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Title: Tethered tertiary amines as solid-state n-type dopants for solution-processable organic semiconductors

Abstract

A scarcity of stable n-type doping strategies compatible with facile processing has been a major impediment to the advancement of organic electronic devices. Localizing dopants near the cores of conductive molecules can lead to improved efficacy of doping. We and others recently showed the effectiveness of tethering dopants covalently to an electron-deficient aromatic molecule using trimethylammonium functionalization with hydroxide counterions linked to a perylene diimide core by alkyl spacers. In this work, we demonstrate that, contrary to previous hypotheses, the main driver responsible for the highly effective doping observed in thin films is the formation of tethered tertiary amine moieties during thin film processing. Furthermore, we demonstrate that tethered tertiary amine groups are powerful and general n-doping motifs for the successful generation of free electron carriers in the solid-state, not only when coupled to the perylene diimide molecular core, but also when linked with other small molecule systems including naphthalene diimide, diketopyrrolopyrrole, and fullerene derivatives. Our findings help expand a promising molecular design strategy for future enhancements of n-type organic electronic materials.

Authors:
 [1];  [2];  [3];  [4];  [2];  [2];  [5];  [6];  [7];  [8];  [6];  [7];  [5]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Santa Barbara, CA (United States). Dept. of Chemistry and Biochemistry
  3. Univ. of California, Santa Barbara, CA (United States). Dept. of Chemical Engineering
  4. Univ. of California, Santa Barbara, CA (United States). Materials Dept.
  5. Univ. of California, Santa Barbara, CA (United States). Dept. of Chemical Engineering; Univ. of California, Santa Barbara, CA (United States). Materials Dept.
  6. Univ. of California, Santa Barbara, CA (United States). Materials Dept
  7. Univ. of California, Santa Barbara, CA (United States). Dept. of Chemistry and Biochemistry; Univ. of California, Santa Barbara, CA (United States). Materials Dept.
  8. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1377413
Grant/Contract Number:  
AC02-05CH11231; DMR 1121053
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 7; Journal Issue: 3; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Russ, Boris, Robb, Maxwell J., Popere, Bhooshan C., Perry, Erin E., Mai, Cheng-Kang, Fronk, Stephanie L., Patel, Shrayesh N., Mates, Thomas E., Bazan, Guillermo C., Urban, Jeffrey J., Chabinyc, Michael L., Hawker, Craig J., and Segalman, Rachel A. Tethered tertiary amines as solid-state n-type dopants for solution-processable organic semiconductors. United States: N. p., 2015. Web. doi:10.1039/c5sc04217h.
Russ, Boris, Robb, Maxwell J., Popere, Bhooshan C., Perry, Erin E., Mai, Cheng-Kang, Fronk, Stephanie L., Patel, Shrayesh N., Mates, Thomas E., Bazan, Guillermo C., Urban, Jeffrey J., Chabinyc, Michael L., Hawker, Craig J., & Segalman, Rachel A. Tethered tertiary amines as solid-state n-type dopants for solution-processable organic semiconductors. United States. doi:10.1039/c5sc04217h.
Russ, Boris, Robb, Maxwell J., Popere, Bhooshan C., Perry, Erin E., Mai, Cheng-Kang, Fronk, Stephanie L., Patel, Shrayesh N., Mates, Thomas E., Bazan, Guillermo C., Urban, Jeffrey J., Chabinyc, Michael L., Hawker, Craig J., and Segalman, Rachel A. Wed . "Tethered tertiary amines as solid-state n-type dopants for solution-processable organic semiconductors". United States. doi:10.1039/c5sc04217h. https://www.osti.gov/servlets/purl/1377413.
@article{osti_1377413,
title = {Tethered tertiary amines as solid-state n-type dopants for solution-processable organic semiconductors},
author = {Russ, Boris and Robb, Maxwell J. and Popere, Bhooshan C. and Perry, Erin E. and Mai, Cheng-Kang and Fronk, Stephanie L. and Patel, Shrayesh N. and Mates, Thomas E. and Bazan, Guillermo C. and Urban, Jeffrey J. and Chabinyc, Michael L. and Hawker, Craig J. and Segalman, Rachel A.},
abstractNote = {A scarcity of stable n-type doping strategies compatible with facile processing has been a major impediment to the advancement of organic electronic devices. Localizing dopants near the cores of conductive molecules can lead to improved efficacy of doping. We and others recently showed the effectiveness of tethering dopants covalently to an electron-deficient aromatic molecule using trimethylammonium functionalization with hydroxide counterions linked to a perylene diimide core by alkyl spacers. In this work, we demonstrate that, contrary to previous hypotheses, the main driver responsible for the highly effective doping observed in thin films is the formation of tethered tertiary amine moieties during thin film processing. Furthermore, we demonstrate that tethered tertiary amine groups are powerful and general n-doping motifs for the successful generation of free electron carriers in the solid-state, not only when coupled to the perylene diimide molecular core, but also when linked with other small molecule systems including naphthalene diimide, diketopyrrolopyrrole, and fullerene derivatives. Our findings help expand a promising molecular design strategy for future enhancements of n-type organic electronic materials.},
doi = {10.1039/c5sc04217h},
journal = {Chemical Science},
number = 3,
volume = 7,
place = {United States},
year = {2015},
month = {12}
}

