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Title: Large bipolaron density at organic semiconductor/electrode interfaces

Abstract

Bipolaron states, in which two electrons or two holes occupy a single molecule or conjugated polymer segment, are typically considered to be negligible in organic semiconductor devices due to Coulomb repulsion between the two charges. Here we use charge modulation spectroscopy to reveal a bipolaron sheet density >1010 cm–2 at the interface between an indium tin oxide anode and the common small molecule organic semiconductor N,N'-Bis(3-methylphenyl)-N,N'-diphenylbenzidine. We find that the magnetocurrent response of hole-only devices correlates closely with changes in the bipolaron concentration, supporting the bipolaron model of unipolar organic magnetoresistance and suggesting that it may be more of an interface than a bulk phenomenon. These results are understood on the basis of a quantitative interface energy level alignment model, which indicates that bipolarons are generally expected to be significant near contacts in the Fermi level pinning regime and thus may be more prevalent in organic electronic devices than previously thought.

Authors:
 [1];  [2];  [3];  [4];  [1];  [3]; ORCiD logo [1]
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  1. Pennsylvania State Univ., University Park, PA (United States). Dept of Electrical Engineering
  2. Pennsylvania State Univ., University Park, PA (United States). Dept of Chemistry
  3. Dow Chemical Co., Midland, MI (United States)
  4. Pennsylvania State Univ., University Park, PA (United States). Dept of Materials Science
Publication Date:
Research Org.:
Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
Contributing Org.:
Dow Chemical Company
OSTI Identifier:
1523500
Grant/Contract Number:  
SC0012365
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 36 MATERIALS SCIENCE; Bipolaron; organic; electrode

Citation Formats

Dhanker, Rijul, Gray, Christopher L., Mukhopadhyay, Sukrit, Nunez, Sean, Cheng, Chiao -Yu, Sokolov, Anatoliy N., and Giebink, Noel C. Large bipolaron density at organic semiconductor/electrode interfaces. United States: N. p., 2017. Web. doi:10.1038/s41467-017-02459-3.
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Dhanker, Rijul, Gray, Christopher L., Mukhopadhyay, Sukrit, Nunez, Sean, Cheng, Chiao -Yu, Sokolov, Anatoliy N., & Giebink, Noel C. Large bipolaron density at organic semiconductor/electrode interfaces. United States. https://doi.org/10.1038/s41467-017-02459-3
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Dhanker, Rijul, Gray, Christopher L., Mukhopadhyay, Sukrit, Nunez, Sean, Cheng, Chiao -Yu, Sokolov, Anatoliy N., and Giebink, Noel C. Thu . "Large bipolaron density at organic semiconductor/electrode interfaces". United States. https://doi.org/10.1038/s41467-017-02459-3. https://www.osti.gov/servlets/purl/1523500.
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@article{osti_1523500,
title = {Large bipolaron density at organic semiconductor/electrode interfaces},
author = {Dhanker, Rijul and Gray, Christopher L. and Mukhopadhyay, Sukrit and Nunez, Sean and Cheng, Chiao -Yu and Sokolov, Anatoliy N. and Giebink, Noel C.},
abstractNote = {Bipolaron states, in which two electrons or two holes occupy a single molecule or conjugated polymer segment, are typically considered to be negligible in organic semiconductor devices due to Coulomb repulsion between the two charges. Here we use charge modulation spectroscopy to reveal a bipolaron sheet density >1010 cm–2 at the interface between an indium tin oxide anode and the common small molecule organic semiconductor N,N'-Bis(3-methylphenyl)-N,N'-diphenylbenzidine. We find that the magnetocurrent response of hole-only devices correlates closely with changes in the bipolaron concentration, supporting the bipolaron model of unipolar organic magnetoresistance and suggesting that it may be more of an interface than a bulk phenomenon. These results are understood on the basis of a quantitative interface energy level alignment model, which indicates that bipolarons are generally expected to be significant near contacts in the Fermi level pinning regime and thus may be more prevalent in organic electronic devices than previously thought.},
doi = {10.1038/s41467-017-02459-3},
journal = {Nature Communications},
number = 1,
volume = 8,
place = {United States},
year = {Thu Dec 21 00:00:00 EST 2017},
month = {Thu Dec 21 00:00:00 EST 2017}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1038/s41467-017-02459-3
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Cited by: 15 works
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Figures / Tables:

