6 research outputs found
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Structural and dynamic disorder, not ionic trapping, controls charge transport in highly doped conducting polymers
Doped organic semiconductors are critical to emerging device applications,
including thermoelectrics, bioelectronics, and neuromorphic computing devices.
It is commonly assumed that low conductivities in these materials result
primarily from charge trapping by the Coulomb potentials of the dopant
counter-ions. Here, we present a combined experimental and theoretical study
rebutting this belief. Using a newly developed doping technique, we find the
conductivity of several classes of high-mobility conjugated polymers to be
strongly correlated with paracrystalline disorder but poorly correlated with
ionic size, suggesting that Coulomb traps do not limit transport. A general
model for interacting electrons in highly doped polymers is proposed and
carefully parameterized against atomistic calculations, enabling the
calculation of electrical conductivity within the framework of transient
localisation theory. Theoretical calculations are in excellent agreement with
experimental data, providing insights into the disordered-limited nature of
charge transport and suggesting new strategies to further improve
conductivities
Structural and dynamic disorder, not ionic trapping, controls charge transport in highly doped conducting polymers
Doped organic semiconductors are critical to emerging device applications,
including thermoelectrics, bioelectronics, and neuromorphic computing devices.
It is commonly assumed that low conductivities in these materials result
primarily from charge trapping by the Coulomb potentials of the dopant
counter-ions. Here, we present a combined experimental and theoretical study
rebutting this belief. Using a newly developed doping technique, we find the
conductivity of several classes of high-mobility conjugated polymers to be
strongly correlated with paracrystalline disorder but poorly correlated with
ionic size, suggesting that Coulomb traps do not limit transport. A general
model for interacting electrons in highly doped polymers is proposed and
carefully parameterized against atomistic calculations, enabling the
calculation of electrical conductivity within the framework of transient
localisation theory. Theoretical calculations are in excellent agreement with
experimental data, providing insights into the disordered-limited nature of
charge transport and suggesting new strategies to further improve
conductivities
HighâEfficiency IonâExchange Doping of Conducting Polymers
Abstract: Molecular dopingâthe use of redoxâactive small molecules as dopants for organic semiconductorsâhas seen a surge in research interest driven by emerging applications in sensing, bioelectronics, and thermoelectrics. However, molecular doping carries with it several intrinsic problems stemming directly from the redoxâactive character of these materials. A recent breakthrough was a doping technique based on ionâexchange, which separates the redox and charge compensation steps of the doping process. Here, the equilibrium and kinetics of ion exchange doping in a model system, poly(2,5âbis(3âalkylthiophenâ2âyl)thieno(3,2âb)thiophene) (PBTTT) doped with FeCl3 and an ionic liquid, is studied, reaching conductivities in excess of 1000 S cmâ1 and ion exchange efficiencies above 99%. Several factors that enable such high performance, including the choice of acetonitrile as the doping solvent, which largely eliminates electrolyte association effects and dramatically increases the doping strength of FeCl3, are demonstrated. In this high ion exchange efficiency regime, a simple connection between electrochemical doping and ion exchange is illustrated, and it is shown that the performance and stability of highly doped PBTTT is ultimately limited by intrinsically poor stability at high redox potential
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Research data supporting "Design of Experiment Optimization of Aligned Polymer Thermoelectrics Doped by Ion-Exchange"
The dxpx files were generated by the software Design-Expert to guide and analyse the design of experiments and study the influence of various rubbing parameters on the polymer chain alignment
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Enhancing the Conductivity and Thermoelectric Performance of Semicrystalline Conducting Polymers Through Controlled Tie Chain Incorporation.
Publication status: PublishedConjugated polymers are promising materials for thermoelectric applications, however, at present few effective and well understood strategies exist to further advance their thermoelectric performance. Here we report a new model system for better understanding the key factors governing their thermoelectric properties: aligned, ribbon-phase poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT) doped by ion-exchange doping. Using a range of microstructural and spectroscopic methods we study the effect of controlled incorporation of tie-chains between the crystalline domains through blending of high and low molecular weight chains. The tie chains provide efficient transport pathways between crystalline domains and lead to significantly enhanced electrical conductivity of 4810.1 S/cm, that is not accompanied by a reduction in Seebeck coefficient nor a large increase in thermal conductivity. We demonstrate respectable power factors of 172.6 ”W m-1 K-2 in this model system. Our approach is generally applicable to a wide range of semicrystalline conjugated polymers and could provide an effective pathway for further enhancing their thermoelectric properties and overcome traditional trade-offs in optimization of thermoelectric performance. This article is protected by copyright. All rights reserved.Financial support from the European Research Council for an Advanced Grant (No. 101020872) and from the Engineering and Physical Sciences Research Council (EP/W017091/1) is gratefully acknowledged. Wenjin Zhu acknowledges the Winton Scholarship through her PhD studies. Henning Sirringhaus acknowledges the support from a Royal Society Research Professorship (RP/R1/201 082)
Recommended from our members
Enhancing the Conductivity and Thermoelectric Performance of Semicrystalline Conducting Polymers Through Controlled Tie Chain Incorporation.
Conjugated polymers are promising materials for thermoelectric applications, however, at present few effective and well understood strategies exist to further advance their thermoelectric performance. Here we report a new model system for better understanding the key factors governing their thermoelectric properties: aligned, ribbon-phase poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT) doped by ion-exchange doping. Using a range of microstructural and spectroscopic methods we study the effect of controlled incorporation of tie-chains between the crystalline domains through blending of high and low molecular weight chains. The tie chains provide efficient transport pathways between crystalline domains and lead to significantly enhanced electrical conductivity of 4810.1 S/cm, that is not accompanied by a reduction in Seebeck coefficient nor a large increase in thermal conductivity. We demonstrate respectable power factors of 172.6 ”W m-1 K-2 in this model system. Our approach is generally applicable to a wide range of semicrystalline conjugated polymers and could provide an effective pathway for further enhancing their thermoelectric properties and overcome traditional trade-offs in optimization of thermoelectric performance. This article is protected by copyright. All rights reserved.Financial support from the European Research Council for an Advanced Grant (No. 101020872) and from the Engineering and Physical Sciences Research Council (EP/W017091/1) is gratefully acknowledged. Wenjin Zhu acknowledges the Winton Scholarship through her PhD studies. Henning Sirringhaus acknowledges the support from a Royal Society Research Professorship (RP/R1/201 082)