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Cited by: 27 works
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Works referenced in this record:

The path to ubiquitous and low-cost organic electronic appliances on plastic
journal, April 2004


Photoinduced electron transfer in supramolecular systems for artificial photosynthesis
journal, May 1992

  • Wasielewski, Michael R.
  • Chemical Reviews, Vol. 92, Issue 3, p. 435-461
  • DOI: 10.1021/cr00011a005

Prospects for Alkaline Anion-Exchange Membranes in Low Temperature Fuel Cells
journal, October 2004


Use of a 1 H -Benzoimidazole Derivative as an n -Type Dopant and To Enable Air-Stable Solution-Processed n -Channel Organic Thin-Film Transistors
journal, July 2010

  • Wei, Peng; Oh, Joon Hak; Dong, Guifang
  • Journal of the American Chemical Society, Vol. 132, Issue 26
  • DOI: 10.1021/ja103173m

On the superlinear increase in conductivity with dopant concentration in excitonic semiconductors
journal, March 2004

  • Gregg, Brian A.; Chen, Si-Guang; Branz, Howard M.
  • Applied Physics Letters, Vol. 84, Issue 10
  • DOI: 10.1063/1.1668326

Photoreduction by amines
journal, April 1973

  • Cohen, Saul G.; Parola, Abraham; Parsons, George H.
  • Chemical Reviews, Vol. 73, Issue 2
  • DOI: 10.1021/cr60282a004

Photoinduced Color Change and Photomechanical Effect of Naphthalene Diimides Bearing Alkylamine Moieties in the Solid State
journal, April 2014

  • Matsunaga, Yuki; Goto, Kenta; Kubono, Koji
  • Chemistry - A European Journal, Vol. 20, Issue 24
  • DOI: 10.1002/chem.201304849

Electroluminescence in conjugated polymers
journal, January 1999

  • Friend, R. H.; Gymer, R. W.; Holmes, A. B.
  • Nature, Vol. 397, Issue 6715
  • DOI: 10.1038/16393

Reduction of aryl halides by consecutive visible light-induced electron transfer processes
journal, November 2014


Doping of organic semiconductors
journal, December 2012


A Self-Doping, O2-Stable, n-Type Interfacial Layer for Organic Electronics
journal, March 2012

  • Reilly, Thomas H.; Hains, Alexander W.; Chen, Hsiang-Yu
  • Advanced Energy Materials, Vol. 2, Issue 4
  • DOI: 10.1002/aenm.201100446

Doping of Conjugated Polythiophenes with Alkyl Silanes
journal, June 2009

  • Kao, Chi Yueh; Lee, Bumsu; Wielunski, Leszek S.
  • Advanced Functional Materials, Vol. 19, Issue 12, p. 1906-1911
  • DOI: 10.1002/adfm.200900120

Fabrication of iodine-doped pentacene thin films for organic thermoelectric devices
journal, January 2011

  • Hayashi, K.; Shinano, T.; Miyazaki, Y.
  • Journal of Applied Physics, Vol. 109, Issue 2
  • DOI: 10.1063/1.3537831

n-Doping of Organic Electronic Materials using Air-Stable Organometallics
journal, November 2011