Fig. 1 Fig. 1: Fig. 1 Polaron and bipolaron spectroscopy. a Absorption spectra of the TPD cation and dication in solution. The solution consists of 55 μM TPD dissolved in dichloromethane with a 0.5M tetrabutylammonium tetrafluoroborate electrolyte. Electrochemically oxidizing the initially clear solution (black line) for 1 h at 0.55 V withmore » respect to a Ag/Ag+ reference electrode causes it to turn orange due to the formation of TPD cations that absorb in the blue and near-infrared (red line). Further oxidizing the solution at 0.9 V for 2 h (blue line) causes it to turn dark green due to a new absorption band at λ = 734 nm originating from TPD dications. The cyclic voltammetry scan in the inset yields first and second oxidation potentials E$^+_{1/2}$ = 0:45 V and E$^{2+}_{1/2}$ = 0:71 V, respectively. b Absorption coefficient of a 50 nm thick film of TPD thermally co-evaporated with 10wt% MoO3. c Charge modulation difference spectra recorded for an ITO (100 nm)/TPD (250 nm)/Ag (100 nm) hole-only device pulsed at −5 V reverse bias (black data points) and 5 V forward bias (red data points) using s-polarized light incident at a 45° angle. Increasing the voltage to 6.5 V (blue data points) confirms the emergence of the bipolaron absorption band at λ ~ 780nm. d Similar data for a 200 nm thick device, demonstrating the optical interference-induced spectral shift that occurs for the polaron and bipolaron absorption bands. The solid lines in (c, d) are produced by a transfer matrix optical model based on the polaron and bipolaron lineshapes in (b) under the assumption that both species are located in a 1 nm thick layer adjacent to the ITO anode« less
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journal, August 2009

Charge transfer-induced horizontal orientation of organic molecules near transition metal oxide surfaces
journal, April 2013

Kinetics of interface state-limited hole injection in α-naphthylphenylbiphenyl diamine (α-NPD) thin layers
journal, March 2009

Isolation and Crystal Structures of Two Singlet Bis(Triarylamine) Dications with Nonquinoidal Geometries
journal, February 2006

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  • Journal of the American Chemical Society, Vol. 128, Issue 6
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Organic semiconductor density of states controls the energy level alignment at electrode interfaces
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  • Nature Communications, Vol. 5, Issue 1
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Towards an understanding of structure–property relationships in hole-transport materials: The influence of molecular conformation on oxidation potential in poly(aryl)amines
journal, January 2005

  • Low, Paul J.; Paterson, Michael A. J.; Yufit, Dmitry S.
  • Journal of Materials Chemistry, Vol. 15, Issue 23
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Optical detection of charge carriers in multilayer organic light-emitting diodes: Experiment and theory
journal, March 2001

  • Book, K.; Nikitenko, V. R.; Bässler, H.
  • Journal of Applied Physics, Vol. 89, Issue 5
  • DOI: 10.1063/1.1343889

Formation of Ohmic hole injection by inserting an ultrathin layer of molybdenum trioxide between indium tin oxide and organic hole-transporting layers
journal, December 2007

  • Matsushima, Toshinori; Kinoshita, Yoshiki; Murata, Hideyuki
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  • DOI: 10.1063/1.2825275

Hole transport in the organic small molecule material α-NPD: evidence for the presence of correlated disorder
journal, June 2010

  • van Mensfoort, S. L. M.; Shabro, V.; de Vries, R. J.
  • Journal of Applied Physics, Vol. 107, Issue 11
  • DOI: 10.1063/1.3407561

Characterization of treated indium–tin–oxide surfaces used in electroluminescent devices
journal, August 1999

  • Mason, M. G.; Hung, L. S.; Tang, C. W.
  • Journal of Applied Physics, Vol. 86, Issue 3
  • DOI: 10.1063/1.370948

Diffusion-Limited Current in Organic Metal-Insulator-Metal Diodes
journal, October 2013

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    Progress and Perspective: Soft Thermoelectric Materials for Wearable and Internet‐of‐Things Applications
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    • Zaia, Edmond W.; Gordon, Madeleine P.; Yuan, Pengyu
    • Advanced Electronic Materials, Vol. 5, Issue 11
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    • Abreu, Ana Virgínia Passos; Ribeiro Junior, Luiz Antonio; Silva, Gesiel Gomes
    • Journal of Molecular Modeling, Vol. 25, Issue 8
    • DOI: 10.1007/s00894-019-4107-3
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