Effect of solvent quality and sidechain architecture on conjugated polymer chain conformation in solution
Conjugated polymers (CPs) are solution-processible for various electronic applications, where solution aggregation and dynamics could impact the morphology in the solid state. Various solvents and solvent mixtures have been used to dissolve and process CPs, but few studies have quantified the effect...
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| Published in | Nanoscale Vol. 16; no. 13; pp. 6495 - 656 |
|---|---|
| Main Authors | , , , , |
| Format | Journal Article |
| Language | English |
| Published |
England
Royal Society of Chemistry
28.03.2024
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| Subjects | |
| Online Access | Get full text |
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| Abstract | Conjugated polymers (CPs) are solution-processible for various electronic applications, where solution aggregation and dynamics could impact the morphology in the solid state. Various solvents and solvent mixtures have been used to dissolve and process CPs, but few studies have quantified the effect of solvent quality on the solution behavior of CPs. Herein, we performed static light scattering and small-angle X-ray scattering combined with molecular dynamics (MD) simulation to investigate CP solution behaviors with solvents of varying quality, including poly(3-alkylthiophene) (P3ATs) with various sidechain lengths from -C
4
H
9
to -C
12
H
25
, poly[bis(3-dodecyl-2-thienyl)-2,2′-dithiophene-5,5′-diyl] (PQT-12) and poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-
b
]thiophene] (PBTTT-12). We found that chlorobenzene is a better solvent than toluene for various CPs, which was evident from the positive second virial coefficient
A
2
ranging from 0.3 to 4.7 × 10
−3
cm
3
mol g
−2
towards P3ATs. For P3ATs in non-polar solvents, longer sidechains promote more positive
A
2
, indicating a better polymer-solvent interaction, wherein
A
2
for toluene increases from −5.9 to 1.4 × 10
−3
cm
3
mol g
−2
, and in CB,
A
2
ranges from 1.0 to 4.7 × 10
−3
cm
3
mol g
−2
when sidechain length increases from -C
6
H
13
to -C
12
H
25
. Moreover, PQT-12 and PBTTT-12 have strong aggregation tendencies in all solutions, with an apparent positive
A
2
(∼0.5 × 10
−3
cm
3
mol g
−2
) due to multi-chain aggregates and peculiar chain folding. These solvent-dependent aggregation behaviors can be well correlated to spectroscopy measurement results. Our coarse-grained MD simulation results further suggested that CPs with long, dense, and branched sidechains can achieve enhanced polymer-solvent interaction, and thus enable overall better solution dispersion. This work provides quantitative insights into the solution behavior of conjugated polymers that can guide both the design and process of CPs toward next-generation organic electronics.
The solubilization of conjugated polymers can be carefully quantified using static light scattering. Our findings reveal that the architecture of sidechains and backbones significantly influences polymer's conformation and aggregation. |
|---|---|
| AbstractList | Conjugated polymers (CPs) are solution-processible for various electronic applications, where solution aggregation and dynamics could impact the morphology in the solid state. Various solvents and solvent mixtures have been used to dissolve and process CPs, but few studies have quantified the effect of solvent quality on the solution behavior of CPs. Herein, we performed static light scattering and small-angle X-ray scattering combined with molecular dynamics (MD) simulation to investigate CP solution behaviors with solvents of varying quality, including poly(3-alkylthiophene) (P3ATs) with various sidechain lengths from –C4H9 to –C12H25, poly[bis(3-dodecyl-2-thienyl)-2,2′-dithiophene-5,5′-diyl] (PQT-12) and poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT-12). We found that chlorobenzene is a better solvent than toluene for various CPs, which was evident from the positive second virial coefficient A2 ranging from 0.3 to 4.7 × 10−3 cm3 mol g−2 towards P3ATs. For P3ATs in non-polar solvents, longer sidechains promote more positive A2, indicating a better polymer–solvent interaction, wherein A2 for toluene increases from −5.9 to 1.4 × 10−3 cm3 mol g−2, and in CB, A2 ranges from 1.0 to 4.7 × 10−3 cm3 mol g−2 when sidechain length increases from –C6H13 to –C12H25. Moreover, PQT-12 and PBTTT-12 have strong aggregation tendencies in all solutions, with an apparent positive A2 (∼0.5 × 10−3 cm3 mol g−2) due to multi-chain