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Title: Polythiophene thin films by surface-initiated polymerization: Mechanistic and structural studies

Abstract

The ability to control nanoscale morphology and molecular organization in organic semiconducting polymer thin films is an important prerequisite for enhancing the efficiency of organic thin-film devices including organic light-emitting and photovoltaic devices. The current “top-down” paradigm for making such devices is based on utilizing solution-based processing (e.g., spin-casting) of soluble semiconducting polymers. This approach typically provides only modest control over nanoscale molecular organization and polymer chain alignment. A promising alternative to using solutions of presynthesized semiconducting polymers pursues instead a “bottom-up” approach to prepare surface-grafted semiconducting polymer thin films by surface-initiated polymerization of small-molecule monomers. Herein, we describe the development of an efficient method to prepare polythiophene thin films utilizing surface-initiated Kumada catalyst transfer polymerization. In this study, we provided evidence that the surface-initiated polymerization occurs by the highly robust controlled (quasi-“living”) chain-growth mechanism. Further optimization of this method enabled reliable preparation of polythiophene thin films with thickness up to 100 nm. Extensive structural studies of the resulting thin films using X-ray and neutron scattering methods as well as ultraviolet photoemission spectroscopy revealed detailed information on molecular organization and the bulk morphology of the films, and enabled further optimization of the polymerization protocol. One of the remarkable findings wasmore » that surface-initiated polymerization delivers polymer thin films showing complex molecular organization, where polythiophene chains assemble into lateral crystalline domains of about 3.2 nm size, with individual polymer chains folded to form in-plane aligned and densely packed oligomeric segments (7-8 thiophene units per each segment) within each domain. Achieving such a complex mesoscale organization is virtually impossible with traditional methods relying on solution processing of presynthesized polymers. Another significant advantage of surface-confined polymer thin films is their remarkable stability toward organic solvents and other processing conditions. In addition to controlled bulk morphology, uniform molecular organization, and stability, a unique feature of the surface-initiated polymerization is that it can be used for the preparation of large-area uniformly nanopatterned polymer thin films. Lastly, this was demonstrated using a combination of particle lithography and surface-initiated polymerization. In general, surface-initiated polymerization is not limited to polythiophene but can be also expanded toward other classes of semiconducting polymers and copolymers.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3];  [4];  [1];  [1]
  1. Louisiana State Univ., Baton Rouge, LA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Indiana Univ., Bloomington, IN (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1339570
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 28; Journal Issue: 13; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Youm, Sang Gil, Hwang, Euiyong, Chavez, Carlos A., Li, Xin, Chatterjee, Sourav, Lusker, Kathie L., Lu, Lu, Strzalka, Joseph, Ankner, John F., Losovyj, Yaroslav, Garno, Jayne C., and Nesterov, Evgueni E. Polythiophene thin films by surface-initiated polymerization: Mechanistic and structural studies. United States: N. p., 2016. Web. doi:10.1021/acs.chemmater.6b01957.
Youm, Sang Gil, Hwang, Euiyong, Chavez, Carlos A., Li, Xin, Chatterjee, Sourav, Lusker, Kathie L., Lu, Lu, Strzalka, Joseph, Ankner, John F., Losovyj, Yaroslav, Garno, Jayne C., & Nesterov, Evgueni E. Polythiophene thin films by surface-initiated polymerization: Mechanistic and structural studies. United States. https://doi.org/10.1021/acs.chemmater.6b01957
Youm, Sang Gil, Hwang, Euiyong, Chavez, Carlos A., Li, Xin, Chatterjee, Sourav, Lusker, Kathie L., Lu, Lu, Strzalka, Joseph, Ankner, John F., Losovyj, Yaroslav, Garno, Jayne C., and Nesterov, Evgueni E. Wed . "Polythiophene thin films by surface-initiated polymerization: Mechanistic and structural studies". United States. https://doi.org/10.1021/acs.chemmater.6b01957. https://www.osti.gov/servlets/purl/1339570.
@article{osti_1339570,
