Packing Dependent Electronic Coupling in Single Poly(3-hexylthiophene) H- and J-Aggregate Nanofibers

Martin, Thomas P.; Wise, Adam J.; Busby, Erik; Gao, Jian; Roehling, John D.; Ford, Michael J.; Larsen, Delmar S.; Moulé, Adam J.; Grey, John K.

doi:10.1021/jp308586k

Cited by 75 publications

(149 citation statements)

References 47 publications

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“…Either J-type intrachain delocalization along the ordered backbone could lead to charges within the same polymer chain, or charges could be generated across neighbouring backbones thanks to interchain H-aggregation. 73 Judging from previous studies with P3HT nanofibres and thin films, 73,84 the polaron yield is generally much higher in the latter case, providing evidence that aggregation of CPT in the ordered phase enhances the observed polaron generation. In line with this we have observed that, with excitation of the ordered phase at 580 nm, polaron formation is slightly favoured at higher temperature (40 1C compared to 5 1C), where the stationary absorption spectra with reduced relative 0-0 intensity suggest that the interchain H-aggregate character is enhanced.…”

mentioning

confidence: 66%

“…It has been shown that intrachain coupling leads to J-aggregate type behaviour in the optical transitions. 10,12,73 The interchain coupling refers to the possibility of through-space delocalization across polymer chains that are aggregated or folded, and which are closely packed to allow molecular orbital overlap. This can be modelled as H-aggregate type behaviour.…”

Section: Polythiophene Photophysicsmentioning

confidence: 99%

“…This can be modelled as H-aggregate type behaviour. 10,12,73 Again, good packing is favoured by order in the polymer backbone (planarity, extension), but also requires ordering of the side chains. Therefore, the regioregularity of the side chains plays an important role in determining the photophysics of polythiophenes, as has been shown for regioregular and regiorandom P3HT thin films and even single chains.…”

Section: Polythiophene Photophysicsmentioning

confidence: 99%

“…15,67,74 In more ordered polythiophene systems, there is competition between inter-and intrachain coupling, and the overall photophysical properties are governed by subtle changes in the packing and chain conformation, which shift the system towards the H-aggregate or J-aggregate limit. 12,73 Stationary absorption spectra allow distinguishing between the disordered phase of polythiophenes (blue-shifted, broad absorption band without vibronic structure) and the ordered phase (red-shifted absorption band with clear vibronic structure). [7][8][9] Moreover, the shape of the vibronic structure in the ordered phase gives information about the extent of interversus intramolecular coupling.…”

Section: Polythiophene Photophysicsmentioning

confidence: 99%

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Salt-induced thermochromism of a conjugated polyelectrolyte

Peterhans

Alloa

Sheima

et al. 2017

Phys. Chem. Chem. Phys.

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We report here the photophysical properties of a water-soluble conjugated polythiophene with cationic side-chains. When dissolved in aqueous buffer solution (PBS, phosphate buffered saline), there is ordering of the polymer chains due to the presence of the salts, in contrast to pure water, where a random-coil conformation is adopted at room temperature. The ordering leads to a pronounced colour change of the solution (the absorption maximum shifts from 400 nm to 525 nm). Combining resonance Raman spectroscopy with density functional theory computations, we show a significant backbone planarization in the ordered phase. Moreover, the ratio of ordered phase to random-coil phase in PBS solution, as well as the extent of intermolecular interactions in the ordered phase, can be tuned by varying the temperature. Femtosecond transient absorption spectroscopy reveals that the excited-state behaviour of the polyelectrolyte is strongly affected by the degree of ordering. While triplet state formation is favoured in the random-coil chains, the ordered chains show a weak yield of polarons, related to interchain interactions. The investigated polyelectrolyte has been previously used as a biological DNA sensor, based on optical transduction when the conformation of the polyelectrolyte changes during assembly with the biomolecule. Therefore, our results, by correlating the photophysical properties of the polyelectrolyte to backbone and intermolecular conformation in a biologically relevant buffer, provide a significant step forward in understanding the mechanism of the biological sensing.

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mentioning

confidence: 66%

Section: Polythiophene Photophysicsmentioning

confidence: 99%

Section: Polythiophene Photophysicsmentioning

confidence: 99%

Section: Polythiophene Photophysicsmentioning

confidence: 99%

See 2 more Smart Citations

Salt-induced thermochromism of a conjugated polyelectrolyte

Peterhans

Alloa

Sheima

et al. 2017

Phys. Chem. Chem. Phys.

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“…There are H-type (face-to-face) and J-type (head-to-tail) aggregates for P3HT 18,19) . While only 0-1 sideband appears in the former type due to the constraint of symmetry, the transition corresponding to 0-0 sideband is strongly allowed in the latter type.…”

Section: Resultsmentioning

confidence: 99%

Photophysical Behaviors at Interfaces between Poly(3-Hexylthiophene) and Zinc Oxide Nanostructures

Feng

Hao

2017

Mater. Trans.

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Development of design rules through understanding exciton dissociation and charge generation dynamics is an important pathway to improve the performance of hybrid inorganic-organic solar cells. In this work, we study the photophysical behavior and dynamics of charge generation in organic/inorganic hybrid based on poly(3-hexylthiophene) (P3HT) and zinc oxide (ZnO) nanostructures by steady-state and time-resolved uorescence spectroscopy. Both lms of P3HT:ZnO nanoparticle (NPs) blend as the active layer and pristine P3HT as the active layer on ZnO nanorod (NRs) array buffer layer can provide ef cient interfaces for exciton dissociation and charge transfer. P3HT can in ltrate into inter-rod space of ZnO NRs and cover them to enhance the 0-0 band against the 0-1 one in the steady-state photoluminescence spectrum. However, the con guration of P3HT: ZnO NPs blend as the active layer on ZnO NRs buffer layer poorly further improves the exciton dissociation, due to the decreased organic-inorganic interface area.

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Controlling Molecular Doping in Organic Semiconductors

2017

Self Cite

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The field of organic electronics thrives on the hope of enabling low-cost, solution-processed electronic devices with mechanical, optoelectronic, and chemical properties not available from inorganic semiconductors. A key to the success of these aspirations is the ability to controllably dope organic semiconductors with high spatial resolution. Here, recent progress in molecular doping of organic semiconductors is summarized, with an emphasis on solution-processed p-type doped polymeric semiconductors. Highlighted topics include how solution-processing techniques can control the distribution, diffusion, and density of dopants within the organic semiconductor, and, in turn, affect the electronic properties of the material. Research in these areas has recently intensified, thanks to advances in chemical synthesis, improved understanding of charged states in organic materials, and a focus on relating fabrication techniques to morphology. Significant disorder in these systems, along with complex interactions between doping and film morphology, is often responsible for charge trapping and low doping efficiency. However, the strong coupling between doping, solubility, and morphology can be harnessed to control crystallinity, create doping gradients, and pattern polymers. These breakthroughs suggest a role for molecular doping not only in device function but also in fabrication-applications beyond those directly analogous to inorganic doping.

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Packing Dependent Electronic Coupling in Single Poly(3-hexylthiophene) H- and J-Aggregate Nanofibers

Cited by 75 publications

References 47 publications

Salt-induced thermochromism of a conjugated polyelectrolyte

Salt-induced thermochromism of a conjugated polyelectrolyte

Photophysical Behaviors at Interfaces between Poly(3-Hexylthiophene) and Zinc Oxide Nanostructures

Controlling Molecular Doping in Organic Semiconductors

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