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Doping is required to increase the electrical conductivity of organic semiconductors for uses in electronic and energy conversion devices. The limited number of commonly used p-type dopants suggests that new dopants or doping mechanisms could improve the efficiency of doping and provide new means for processing doped polymers. Drawing on Lewis acid–base pair chemistry, we combined Lewis acid dopant B(C 6 F 5 ) 3 (BCF) with the weak Lewis base benzoyl peroxide (BPO). The detailed behavior of p-type doping of the model polymer poly(3-hexylthiophene) (P3HT) with this Lewis acid–base pair in solution was examined. Solution 19 F-NMR spectra confirmed the formation of the expected counterion, as well as side products from reactions with solvent. BCF : BPO was also found to efficiently dope a range of semiconducting polymers with varying chemical structures demonstrating that the BCF : BPO combination has an effective electron affinity of at least 5.3 eV. In thin films of regioregular P3HT cast from the doped solutions, delocalized polarons formed due to the large counterions leading to a large polaron-counterion distance. At and above 0.2 eq. BCF : BPO doping, amorphous areas of the film became doped, disrupting the structural order of the films. Despite the change in structural order, thin films of regioregular P3HT doped with 0.2 eq. BCF : BPO had a conductivity of 25 S cm −1 . This study demonstrates the effectiveness of a two-component Lewis acid–base doping mechanism and suggests additional two-component Lewis acid–base chemistries should be explored.
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Direct detection of molecular hydrogen upon p- and n-doping of organic semiconductors with complex oxidants or reductants
Molecular doping can increase the conductivity of organic semiconductors and plays an increasingly important role in emerging and established plastic electronics applications. 4-(1,3-Dimethyl-2,3-dihydro-1 H -benzimidazol-2-yl)- N , N -dimethylaniline (N-DMBI-H) and tris(pentafluorophenyl)borane (BCF) are established n- and p-dopants, respectively, but neither functions as a simple one-electron redox agent. Molecular hydrogen has been suggested to be a byproduct in several proposed mechanisms for doping using both N-DMBI-H and BCF. In this paper we show for the first time the direct detection of molecular hydrogen in the uncatalysed doping of a variety of polymeric and molecular semiconductors using these dopants. Our results provide insight into the doping mechanism, providing information complementary to that obtained from more commonly applied methods such as optical, electron spin resonance, and electrical measurements.
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- Award ID(s):
- 2216857
- PAR ID:
- 10410576
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- Volume:
- 11
- Issue:
- 15
- ISSN:
- 2050-7488
- Page Range / eLocation ID:
- 8192 to 8201
- 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/D3TA00231D
