Understanding Solution State Conformation and Aggregate Structure of Conjugated Polymers via Small Angle X-ray Scattering
Abstract
Donor-acceptor (D-A) conjugated polymers are high-performance organic electronic materials that exhibit complex aggregation behavior. Understanding the solution state conformation and aggregation of conjugated polymers is crucial for controlling morphology during thin-film deposition and the subsequent electronic performance. However, a precise multiscale structure of solution state aggregates is lacking. Here, we present an in-depth small-angle X-ray scattering (SAXS) analysis of the solution state structure of an isoindigo-bithiophene-based D-A polymer (PII-2T) in chlorobenzene and decane as our primary system. Modeling the system as a combination of hierarchical fibrillar aggregates mixed with dispersed polymers, we extract information about conformation and multiscale aggregation and also clarify the physical origin of features often observed but unaddressed or misinterpreted in small-angle scattering patterns of conjugated polymers. The persistence length of the D-A polymer extracted from SAXS agrees well with a theoretical model based on the dihedral potentials. Additionally, we show that the broad high q structure factor peak seen in scattering profiles can be attributed to lamellar stacking occurring within the fibril aggregates and that the low q aggregate scattering is strongly influenced by the polymer molecular weight. Overall, the SAXS profiles of D-A polymers in general exhibit a sensitive dependence on the co-existence of fibrillarmore »
- Authors:
-
[1];
[1];
[2];
[3];
[1]
- University of Illinois at Urbana-Champaign, IL (United States)
- University of Mons (Belguim)
- Argonne National Laboratory (ANL), Lemont, IL (United States). Advanced Photon Source (APS)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS); National Science Foundation (NSF); US Department of the Navy, Office of Naval Research (ONR); European Union’s Horizon 2020; Marie Sklodowska Curie Grant; Fonds de la Recherche Scientifiques de Belgique (F.R.S.-FNRS); Coronavirus CARES Act
- OSTI Identifier:
- 1961590
- Grant/Contract Number:
- AC02-06CH11357; 18-47828; SC0014664; N00014-19-1-2146; N00014-22-1-2202; 17-27605; 722651; 2.5020.11; 1117545
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 55; Journal Issue: 11; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; conformation; conjugated polymers
Citation Formats
Kwok, Justin J., Park, Kyung Sun, Patel, Bijal B., Dilmurat, Rishat, Beljonne, David, Zuo, Xiaobing, Lee, Byeongdu, and Diao, Ying. Understanding Solution State Conformation and Aggregate Structure of Conjugated Polymers via Small Angle X-ray Scattering. United States: N. p., 2022.
Web. doi:10.1021/acs.macromol.1c02449.
Kwok, Justin J., Park, Kyung Sun, Patel, Bijal B., Dilmurat, Rishat, Beljonne, David, Zuo, Xiaobing, Lee, Byeongdu, & Diao, Ying. Understanding Solution State Conformation and Aggregate Structure of Conjugated Polymers via Small Angle X-ray Scattering. United States. https://doi.org/10.1021/acs.macromol.1c02449
Kwok, Justin J., Park, Kyung Sun, Patel, Bijal B., Dilmurat, Rishat, Beljonne, David, Zuo, Xiaobing, Lee, Byeongdu, and Diao, Ying. Thu .
"Understanding Solution State Conformation and Aggregate Structure of Conjugated Polymers via Small Angle X-ray Scattering". United States. https://doi.org/10.1021/acs.macromol.1c02449. https://www.osti.gov/servlets/purl/1961590.
@article{osti_1961590,
title = {Understanding Solution State Conformation and Aggregate Structure of Conjugated Polymers via Small Angle X-ray Scattering},
author = {Kwok, Justin J. and Park, Kyung Sun and Patel, Bijal B. and Dilmurat, Rishat and Beljonne, David and Zuo, Xiaobing and Lee, Byeongdu and Diao, Ying},
abstractNote = {Donor-acceptor (D-A) conjugated polymers are high-performance organic electronic materials that exhibit complex aggregation behavior. Understanding the solution state conformation and aggregation of conjugated polymers is crucial for controlling morphology during thin-film deposition and the subsequent electronic performance. However, a precise multiscale structure of solution state aggregates is lacking. Here, we present an in-depth small-angle X-ray scattering (SAXS) analysis of the solution state structure of an isoindigo-bithiophene-based D-A polymer (PII-2T) in chlorobenzene and decane as our primary system. Modeling the system as a combination of hierarchical fibrillar aggregates mixed with dispersed polymers, we extract information about conformation and multiscale aggregation and also clarify the physical origin of features often observed but unaddressed or misinterpreted in small-angle scattering patterns of conjugated polymers. The persistence length of the D-A polymer extracted from SAXS agrees well with a theoretical model based on the dihedral potentials. Additionally, we show that the broad high q structure factor peak seen in scattering profiles can be attributed to lamellar stacking occurring within the fibril aggregates and that the low q aggregate scattering is strongly influenced by the polymer molecular weight. Overall, the SAXS profiles of D-A polymers in general exhibit a sensitive dependence on the co-existence of fibrillar aggregate and dispersed polymer chain populations. We corroborate our findings from SAXS with electron microscopy of freeze-dried samples for direct imaging of fibrillar aggregates. Finally, we demonstrate the generality of our approach by fitting the scattering profiles of a variety of D-A polymers based on thieno-isoindigo (PTII-2T), diketopyrrolopyrrole (DPP2T-TT, DPP-BTZ, PDPP2FT-C-16), naphthalenediimide (P(NDI2OD-T2)), and a conjugated block copolymer P3HT-b-DPPT-T. The results presented here establish a picture of the D-A polymer solution state structure and provide a general method of interpreting and analyzing their scattering profiles.},
doi = {10.1021/acs.macromol.1c02449},
journal = {Macromolecules},
number = 11,
volume = 55,
place = {United States},
year = {Thu May 19 00:00:00 EDT 2022},
month = {Thu May 19 00:00:00 EDT 2022}
}
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