems remains elusive. It is challenging to predict the electrical and thermoelectric properties of doped organic semiconductors due to the large number of variables impacting these properties, including film morphology, dopant and polymer energetics, dopant size, and degree of polaron delocalization. Herein, a series of dopants with varying sizes and electron affinities (EAs) are combined with polymers of differing ionization energies (IEs) to investigate how the difference between polymer IE and dopant EA influences the doping efficiency and electrical conductivity, and how the dopant size influences the thermoelectric properties. Our experiments demonstrate that at low doping levels the doping efficiency strongly depends on the difference between the polymer IE and dopant EA; the effectiveness of doping on increasing electrical conductivity drastically decreases at high loadings for the molybdenum dithiolene complexes, while FeCl 3 remains effective at high loadings; and the large molybdenum complexes lead to more delocalized polarons as compared to FeCl 3 . To take advantage of the complementary doping characteristics of the molybdenum complexes and FeCl 3 , both dopants are employed simultaneously to reach high power factors at relatively low dopant concentrations.
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Tuning of the elastic modulus of a soft polythiophene through molecular doping
Molecular doping of a polythiophene with oligoethylene glycol side chains is found to strongly modulate not only the electrical but also the mechanical properties of the polymer. An oxidation level of up to 18% results in an electrical conductivity of more than 52 S cm −1 and at the same time significantly enhances the elastic modulus from 8 to more than 200 MPa and toughness from 0.5 to 5.1 MJ m −3 . These changes arise because molecular doping strongly influences the glass transition temperature T g and the degree of π-stacking of the polymer, as indicated by both X-ray diffraction and molecular dynamics simulations. Surprisingly, a comparison of doped materials containing mono- or dianions reveals that – for a comparable oxidation level – the presence of multivalent counterions has little effect on the stiffness. Evidently, molecular doping is a powerful tool that can be used for the design of mechanically robust conducting materials, which may find use within the field of flexible and stretchable electronics.
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- Award ID(s):
- 1921854
- PAR ID:
- 10302332
- Date Published:
- Journal Name:
- Materials Horizons
- ISSN:
- 2051-6347
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d1mh01079d