aggregates and peculiar chain folding. These solvent-dependent aggregation behaviors can be well correlated to spectroscopy measurement results. Our coarse-grained MD simulation results further suggested that CPs with long, dense, and branched sidechains can achieve enhanced polymer–solvent interaction, and thus enable overall better solution dispersion. This work provides quantitative insights into the solution behavior of conjugated polymers that can guide both the design and process of CPs toward next-generation organic electronics. Conjugated polymers (CPs) are solution-processible for various electronic applications, where solution aggregation and dynamics could impact the morphology in the solid state. Various solvents and solvent mixtures have been used to dissolve and process CPs, but few studies have quantified the effect of solvent quality on the solution behavior of CPs. Herein, we performed static light scattering and small-angle X-ray scattering combined with molecular dynamics (MD) simulation to investigate CP solution behaviors with solvents of varying quality, including poly(3-alkylthiophene) (P3ATs) with various sidechain lengths from -C H to -C H , poly[bis(3-dodecyl-2-thienyl)-2,2'-dithiophene-5,5'-diyl] (PQT-12) and poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2- ]thiophene] (PBTTT-12). We found that chlorobenzene is a better solvent than toluene for various CPs, which was evident from the positive second virial coefficient ranging from 0.3 to 4.7 × 10 cm mol g towards P3ATs. For P3ATs in non-polar solvents, longer sidechains promote more positive , indicating a better polymer-solvent interaction, wherein for toluene increases from -5.9 to 1.4 × 10 cm mol g , and in CB, ranges from 1.0 to 4.7 × 10 cm mol g when sidechain length increases from -C H to -C H . Moreover, PQT-12 and PBTTT-12 have strong aggregation tendencies in all solutions, with an apparent positive (∼0.5 × 10 cm mol g ) due to multi-chain aggregates and peculiar chain folding. These solvent-dependent aggregation behaviors can be well correlated to spectroscopy measurement results. Our coarse-grained MD simulation results further suggested that CPs with long, dense, and branched sidechains can achieve enhanced polymer-solvent interaction, and thus enable overall better solution dispersion. This work provides quantitative insights into the solution behavior of conjugated polymers that can guide both the design and process of CPs toward next-generation organic electronics. Conjugated polymers (CPs) are solution-processible for various electronic applications, where solution aggregation and dynamics could impact the morphology in the solid state. Various solvents and solvent mixtures have been used to dissolve and process CPs, but few studies have quantified the effect of solvent quality on the solution behavior of CPs. Herein, we performed static light scattering and small-angle X-ray scattering combined with molecular dynamics (MD) simulation to investigate CP solution behaviors with solvents of varying quality, including poly(3-alkylthiophene) (P3ATs) with various sidechain lengths from -C 4 H 9 to -C 12 H 25 , poly[bis(3-dodecyl-2-thienyl)-2,2′-dithiophene-5,5′-diyl] (PQT-12) and poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2- b ]thiophene] (PBTTT-12). We found that chlorobenzene is a better solvent than toluene for various CPs, which was evident from the positive second virial coefficient A 2 ranging from 0.3 to 4.7 × 10 −3 cm 3 mol g −2 towards P3ATs. For P3ATs in non-polar solvents, longer sidechains promote more positive A 2 , indicating a better polymer-solvent interaction, wherein A 2 for toluene increases from −5.9 to 1.4 × 10 −3 cm 3 mol g −2 , and in CB, A 2 ranges from 1.0 to 4.7 × 10 −3 cm 3 mol g −2 when sidechain length increases from -C 6 H 13 to -C 12 H 25 . Moreover, PQT-12 and PBTTT-12 have strong aggregation tendencies in all solutions, with an apparent positive A 2 (∼0.5 × 10 −3 cm 3 mol g −2 ) due to multi-chain aggregates and peculiar chain folding. These solvent-dependent aggregation behaviors can be well correlated to spectroscopy measurement results. Our coarse-grained MD simulation results further suggested that CPs with long, dense, and branched sidechains can achieve enhanced polymer-solvent interaction, and thus enable overall better solution dispersion. This work provides quantitative insights into the solution behavior of conjugated polymers that can guide both the design and process of CPs toward next-generation organic electronics. The solubilization of conjugated polymers