Towards understanding the doping mechanism of organic semiconductors by Lewis acids
Abstract
Precise doping of organic semiconductors allows control over the conductivity of these materials, an essential parameter in electronic applications. Although Lewis acids have recently shown promise as dopants for solution-processed polymers, their doping mechanism is not yet fully understood. In this study, we found that B(C6F5)3 is a superior dopant to the other Lewis acids investigated (BF3, BBr3 and AlCl3). Experiments indicate that Lewis acid–base adduct formation with polymers inhibits the doping process. Electron–nuclear double-resonance and nuclear magnetic resonance experiments, together with density functional theory, show that p-type doping occurs by generation of a water–Lewis acid complex with substantial Brønsted acidity, followed by protonation of the polymer backbone and electron transfer from a neutral chain segment to a positively charged, protonated one. Here, this study provides insight into a potential path for protonic acid doping and shows how trace levels of water can transform Lewis acids into powerful Brønsted acids.
- Authors:
-
[1];
[2];
[4];
[3];
[1];
[1]
- Univ. of California, Santa Barbara, CA (United States). Center for Polymers and Organic Solids
- Donghua Univ., Shanghai (China). Center for Advanced Low-Dimension Materials
- Humboldt Univ. of Berlin (Germany)
- Univ. of Kentucky, Lexington, KY (United States)
- Publication Date:
- Research Org.:
- Univ. of California, Santa Barbara, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Science Foundation (NSF); German Research Foundation (DFG)
- OSTI Identifier:
- 1593929
- Grant/Contract Number:
- SC0017659; SC0018208; AC02-05CH11231; 1650114
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Materials
- Additional Journal Information:
- Journal Volume: 18; Journal Issue: 12; Journal ID: ISSN 1476-1122
- Publisher:
- Springer Nature - Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Yurash, Brett, Cao, David Xi, Brus, Viktor V., Leifert, Dirk, Wang, Ming, Dixon, Alana, Seifrid, Martin, Mansour, Ahmed, Lungwitz, Dominique, Liu, Tuo, Santiago, Peter J., Graham, Kenneth R., Koch, Norbert, Bazan, Guillermo C., and Nguyen, Thuc-Quyen. Towards understanding the doping mechanism of organic semiconductors by Lewis acids. United States: N. p., 2019.
Web. doi:10.1038/s41563-019-0479-0.
Yurash, Brett, Cao, David Xi, Brus, Viktor V., Leifert, Dirk, Wang, Ming, Dixon, Alana, Seifrid, Martin, Mansour, Ahmed, Lungwitz, Dominique, Liu, Tuo, Santiago, Peter J., Graham, Kenneth R., Koch, Norbert, Bazan, Guillermo C., & Nguyen, Thuc-Quyen. Towards understanding the doping mechanism of organic semiconductors by Lewis acids. United States. https://doi.org/10.1038/s41563-019-0479-0
Yurash, Brett, Cao, David Xi, Brus, Viktor V., Leifert, Dirk, Wang, Ming, Dixon, Alana, Seifrid, Martin, Mansour, Ahmed, Lungwitz, Dominique, Liu, Tuo, Santiago, Peter J., Graham, Kenneth R., Koch, Norbert, Bazan, Guillermo C., and Nguyen, Thuc-Quyen. Mon .
"Towards understanding the doping mechanism of organic semiconductors by Lewis acids". United States. https://doi.org/10.1038/s41563-019-0479-0. https://www.osti.gov/servlets/purl/1593929.
@article{osti_1593929,
title = {Towards understanding the doping mechanism of organic semiconductors by Lewis acids},
author = {Yurash, Brett and Cao, David Xi and Brus, Viktor V. and Leifert, Dirk and Wang, Ming and Dixon, Alana and Seifrid, Martin and Mansour, Ahmed and Lungwitz, Dominique and Liu, Tuo and Santiago, Peter J. and Graham, Kenneth R. and Koch, Norbert and Bazan, Guillermo C. and Nguyen, Thuc-Quyen},
abstractNote = {Precise doping of organic semiconductors allows control over the conductivity of these materials, an essential parameter in electronic applications. Although Lewis acids have recently shown promise as dopants for solution-processed polymers, their doping mechanism is not yet fully understood. In this study, we found that B(C6F5)3 is a superior dopant to the other Lewis acids investigated (BF3, BBr3 and AlCl3). Experiments indicate that Lewis acid–base adduct formation with polymers inhibits the doping process. Electron–nuclear double-resonance and nuclear magnetic resonance experiments, together with density functional theory, show that p-type doping occurs by generation of a water–Lewis acid complex with substantial Brønsted acidity, followed by protonation of the polymer backbone and electron transfer from a neutral chain segment to a positively charged, protonated one. Here, this study provides insight into a potential path for protonic acid doping and shows how trace levels of water can transform Lewis acids into powerful Brønsted acids.},
doi = {10.1038/s41563-019-0479-0},
journal = {Nature Materials},
number = 12,
volume = 18,
place = {United States},
year = {2019},
month = {9}
}
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