Tuning counterion chemistry to reduce carrier localization in doped semiconducting carbon nanotube networks

Murrey, Tucker L.; Aubry, Taylor J.; Ruiz, Omar León; Thurman, Kira A.; Eckstein, Klaus H.; Doud, Evan A.; Stauber, Julia M.; Spokoyny, Alexander M.; Schwartz, Benjamin J.; Hertel, Tobias; Blackburn, Jeffrey L.; Ferguson, Andrew J.

doi:10.1016/j.xcrp.2023.101407

Cited by 15 publications

(19 citation statements)

References 39 publications

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“…In aqueous solutions, the high relative permittivity of ϵ r ≈ 80 contrasts with the considerably weaker screening found in organic solvents used for polymer-dispersed nanotubes. For example, in Poly(9,9-dioctylfluorene- co -benzothiadiazole) (PFO-BPy)-dispersed s-SWNTs suspended in toluene and doped with Au(III)Cl 3 , the binding energy for defect states associated with adsorbed chlorine ions is estimated at roughly 100 meV …”

Section: Resultsmentioning

confidence: 99%

“…In support of these predictions, a study by Murrey et al showed that sterically more distanced counterions, such as those associated with icosahedral dodecaborane (DDB) clusters, result in weaker binding of Coulomb defect states. In the study by Murrey et al, this was revealed by changes in the carrier transport properties of DDB-doped s-SWNTs, confirming the role of ion-tube separation in modulating Coulombic interactions …”

Section: Resultsmentioning

confidence: 99%

“…For example, in Poly(9,9-dioctylfluorene-co-benzothiadiazole) (PFO-BPy)dispersed s-SWNTs suspended in toluene and doped with Au(III)Cl 3 , the binding energy for defect states associated with adsorbed chlorine ions is estimated at roughly 100 meV. 35 In support of these predictions, a study by Murrey et al showed that sterically more distanced counterions, such as those associated with icosahedral dodecaborane (DDB) clusters, result in weaker binding of Coulomb defect states. In the study by Murrey et al, this was revealed by changes in the carrier transport properties of DDB-doped s-SWNTs, confirming the role of ion-tube separation in modulating Coulombic interactions.…”

Section: ■ Methodsmentioning

confidence: 99%

“…In the study by Murrey et al, this was revealed by changes in the carrier transport properties of DDB-doped s-SWNTs, confirming the role of ion-tube separation in modulating Coulombic interactions. 35 Interaction of Proximal Defects. Now, we examine the effect of the counterion proximity on the electronic structure of s-SWNTs, a phenomenon that becomes increasingly important at higher doping levels.…”

Section: ■ Methodsmentioning

confidence: 99%

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Electronic Structure and Scaling of Coulomb Defects in Carbon Nanotubes from Modified Hückel Calculations

Eckstein,

Hertel

2023

J. Phys. Chem. C

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: ■ Methodsmentioning

confidence: 99%

Section: ■ Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Electronic Structure and Scaling of Coulomb Defects in Carbon Nanotubes from Modified Hückel Calculations

Eckstein,

Hertel

2023

J. Phys. Chem. C

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“…In contrast, other studies have favored an inhomogeneous description, specifically regarding electronic transport phenomena or the mechanism of NR exciton decay. ,− Such models were particularly successful in describing the dependence of fluorescence quantum yields in SWNTs on nanotube length, ,,− the effect of defects on PL-imaging of SWNTs, , and the influence of diffusive exciton transport on NR decay observed in time-domain investigations of exciton dynamics. ,− Moreover, localization of excess charge carriers has also been instrumental for the interpretation of Breit–Wigner–Fano resonances in the IR spectra of doped SWNTs. , …”

Section: Introductionmentioning

confidence: 99%

Trions, Exciton Dynamics, and Spectral Modifications in Doped Carbon Nanotubes: A Singular Defect-Driven Mechanism

Eckstein,

Kunkel,

Voelckel

et al. 2023

J. Phys. Chem. C

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Doping substantially influences the electronic and photophysical properties of semiconducting single-walled carbon nanotubes (s-SWNTs). Although prior studies have noted that surplus charge carriers modify optical spectra and accelerate nonradiative exciton decay in doped s-SWNTs, a direct mechanistic correlation of trion formation, exciton dynamics, and energetics remains elusive. This work examines the influence of doping-induced nonradiative decay and exciton confinement on s-SWNT photophysics. Using photoluminescence, continuous-wave absorption, and pump–probe spectroscopy, we show that localization of and barrier formation by trapped charges can be jointly quantified using diffusive exciton transport and particle-in-the-box models, yielding a one-to-one correlation between charge carrier concentrations derived from these models. The study highlights the multifaceted role of exohedral counterions, which trap charges to create quenching sites, form barriers to exciton movement, and host trion states. This contributes significantly to understanding and optimizing the photophysical properties of doped SWNTs.

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Combination of Counterion Size and Doping Concentration Determines the Electronic and Thermoelectric Properties of Semiconducting Polymers

Baustert,

Bombile,

Rahman

et al. 2024

Advanced Materials

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In both chemical and electrochemical doping of organic semiconductors (OSCs), a counterion, either from the electrolyte or ionized dopant, balances the charge introduced to the OSC. Despite the large influence of this counterion on the OSC optical and electronic response, there remains substantial debate on how a fundamental parameter, ion size, impacts these properties. This work addresses this discrepancy by accounting for two doping regimes. In the low‐doping regime the Coulomb binding energies between polarons on the π‐conjugated polymers and the counterions are significant, and larger counterions lead to decreased Coulomb interactions, more delocalized polarons, and higher electrical conductivities. In the high‐doping regime the Coulomb binding energies become negligible due to the increased dielectric constant of the films and a smoothing of the energy landscape; thereby, the electrical conductivities depend primarily on the extent of morphological disorder in the OSC. Moreover, in regioregular poly(3‐hexylthiophene), rr‐P3HT, smaller counterions lead to greater bipolaron concentrations in the low‐doping regime due to the increased Coulomb interactions. Emphasizing the impact of the counterion size, we show that larger counterions can lead toincreased thermoelectric power factors for rr‐P3HT.This article is protected by copyright. All rights reserved

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Tuning counterion chemistry to reduce carrier localization in doped semiconducting carbon nanotube networks

Cited by 15 publications

References 39 publications

Electronic Structure and Scaling of Coulomb Defects in Carbon Nanotubes from Modified Hückel Calculations

Electronic Structure and Scaling of Coulomb Defects in Carbon Nanotubes from Modified Hückel Calculations

Trions, Exciton Dynamics, and Spectral Modifications in Doped Carbon Nanotubes: A Singular Defect-Driven Mechanism

Combination of Counterion Size and Doping Concentration Determines the Electronic and Thermoelectric Properties of Semiconducting Polymers

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