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

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:
Grant/Contract Number:
AC02-05CH11231; DMR 1121053
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
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)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
OSTI Identifier:
1377413

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., 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.. 2015. "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}
}

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

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

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

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

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