High Dielectric Constant Semiconducting Poly(3-alkylthiophene)s from Side Chain Modification with Polar Sulfinyl and Sulfonyl Groups

doi:https://doi.org/10.1021/acs.macromol.8b01895

Title: High Dielectric Constant Semiconducting Poly(3-alkylthiophene)s from Side Chain Modification with Polar Sulfinyl and Sulfonyl Groups

Abstract

In this paper, there is growing interest in designing and developing high dielectric constant (ε _r) organic semiconductors because they have the potential to further enhance device performance by promoting exciton dissociation, reducing bimolecular charge carrier recombination, and potentially enhancing charge carrier mobility via charge screening. In this study, a new class of semiconducting polymers with high ε _r, i.e., sulfinylated and sulfonylated poly(3-alkylthiophene)s (P3ATs), were synthesized. Because of efficient rotation of highly polar methylsulfinyl and methylsulfonyl side groups (i.e., orientational polarization), high ε _r values were achieved for these functionalized P3ATs based on an accurate capacitance measurement using a gold/semiconducting polymer/SiO ₂/n-doped Si configuration. For example, the ε _r at megahertz and room temperature increased from 3.75 for the regioregular poly(3-hexylthiophene) (P3HT) to 7.4 for the sulfinylated and 8.1–9.3 for sulfonylated P3AT polymers. These values are among the highest ε _r reported for conjugated polymers so far. Grazing-incident wide-angle X-ray diffraction results showed that these polar groups decreased the crystallinity for the polythiophene backbones and interfered with the π–π stacking in the crystalline structure. Consequently, their optical properties, including UV–vis absorption and fluorescence, changed in thin films. From this study, the sulfinylated polymer may be promising to provide amore »« less

Authors:

^[1];

^[1]; Pejić, Sandra ^[1]; Li, Ruipeng ^[2]; Fukuto, Masafumi ^[2];

^[1];

^[1]

Case Western Reserve Univ., Cleveland, OH (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Publication Date:: 2018-11-14

Research Org.:: Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1491148

Report Number(s):: BNL-210851-2019-JAAM
Journal ID: ISSN 0024-9297

Grant/Contract Number:: SC0012704

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Macromolecules

Additional Journal Information:: Journal Volume: 51; Journal Issue: 22; Journal ID: ISSN 0024-9297

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE

Citation Formats


                    Wang, Chunlai, Zhang, Zhongbo, Pejić, Sandra, Li, Ruipeng, Fukuto, Masafumi, Zhu, Lei, and Sauvé, Geneviève. High Dielectric Constant Semiconducting Poly(3-alkylthiophene)s from Side Chain Modification with Polar Sulfinyl and Sulfonyl Groups.  United States: N. p., 2018. 
        Web.  doi:10.1021/acs.macromol.8b01895.

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                    Wang, Chunlai, Zhang, Zhongbo, Pejić, Sandra, Li, Ruipeng, Fukuto, Masafumi, Zhu, Lei, & Sauvé, Geneviève. High Dielectric Constant Semiconducting Poly(3-alkylthiophene)s from Side Chain Modification with Polar Sulfinyl and Sulfonyl Groups.  United States.  https://doi.org/10.1021/acs.macromol.8b01895

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                    Wang, Chunlai, Zhang, Zhongbo, Pejić, Sandra, Li, Ruipeng, Fukuto, Masafumi, Zhu, Lei, and Sauvé, Geneviève. Wed .  
        "High Dielectric Constant Semiconducting Poly(3-alkylthiophene)s from Side Chain Modification with Polar Sulfinyl and Sulfonyl Groups".  United States.  https://doi.org/10.1021/acs.macromol.8b01895.  https://www.osti.gov/servlets/purl/1491148.

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@article{osti_1491148,

  title        = {High Dielectric Constant Semiconducting Poly(3-alkylthiophene)s from Side Chain Modification with Polar Sulfinyl and Sulfonyl Groups},

  author       = {Wang, Chunlai and Zhang, Zhongbo and Pejić, Sandra and Li, Ruipeng and Fukuto, Masafumi and Zhu, Lei and Sauvé, Geneviève},

  abstractNote = {In this paper, there is growing interest in designing and developing high dielectric constant (εr) organic semiconductors because they have the potential to further enhance device performance by promoting exciton dissociation, reducing bimolecular charge carrier recombination, and potentially enhancing charge carrier mobility via charge screening. In this study, a new class of semiconducting polymers with high εr, i.e., sulfinylated and sulfonylated poly(3-alkylthiophene)s (P3ATs), were synthesized. Because of efficient rotation of highly polar methylsulfinyl and methylsulfonyl side groups (i.e., orientational polarization), high εr values were achieved for these functionalized P3ATs based on an accurate capacitance measurement using a gold/semiconducting polymer/SiO2/n-doped Si configuration. For example, the εr at megahertz and room temperature increased from 3.75 for the regioregular poly(3-hexylthiophene) (P3HT) to 7.4 for the sulfinylated and 8.1–9.3 for sulfonylated P3AT polymers. These values are among the highest εr reported for conjugated polymers so far. Grazing-incident wide-angle X-ray diffraction results showed that these polar groups decreased the crystallinity for the polythiophene backbones and interfered with the π–π stacking in the crystalline structure. Consequently, their optical properties, including UV–vis absorption and fluorescence, changed in thin films. From this study, the sulfinylated polymer may be promising to provide a balance between high εr and preserving favorable polythiophene π–π stacking structure for device applications.},

  doi          = {10.1021/acs.macromol.8b01895},

  url          = {https://www.osti.gov/biblio/1491148},
  journal      = {Macromolecules},

  issn         = {0024-9297},

  number       = 22,

  volume       = 51,

  place        = {United States},

  year         = {2018},

  month        = {11}

}

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Works referencing / citing this record:

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https://doi.org/10.1039/c9ta08654d

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Title: High Dielectric Constant Semiconducting Poly(3-alkylthiophene)s from Side Chain Modification with Polar Sulfinyl and Sulfonyl Groups

Abstract

Citation Formats

A zinc( ii ) complex of di(naphthylethynyl)azadipyrromethene with low synthetic complexity leads to OPV with high industrial accessibility journal, January 2019

A zinc( ii ) complex of di(naphthylethynyl)azadipyrromethene with low synthetic complexity leads to OPV with high industrial accessibility
journal, January 2019