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Fine Molecular Tuning of Diketopyrrolopyrrole-Based Polymer Semiconductors for Efficient Charge Transport: Effects of Intramolecular Conjugation Structure

Title
Fine Molecular Tuning of Diketopyrrolopyrrole-Based Polymer Semiconductors for Efficient Charge Transport: Effects of Intramolecular Conjugation Structure
Author(s)
Yu, Seong HoonPark, Kwang HunKim, Yun-HiChung, Dae SungKwon, Soon-Ki
Issued Date
2017-06
Citation
Macromolecules, v.50, no.11, pp.4227 - 4234
Type
Article
Keywords
Carrier MobilityCarrier TransportCharge CarriersCrystalline MaterialsCrystalline StructureDensity Functional TheoryDonor Acceptor CopolymersField Effect TransistorsGrazing Incident X Ray DiffractionsHigh Hole MobilityHigh PerformanceIntermolecular InteractionsLow Voltage OperationOxide Gate DielectricsPolymer SemiconductorsPolymeric SemiconductorsPolymersTemperature DependenceTemperature DistributionThin Filmsactivation EnergyUltraviolet SpectroscopyUV Visible Absorption SpectraX Ray AbsorptionX Ray Absorption Fine Structure SpectroscopyX Ray Absorption Near Edge Structure SpectroscopyX Ray Diffraction
ISSN
0024-9297
Abstract
To improve the charge carrier mobility of diketopyrrolopyrrole donor-acceptor copolymer semiconductors, the length of the donor building block is controlled using vinylene moieties, and its effects on crystalline structure and charge transport are systematically studied. We synthesize P29-DPP-TBT with two vinylene linkages between thiophene units and compare it with P29-DPP-TVT with single vinylene linkage. Density functional theory calculations predict enhanced backbone planarity of P29-DPP-TBT compared to P29-DPP-TVT, which can be related to the increased conjugation length of P29-DPP-TBT as proved by the increased free exciton bandwidth extracted from UV-vis absorption spectra and the wavenumber shift of the C-C peaks to higher values in Raman spectra. From two-dimensional grazing incident X-ray diffraction studies, it is turned out that the paracrystalline disorder is lower in P29-DPP-TBT than in P29-DPP-TVT. Near-edge X-ray absorption fine structure spectroscopy reveal that more edge-on structure of polymer backbone is formed in the case of P29-DPP-TBT. By measuring the temperature dependence of the charge carrier mobilities, it is turned out that the activation energy for charge hopping is lower for P29-DPP-TBT than for P29-DPP-TVT. Collectively, these results imply that the substitution of extended π-conjugated donor moiety of polymeric semiconductors can yield a more planar backbone structure and thus enhanced intermolecular interaction which enables more perfect crystalline structure as well as enhanced charge transport behavior. © 2017 American Chemical Society.
URI
http://hdl.handle.net/20.500.11750/4726
DOI
10.1021/acs.macromol.7b00624
Publisher
American Chemical Society
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Department of Energy Science and Engineering Polymer Energy Materials Lab 1. Journal Articles

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