  • Guo, Song; Kim, Sang Bok; Mohapatra, Swagat K.
  • Advanced Materials, Vol. 24, Issue 5, p. 699-703
  • DOI: 10.1002/adma.201103238

Molecular Interactions and Ordering in Electrically Doped Polymers: Blends of PBTTT and F 4 TCNQ
journal, September 2014

  • Cochran, Justin E.; Junk, Matthias J. N.; Glaudell, A. M.
  • Macromolecules, Vol. 47, Issue 19
  • DOI: 10.1021/ma501547h

Effect of Gate Electrode Work-Function on Source Charge Injection in Electrolyte-Gated Organic Field-Effect Transistors
journal, August 2013

  • Fabiano, Simone; Braun, Slawomir; Fahlman, Mats
  • Advanced Functional Materials, Vol. 24, Issue 5
  • DOI: 10.1002/adfm.201302070

Ambient Stable Zwitterionic Perylene Bisimide-Centered Radical
journal, November 2014

  • Schmidt, David; Bialas, David; Würthner, Frank
  • Angewandte Chemie, Vol. 127, Issue 12
  • DOI: 10.1002/ange.201408067

Power Factor Enhancement in Solution-Processed Organic n-Type Thermoelectrics Through Molecular Design
journal, March 2014

  • Russ, Boris; Robb, Maxwell J.; Brunetti, Fulvio G.
  • Advanced Materials, Vol. 26, Issue 21
  • DOI: 10.1002/adma.201306116

Influence of starting conformations on intramolecular exciplex formation in .omega.-phenyl-.alpha.-N,N-dimethylaminoalkanes
journal, June 1980

  • Van der Auweraer, M.; Gilbert, A.; De Schryver, F. C.
  • Journal of the American Chemical Society, Vol. 102, Issue 12
  • DOI: 10.1021/ja00532a006

A Universal Method to Produce Low-Work Function Electrodes for Organic Electronics
journal, April 2012


Air-Stable Complementary-like Circuits Based on Organic Ambipolar Transistors
journal, July 2006

  • Anthopoulos, T. D.; Setayesh, S.; Smits, E.
  • Advanced Materials, Vol. 18, Issue 14
  • DOI: 10.1002/adma.200502677

Self-Organization of Amine-Based Cathode Interfacial Materials in Inverted Polymer Solar Cells
journal, January 2014


Achieving High-Efficiency Polymer White-Light-Emitting Devices
journal, January 2006


Doping of Fullerenes via Anion-Induced Electron Transfer and Its Implication for Surfactant Facilitated High Performance Polymer Solar Cells
journal, June 2013

  • Li, Chang-Zhi; Chueh, Chu-Chen; Ding, Feizhi
  • Advanced Materials, Vol. 25, Issue 32
  • DOI: 10.1002/adma.201300580

Photophysics of the intramolecular exciplex formation in .omega.-(1-pyrenyl)-.alpha.-(dimethylamino)alkanes
journal, January 1987

  • Swinnen, A. M.; Van der Auweraer, M.; De Schryver, F. C.
  • Journal of the American Chemical Society, Vol. 109, Issue 2
  • DOI: 10.1021/ja00236a005

Fulleropyrrolidine interlayers: Tailoring electrodes to raise organic solar cell efficiency
journal, September 2014


Mechanistic Study on the Solution-Phase n-Doping of 1,3-Dimethyl-2-aryl-2,3-dihydro-1 H -benzoimidazole Derivatives
journal, September 2013

  • Naab, Benjamin D.; Guo, Song; Olthof, Selina
  • Journal of the American Chemical Society, Vol. 135, Issue 40
  • DOI: 10.1021/ja403906d

Molecular Understanding of Organic Solar Cells: The Challenges
journal, November 2009

  • Brédas, Jean-Luc; Norton, Joseph E.; Cornil, Jérôme
  • Accounts of Chemical Research, Vol. 42, Issue 11
  • DOI: 10.1021/ar900099h

Polymer solar cells
journal, February 2012


Electron Hopping in π-Stacked Covalent and Self-Assembled Perylene Diimides Observed by ENDOR Spectroscopy
journal, February 2006