can be carefully quantified using static light scattering. Our findings reveal that the architecture of sidechains and backbones significantly influences polymer's conformation and aggregation. Conjugated polymers (CPs) are solution-processible for various electronic applications, where solution aggregation and dynamics could impact the morphology in the solid state. Various solvents and solvent mixtures have been used to dissolve and process CPs, but few studies have quantified the effect of solvent quality on the solution behavior of CPs. Herein, we performed static light scattering and small-angle X-ray scattering combined with molecular dynamics (MD) simulation to investigate CP solution behaviors with solvents of varying quality, including poly(3-alkylthiophene) (P3ATs) with various sidechain lengths from -C4H9 to -C12H25, poly[bis(3-dodecyl-2-thienyl)-2,2'-dithiophene-5,5'-diyl] (PQT-12) and poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT-12). We found that chlorobenzene is a better solvent than toluene for various CPs, which was evident from the positive second virial coefficient A2 ranging from 0.3 to 4.7 × 10-3 cm3 mol g-2 towards P3ATs. For P3ATs in non-polar solvents, longer sidechains promote more positive A2, indicating a better polymer-solvent interaction, wherein A2 for toluene increases from -5.9 to 1.4 × 10-3 cm3 mol g-2, and in CB, A2 ranges from 1.0 to 4.7 × 10-3 cm3 mol g-2 when sidechain length increases from -C6H13 to -C12H25. Moreover, PQT-12 and PBTTT-12 have strong aggregation tendencies in all solutions, with an apparent positive A2 (∼0.5 × 10-3 cm3 mol g-2) due to multi-chain aggregates and peculiar chain folding. These solvent-dependent aggregation behaviors can be well correlated to spectroscopy measurement results. Our coarse-grained MD simulation results further suggested that CPs with long, dense, and branched sidechains can achieve enhanced polymer-solvent interaction, and thus enable overall better solution dispersion. This work provides quantitative insights into the solution behavior of conjugated polymers that can guide both the design and process of CPs toward next-generation organic electronics.Conjugated polymers (CPs) are solution-processible for various electronic applications, where solution aggregation and dynamics could impact the morphology in the solid state. Various solvents and solvent mixtures have been used to dissolve and process CPs, but few studies have quantified the effect of solvent quality on the solution behavior of CPs. Herein, we performed static light scattering and small-angle X-ray scattering combined with molecular dynamics (MD) simulation to investigate CP solution behaviors with solvents of varying quality, including poly(3-alkylthiophene) (P3ATs) with various sidechain lengths from -C4H9 to -C12H25, poly[bis(3-dodecyl-2-thienyl)-2,2'-dithiophene-5,5'-diyl] (PQT-12) and poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT-12). We found that chlorobenzene is a better solvent than toluene for various CPs, which was evident from the positive second virial coefficient A2 ranging from 0.3 to 4.7 × 10-3 cm3 mol g-2 towards P3ATs. For P3ATs in non-polar solvents, longer sidechains promote more positive A2, indicating a better polymer-solvent interaction, wherein A2 for toluene increases from -5.9 to 1.4 × 10-3 cm3 mol g-2, and in CB, A2 ranges from 1.0 to 4.7 × 10-3 cm3 mol g-2 when sidechain length increases from -C6H13 to -C12H25. Moreover, PQT-12 and PBTTT-12 have strong aggregation tendencies in all solutions, with an apparent positive A2 (∼0.5 × 10-3 cm3 mol g-2) due to multi-chain aggregates and peculiar chain folding. These solvent-dependent aggregation behaviors can be well correlated to spectroscopy measurement results. Our coarse-grained MD simulation results further suggested that CPs with long, dense, and branched sidechains can achieve enhanced polymer-solvent interaction, and thus enable overall better solution dispersion. This work provides quantitative insights into the solution behavior of conjugated polymers that can guide both the design and process of CPs toward next-generation organic electronics. Conjugated polymers (CPs) are solution-processible for various electronic applications, where solution aggregation and dynamics could impact the morphology in the solid state. Various solvents and solvent mixtures have been used to dissolve and process CPs, but few studies have quantified the effect of solvent quality on the solution behavior of CPs. Herein, we performed static light scattering and small-angle X-ray