Structural and electronic properties of doped oligothiophenes in the presence of p-toluenesulfonate acids

Chaalane, Amar; Mahi, Djillali; Dkhissi, Ahmed

doi:10.1007/s00214-015-1663-1

Cited by 3 publications

(8 citation statements)

References 34 publications

(44 reference statements)

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“…Since the processing prior to the washing is identical, we analogously propose a π-stacked structure for the semiconducting PT. The detected new lattice distance of 3.6 Å is close to the calculated intermolecular distance for tosylate-doped oligothiophenes (3.7 Å) 10 and also in the same range as the π-stacking distances of both P3HT (3.8 Å) 22 and PEDOT (3.4 Å). 23 The small peak arising in the vertical direction is consequently interpreted as the side-by-side distance between the backbones.…”

Section: Acs Omegasupporting

confidence: 81%

“…They found the sidewise arrangement to be most stable, with an intermolecular distance of 3.56 Å between the sulfur atoms of polythiophene and tosylate, respectively. 10 Therefore, we propose the formation of a similar crystal structure for the PT thin films synthesized under iron excess in our study. The highly doped PT chains arrange in a lamellar structure, giving rise to the new Bragg peak arising in the GIWAXS pattern for X FeTos = 0.75.…”

Section: ■ Results and Discussionmentioning

confidence: 56%

“…Simulations show that the tosylates align perpendicular to the polythiophene backbones. 10 We are interested in fabricating an insoluble semiconducting material with improved performance, exploiting the doping procedure during the processing. We therefore spin coat the metastable mixture and subsequently rinse out all residual monomers and oxidant molecules.…”

Section: Resultsmentioning

confidence: 99%

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Directing the Aggregation of Native Polythiophene during in Situ Polymerization

et al. 2018

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The performance of semiconducting polymers strongly depends on their intra- and intermolecular electronic interactions. Therefore, the morphology and particularly crystallinity and crystal structure play a crucial role in enabling a sufficient overlap between the orbitals of neighboring polymers. A new solution-based in situ polymerization for the fabrication of native polythiophene thin films is presented, which exploits the film formation process to influence the polymer crystal structure in the resulting thin films. The synthesis of the insoluble polythiophene is based on an oxidative reaction in which the oxidizing agent, iron(III) p -toluenesulfonate (FeTos), initially oxidizes the monomers to enable the polymer chain growth and secondly the final polymers, thereby chemically doping the polythiophene. To exploit the fact that the doped polythiophene has a different crystal packing structure compared to the undoped polythiophene, we investigate the structural effect of this inherent doping process by varying the amounts of FeTos in the reaction mixture, creating polythiophene thin films with different degrees of doping. The structural investigation performed by means of grazing incidence wide-angle X-ray scattering (GIWAXS) suggests that the strongly doped polymer chains aggregate in a π-stacked manner in the film formation process. Moreover, this π-stacking can be maintained after the removal of the dopant molecules. GIWAXS measurements, molecular dynamics simulations, and spectroscopic analysis suggest the presence of polythiophene in a novel and stable crystal structure with an enhanced intermolecular interaction.

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Section: Acs Omegasupporting

confidence: 81%

Section: ■ Results and Discussionmentioning

confidence: 56%

Section: Resultsmentioning

confidence: 99%

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Directing the Aggregation of Native Polythiophene during in Situ Polymerization

et al. 2018

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“…The Cl atoms now reside between the two layers away from the center of the thiophene rings, similar to the monolayer case. Computational studies involving para -toluenesulfonic acid ( p -TSA) intercalated in polythiophene bilayers have also shown this movement of the anion away from the center of the bilayer, allowing for tighter packing of the thiophene units …”

Section: Geometry and Electronic Structure Of Polythiophenementioning

confidence: 99%

“…Computational studies involving para-toluenesulfonic acid (p-TSA) intercalated in polythiophene bilayers have also shown this movement of the anion away from the center of the bilayer, allowing for tighter packing of the thiophene units. 171 Flipping of the second layer of polythiophene by 180°has also been considered for creating bulk or bilayer structures. Note that it is speculated a more favorable structure is formed based on donor−acceptor pair between the S atom and the carbon backbone, which has not been verified experimentally yet.…”

Section: Geometry and Electronic Structure Of Polythiophenementioning

confidence: 99%

Polythiophene: From Fundamental Perspectives to Applications

et al. 2017

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The field of organic electronics has been heavily impacted by the discovery and development of π-conjugated conducting polymers. These polymers show great potential for integration into future optical and electronic devices due to their capacity to transition between semiconducting and conducting states as well as the ability to alter mechanical properties by controlled doping, chemical modification, and stacking or creating composites with other materials. Among π-conjugated polymers, polythiophene and its derivatives has been one of the most extensively studied and is widely investigated computationally and experimentally for use in electronic devices such as light-emitting diodes, water purification devices, hydrogen storage, and biosensors. Various theoretical modeling studies of polythiophene ranging from an oligothiophene approach to infinite chain lengths (periodic boundary conditions) have been undertaken to study a variety of electronic and structural properties of these polymers. In this review, we discuss the recent advances in the understanding of pristine polythiophene and its derivatives from fundamental perspectives to device applications.

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Polaron formation mechanisms in conjugated polymers

Bombile

Janik

Milner

2018

Phys. Chem. Chem. Phys.

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In semiconducting polymers, interactions with conformational degrees of freedom can localize charge carriers, and strongly affect charge transport. Polarons can form when charges induce deformations of the surrounding medium, including local vibrational modes or dielectric polarization. These deformations then interact attractively with the charge, tending to localize it. First we investigate vibrational polaron formation in poly(3-hexylthiophene) [P3HT], with a tight-binding model for charges hopping between adjacent rings, coupled to ring distortions. We use density functional theory (DFT) calculations to determine coupling constants, including the "spring constant" for ring distortions and the coupling to the charge carrier. On single chains, we find only broad, weakly bound polarons by this mechanism. In 2d crystalline layers of P3HT, even weak transverse hopping between chains destabilizes this polaron. Then, we consider polarons stabilized by dielectric polarization, described semiclassically with a polarizable continuum interacting with the carrier wavefunction. In contrast to vibrational polarons, we find dielectrically stabilized polarons in P3HT are narrower, more strongly bound, and stable in 2d crystalline layers.

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Structural and electronic properties of doped oligothiophenes in the presence of p-toluenesulfonate acids

Cited by 3 publications

References 34 publications

Directing the Aggregation of Native Polythiophene during in Situ Polymerization

Directing the Aggregation of Native Polythiophene during in Situ Polymerization

Polythiophene: From Fundamental Perspectives to Applications

Polaron formation mechanisms in conjugated polymers

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