  • Tauber, Michael J.; Kelley, Richard F.; Giaimo, Jovan M.
  • Journal of the American Chemical Society, Vol. 128, Issue 6
  • DOI: 10.1021/ja057031k

A water/alcohol-soluble copolymer based on fluorene and perylene diimide as a cathode interlayer for inverted polymer solar cells
journal, January 2015

  • Zhao, Zhenfeng; He, Jiebing; Wang, Jiuxing
  • Journal of Materials Chemistry C, Vol. 3, Issue 17
  • DOI: 10.1039/C5TC00450K

Poly(ethylene imine) Impurities Induce n-doping Reaction in Organic (Semi)Conductors
journal, July 2014

  • Fabiano, Simone; Braun, Slawomir; Liu, Xianjie
  • Advanced Materials, Vol. 26, Issue 34
  • DOI: 10.1002/adma.201401986

Air-stable fabric thermoelectric modules made of N- and P-type carbon nanotubes
journal, January 2012

  • Yu, Choongho; Murali, Advaith; Choi, Kyungwho
  • Energy & Environmental Science, Vol. 5, Issue 11
  • DOI: 10.1039/c2ee22838f

Solution phase n-doping of C 60 and PCBM using tetrabutylammonium fluoride
journal, January 2014

  • Weber, C. D.; Bradley, C.; Lonergan, M. C.
  • J. Mater. Chem. A, Vol. 2, Issue 2
  • DOI: 10.1039/C3TA14132B

Mechanism of Tetraalkylammonium Headgroup Degradation in Alkaline Fuel Cell Membranes
journal, March 2008

  • Chempath, Shaji; Einsla, Brian R.; Pratt, Lawrence R.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 9
  • DOI: 10.1021/jp7115577

One-Step Synthesis of Unsymmetrical N -Alkyl- N ′-aryl Perylene Diimides
journal, June 2014

  • Robb, Maxwell J.; Newton, Brandon; Fors, Brett P.
  • The Journal of Organic Chemistry, Vol. 79, Issue 13
  • DOI: 10.1021/jo500945k

Optimization of the thermoelectric figure of merit in the conducting polymer poly(3,4-ethylenedioxythiophene)
journal, May 2011

  • Bubnova, Olga; Khan, Zia Ullah; Malti, Abdellah
  • Nature Materials, Vol. 10, Issue 6, p. 429-433
  • DOI: 10.1038/nmat3012

Hydroxide based decomposition pathways of alkyltrimethylammonium cations
journal, May 2012


Small molecule semiconductors for high-efficiency organic photovoltaics
journal, January 2012

  • Lin, Yuze; Li, Yongfang; Zhan, Xiaowei
  • Chemical Society Reviews, Vol. 41, Issue 11
  • DOI: 10.1039/c2cs15313k

Organic Thin Film Transistors for Large Area Electronics
journal, January 2002


The chemical and structural origin of efficient p-type doping in P3HT
journal, May 2013


Solubility-Limited Extrinsic n-Type Doping of a High Electron Mobility Polymer for Thermoelectric Applications
journal, January 2014

  • Schlitz, Ruth A.; Brunetti, Fulvio G.; Glaudell, Anne M.
  • Advanced Materials, Vol. 26, Issue 18
  • DOI: 10.1002/adma.201304866

    Works referencing / citing this record:

    Air-Stable n-Type Thermoelectric Materials Enabled by Organic Diradicaloids
    journal, March 2019

    • Yuan, Dafei; Guo, Yuan; Zeng, Yan
    • Angewandte Chemie International Edition, Vol. 58, Issue 15
    • DOI: 10.1002/anie.201814544

    Air‐Stable n‐Type Thermoelectric Materials Enabled by Organic Diradicaloids
    journal, March 2019


    Air‐Stable n‐Type Thermoelectric Materials Enabled by Organic Diradicaloids
    journal, March 2019


    Air-Stable n-Type Thermoelectric Materials Enabled by Organic Diradicaloids
    journal, March 2019

    • Yuan, Dafei; Guo, Yuan; Zeng, Yan
    • Angewandte Chemie International Edition, Vol. 58, Issue 15
    • DOI: 10.1002/anie.201814544