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Title: An experimental and computational study of donor–linker–acceptor block copolymers for organic photovoltaics

Abstract

Block copolymers with donor and acceptor conjugated polymer blocks provide an approach to dictating the donor–accepter interfacial structure and understanding its relationship to charge separation and photovoltaic performance. In this paper, we report the preparation of a series of donor-linker-acceptor block copolymers with poly(3-hexylthiophene) (P3HT) donor blocks, poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(thiophen-5-yl)-2,1,3-benzothiadiazole]-2',2"-diyl) (PFTBT) acceptor blocks, and varying lengths of oligo-ethylene glycol (OEG) chains as the linkers. Morphological analysis shows that the linkers increase polymer crystallinity while a combination of optical and photovoltaic measurements shows that the insertion of a flexible spacer reduces fluorescence quenching and photovoltaic efficiencies of solution processed photovoltaic devices. Density functional theory (DFT) simulations indicate that the linking groups reduce both charge separation and recombination rates, and block copolymers with flexible linkers will likely rotate to assume a nonplanar orientation, resulting in a significant loss of overlap at the donor–linker–acceptor interface. Finally, this work provides a systematic study of the role of linker length on the photovoltaic performance of donor–linker–acceptor block copolymers and indicates that linkers should be designed to control both the electronic properties and relative orientations of conjugated polymers at the interface.

Authors:
 [1];  [2];  [3];  [3];  [4];  [2]; ORCiD logo [5]
  1. Rice Univ., Houston, TX (United States). Dept. of Chemical and Biomolecular Engineering
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences. Computational Sciences and Engineering
  3. Rochester Inst. of Technology, NY (United States). School of Chemistry and Materials Sciences
  4. Argonne National Lab. (ANL), Argonne, IL (United States). X-Ray Science Division
  5. Rice Univ., Houston, TX (United States). Dept. of Chemical and Biomolecular Engineering. Dept. of Materials Science and NanoEngineering
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Argonne National Lab. (ANL), Argonne, IL (United States); Rice Univ., Houston, TX (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF); Welch Foundation (United States)
OSTI Identifier:
1474655
Alternate Identifier(s):
OSTI ID: 1474418
Grant/Contract Number:  
AC05-00OR22725; AC02-06CH11357; DMR-1352099; C-1888
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Polymer Science. Part B, Polymer Physics
Additional Journal Information:
Journal Volume: 56; Journal Issue: 16; Journal ID: ISSN 0887-6266
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; acceptor; block copolymers; donor; linking groups; organic photovoltaics

Citation Formats

Hu, Zhiqi, Jakowski, Jacek, Zheng, Chenyu, Collison, Christopher J., Strzalka, Joseph, Sumpter, Bobby G., and Verduzco, Rafael. An experimental and computational study of donor–linker–acceptor block copolymers for organic photovoltaics. United States: N. p., 2018. Web. doi:10.1002/polb.24633.
Hu, Zhiqi, Jakowski, Jacek, Zheng, Chenyu, Collison, Christopher J., Strzalka, Joseph, Sumpter, Bobby G., & Verduzco, Rafael. An experimental and computational study of donor–linker–acceptor block copolymers for organic photovoltaics. United States. doi:10.1002/polb.24633.
Hu, Zhiqi, Jakowski, Jacek, Zheng, Chenyu, Collison, Christopher J., Strzalka, Joseph, Sumpter, Bobby G., and Verduzco, Rafael. Fri . "An experimental and computational study of donor–linker–acceptor block copolymers for organic photovoltaics". United States. doi:10.1002/polb.24633. https://www.osti.gov/servlets/purl/1474655.
@article{osti_1474655,
title = {An experimental and computational study of donor–linker–acceptor block copolymers for organic photovoltaics},
author = {Hu, Zhiqi and Jakowski, Jacek and Zheng, Chenyu and Collison, Christopher J. and Strzalka, Joseph and Sumpter, Bobby G. and Verduzco, Rafael},
abstractNote = {Block copolymers with donor and acceptor conjugated polymer blocks provide an approach to dictating the donor–accepter interfacial structure and understanding its relationship to charge separation and photovoltaic performance. In this paper, we report the preparation of a series of donor-linker-acceptor block copolymers with poly(3-hexylthiophene) (P3HT) donor blocks, poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(thiophen-5-yl)-2,1,3-benzothiadiazole]-2',2"-diyl) (PFTBT) acceptor blocks, and varying lengths of oligo-ethylene glycol (OEG) chains as the linkers. Morphological analysis shows that the linkers increase polymer crystallinity while a combination of optical and photovoltaic measurements shows that the insertion of a flexible spacer reduces fluorescence quenching and photovoltaic efficiencies of solution processed photovoltaic devices. Density functional theory (DFT) simulations indicate that the linking groups reduce both charge separation and recombination rates, and block copolymers with flexible linkers will likely rotate to assume a nonplanar orientation, resulting in a significant loss of overlap at the donor–linker–acceptor interface. Finally, this work provides a systematic study of the role of linker length on the photovoltaic performance of donor–linker–acceptor block copolymers and indicates that linkers should be designed to control both the electronic properties and relative orientations of conjugated polymers at the interface.},
doi = {10.1002/polb.24633},
journal = {Journal of Polymer Science. Part B, Polymer Physics},
number = 16,
volume = 56,
place = {United States},
year = {2018},
month = {8}
}

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