scattering combined with molecular dynamics (MD) simulation to investigate CP solution behaviors with solvents of varying quality, including poly(3-alkylthiophene) (P3ATs) with various sidechain lengths from –C 4 H 9 to –C 12 H 25 , poly[bis(3-dodecyl-2-thienyl)-2,2′-dithiophene-5,5′-diyl] (PQT-12) and poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2- b ]thiophene] (PBTTT-12). We found that chlorobenzene is a better solvent than toluene for various CPs, which was evident from the positive second virial coefficient A 2 ranging from 0.3 to 4.7 × 10 −3 cm 3 mol g −2 towards P3ATs. For P3ATs in non-polar solvents, longer sidechains promote more positive A 2 , indicating a better polymer–solvent interaction, wherein A 2 for toluene increases from −5.9 to 1.4 × 10 −3 cm 3 mol g −2 , and in CB, A 2 ranges from 1.0 to 4.7 × 10 −3 cm 3 mol g −2 when sidechain length increases from –C 6 H 13 to –C 12 H 25 . Moreover, PQT-12 and PBTTT-12 have strong aggregation tendencies in all solutions, with an apparent positive A 2 (∼0.5 × 10 −3 cm 3 mol g −2 ) due to multi-chain aggregates and peculiar chain folding. These solvent-dependent aggregation behaviors can be well correlated to spectroscopy measurement results. Our coarse-grained MD simulation results further suggested that CPs with long, dense, and branched sidechains can achieve enhanced polymer–solvent interaction, and thus enable overall better solution dispersion. This work provides quantitative insights into the solution behavior of conjugated polymers that can guide both the design and process of CPs toward next-generation organic electronics. |
| Author | Gu, Xiaodan Xia, Wenjie Fang, Lei Ma, Guorong Li, Zhaofan |
| AuthorAffiliation | Department of Chemistry The University of Southern Mississippi Iowa State University Department of Aerospace Engineering Texas A&M University School of Polymer Science and Engineering |
| AuthorAffiliation_xml | – sequence: 0 name: Department of Aerospace Engineering – sequence: 0 name: School of Polymer Science and Engineering – sequence: 0 name: Department of Chemistry – sequence: 0 name: Iowa State University – sequence: 0 name: The University of Southern Mississippi – sequence: 0 name: Texas A&M University |
| Author_xml | – sequence: 1 givenname: Guorong surname: Ma fullname: Ma, Guorong – sequence: 2 givenname: Zhaofan surname: Li fullname: Li, Zhaofan – sequence: 3 givenname: Lei surname: Fang fullname: Fang, Lei – sequence: 4 givenname: Wenjie surname: Xia fullname: Xia, Wenjie – sequence: 5 givenname: Xiaodan surname: Gu fullname: Gu, Xiaodan |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/38465951$$D View this record in MEDLINE/PubMed |
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| CitedBy_id | crossref_primary_10_1021_acs_macromol_4c01496 crossref_primary_10_1557_s43579_024_00654_0 crossref_primary_10_1039_D4CC03217A crossref_primary_10_1002_pol_20230689 |
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| DOI | 10.1039/d3nr05721f |
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| Notes | https://doi.org/10.1039/d3nr05721f Electronic supplementary information (ESI) available: Sample preparation, dn/dc measurement, HSP calculation, DSC measurements, scattering, and spectroscopy measurements of the samples in solution and solid states. Additional coarse grain modelling data. See DOI Xiaodan Gu received his PhD from the Department of Polymer Science and Engineering at the University of Massachusetts Amherst in 2014. Subsequently, he did a post-doctoral study at Stanford University and SLAC National Accelerator Laboratory. Since 2017, he has been a Nina Bell Suggs Endowed Associate Professor from the School of Polymer Science and Engineering at the University of Southern Mississippi. His current research interest revolves around various fundamental polymer physics phenomena related to conjugated polymers and their derivative devices. His group studies the structure, dynamics, and morphology of conjugated polymers and aims to link their molecular structures to their macroscopic properties through advanced metrology with an emphasis on scattering techniques. ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 content type line 23 |
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| SubjectTerms | Behavior Chlorobenzene Molecular conformation Molecular dynamics Polymers Solvents Toluene Virial coefficients X-ray scattering |
| Title | Effect of solvent quality and sidechain architecture on conjugated polymer chain conformation in solution |
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