Complex Relationship between Side-Chain Polarity, Conductivity, and Thermal Stability in Molecularly Doped Conjugated Polymers
Abstract
Molecularly doped conjugated polymers with polar side chains are an emerging class of conducting materials exhibiting enhanced and thermally stable conductivity. In this work, we study the electronic conductivity (σ) and the corresponding thermal stability of two polythiophene derivatives comprising oligoethylene glycol side chains: one having oxygen attached to the thiophene ring (poly(3-(methoxyethoxyethoxy)thiophene) (P3MEET)) and the other having a methylene spacer between the oxygen and the thiophene ring (poly(3-(methoxyethoxyethoxymethyl)thiophene) (P3MEEMT)). Thin films were vapor-doped with fluorinated derivatives of tetracyanoquinodimethane (FnTCNQ, n = 4, 2, 1) to determine the role of dopant strength (electron affinity) in maximum achievable σ. Specifically, when vapor doping with F4TCNQ, P3MEET achieved a substantially higher σ of 37.1 ± 10.1 S/cm compared to a σ of 0.82 ± 0.06 S/cm for P3MEEMT. Structural characterization using a combination of X-ray and optical spectroscopy reveals that the higher degree of conformational order of polymer chains in the amorphous domain upon doping with F4TCNQ in P3MEET is a major contributing factor for the higher σ of P3MEET. Additionally, vapor-doped P3MEET exhibited superior thermal stability compared to P3MEEMT, highlighting that the presence of polar side chains alone does not ensure higher thermal stability. Molecular dynamics simulations indicate that the dopant–side-chainmore »
- Authors:
-
[1];
[3];
[1];
[4];
[4];
[1];
[2];
[3];
[5];
[5]
- Univ. of Chicago, IL (United States)
- Cornell Univ., Ithaca, NY (United States)
- Univ. of Washington, Seattle, WA (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
- OSTI Identifier:
- 1787870
- Grant/Contract Number:
- AC02-06CH11357; 1922259
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 33; Journal Issue: 2; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; impurities; thermal stability; electrical conductivity; doping; polymers
Citation Formats
Dong, Ban Xuan, Nowak, Christian, Onorato, Jonathan W., Ma, Tengzhou, Niklas, Jens, Poluektov, Oleg G., Grocke, Garrett, DiTusa, Mark F., Escobedo, Fernando A., Luscombe, Christine K., Nealey, Paul F., and Patel, Shrayesh N. Complex Relationship between Side-Chain Polarity, Conductivity, and Thermal Stability in Molecularly Doped Conjugated Polymers. United States: N. p., 2021.
Web. doi:10.1021/acs.chemmater.0c04153.
Dong, Ban Xuan, Nowak, Christian, Onorato, Jonathan W., Ma, Tengzhou, Niklas, Jens, Poluektov, Oleg G., Grocke, Garrett, DiTusa, Mark F., Escobedo, Fernando A., Luscombe, Christine K., Nealey, Paul F., & Patel, Shrayesh N. Complex Relationship between Side-Chain Polarity, Conductivity, and Thermal Stability in Molecularly Doped Conjugated Polymers. United States. https://doi.org/10.1021/acs.chemmater.0c04153
Dong, Ban Xuan, Nowak, Christian, Onorato, Jonathan W., Ma, Tengzhou, Niklas, Jens, Poluektov, Oleg G., Grocke, Garrett, DiTusa, Mark F., Escobedo, Fernando A., Luscombe, Christine K., Nealey, Paul F., and Patel, Shrayesh N. Wed .
"Complex Relationship between Side-Chain Polarity, Conductivity, and Thermal Stability in Molecularly Doped Conjugated Polymers". United States. https://doi.org/10.1021/acs.chemmater.0c04153. https://www.osti.gov/servlets/purl/1787870.
@article{osti_1787870,
title = {Complex Relationship between Side-Chain Polarity, Conductivity, and Thermal Stability in Molecularly Doped Conjugated Polymers},
author = {Dong, Ban Xuan and Nowak, Christian and Onorato, Jonathan W. and Ma, Tengzhou and Niklas, Jens and Poluektov, Oleg G. and Grocke, Garrett and DiTusa, Mark F. and Escobedo, Fernando A. and Luscombe, Christine K. and Nealey, Paul F. and Patel, Shrayesh N.},
abstractNote = {Molecularly doped conjugated polymers with polar side chains are an emerging class of conducting materials exhibiting enhanced and thermally stable conductivity. In this work, we study the electronic conductivity (σ) and the corresponding thermal stability of two polythiophene derivatives comprising oligoethylene glycol side chains: one having oxygen attached to the thiophene ring (poly(3-(methoxyethoxyethoxy)thiophene) (P3MEET)) and the other having a methylene spacer between the oxygen and the thiophene ring (poly(3-(methoxyethoxyethoxymethyl)thiophene) (P3MEEMT)). Thin films were vapor-doped with fluorinated derivatives of tetracyanoquinodimethane (FnTCNQ, n = 4, 2, 1) to determine the role of dopant strength (electron affinity) in maximum achievable σ. Specifically, when vapor doping with F4TCNQ, P3MEET achieved a substantially higher σ of 37.1 ± 10.1 S/cm compared to a σ of 0.82 ± 0.06 S/cm for P3MEEMT. Structural characterization using a combination of X-ray and optical spectroscopy reveals that the higher degree of conformational order of polymer chains in the amorphous domain upon doping with F4TCNQ in P3MEET is a major contributing factor for the higher σ of P3MEET. Additionally, vapor-doped P3MEET exhibited superior thermal stability compared to P3MEEMT, highlighting that the presence of polar side chains alone does not ensure higher thermal stability. Molecular dynamics simulations indicate that the dopant–side-chain nonbond energy is lower in the P3MEET:F4TCNQ mixture, suggesting more favorable dopant–side-chain interaction, which is a factor in improving the thermal stability of a polymer/dopant pair. Our results reveal that additional factors such as polymer ionization energy and side-chain–dopant interaction should be taken into account for the design of thermally stable, highly conductive polymers.},
doi = {10.1021/acs.chemmater.0c04153},
journal = {Chemistry of Materials},
number = 2,
volume = 33,
place = {United States},
year = {Wed Jan 06 00:00:00 EST 2021},
month = {Wed Jan 06 00:00:00 EST 2021}
}
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