title = {Polythiophene thin films by surface-initiated polymerization: Mechanistic and structural studies},
author = {Youm, Sang Gil and Hwang, Euiyong and Chavez, Carlos A. and Li, Xin and Chatterjee, Sourav and Lusker, Kathie L. and Lu, Lu and Strzalka, Joseph and Ankner, John F. and Losovyj, Yaroslav and Garno, Jayne C. and Nesterov, Evgueni E.},
abstractNote = {The ability to control nanoscale morphology and molecular organization in organic semiconducting polymer thin films is an important prerequisite for enhancing the efficiency of organic thin-film devices including organic light-emitting and photovoltaic devices. The current “top-down” paradigm for making such devices is based on utilizing solution-based processing (e.g., spin-casting) of soluble semiconducting polymers. This approach typically provides only modest control over nanoscale molecular organization and polymer chain alignment. A promising alternative to using solutions of presynthesized semiconducting polymers pursues instead a “bottom-up” approach to prepare surface-grafted semiconducting polymer thin films by surface-initiated polymerization of small-molecule monomers. Herein, we describe the development of an efficient method to prepare polythiophene thin films utilizing surface-initiated Kumada catalyst transfer polymerization. In this study, we provided evidence that the surface-initiated polymerization occurs by the highly robust controlled (quasi-“living”) chain-growth mechanism. Further optimization of this method enabled reliable preparation of polythiophene thin films with thickness up to 100 nm. Extensive structural studies of the resulting thin films using X-ray and neutron scattering methods as well as ultraviolet photoemission spectroscopy revealed detailed information on molecular organization and the bulk morphology of the films, and enabled further optimization of the polymerization protocol. One of the remarkable findings was that surface-initiated polymerization delivers polymer thin films showing complex molecular organization, where polythiophene chains assemble into lateral crystalline domains of about 3.2 nm size, with individual polymer chains folded to form in-plane aligned and densely packed oligomeric segments (7-8 thiophene units per each segment) within each domain. Achieving such a complex mesoscale organization is virtually impossible with traditional methods relying on solution processing of presynthesized polymers. Another significant advantage of surface-confined polymer thin films is their remarkable stability toward organic solvents and other processing conditions. In addition to controlled bulk morphology, uniform molecular organization, and stability, a unique feature of the surface-initiated polymerization is that it can be used for the preparation of large-area uniformly nanopatterned polymer thin films. Lastly, this was demonstrated using a combination of particle lithography and surface-initiated polymerization. In general, surface-initiated polymerization is not limited to polythiophene but can be also expanded toward other classes of semiconducting polymers and copolymers.},
doi = {10.1021/acs.chemmater.6b01957},
journal = {Chemistry of Materials},
number = 13,
volume = 28,
place = {United States},
year = {Wed Jun 15 00:00:00 EDT 2016},
month = {Wed Jun 15 00:00:00 EDT 2016}
}

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The Effect of Solvent Additives on Morphology and Excited-State Dynamics in PCPDTBT:PCBM Photovoltaic Blends
journal, June 2012

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Electrochemical, Magnetic, and Electrical Properties of α,ω-Capped Sexithiophene Films. 1. Neutral−Polaron and Polaron−Bipolaron Conductivities
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Detection of Explosives with a Fluorescent Nanofibril Film
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Organic Thin Film Transistors for Large Area Electronics
journal, January 2002


Works referencing / citing this record:

Electrochromic and electrochemical properties of copolymer films based on EDOT and phenylthiophene derivatives
journal, January 2019

  • Lacerda, Glenda Ribeiro de Barros Silveira; Calado, Claudinei Rezende; Calado, Hállen Daniel Rezende
  • Journal of Solid State Electrochemistry, Vol. 23, Issue 3
  • DOI: 10.1007/s10008-018-04185-2

Surface Coupling of Octaethylporphyrin with Silicon Tetrachloride
journal, February 2019

  • Chambers, Phillip C.; Kuruppu Arachchige, Neepa M. K.; Taylor, Ashley M.
  • ACS Omega, Vol. 4, Issue 2
  • DOI: 10.1021/acsomega.8b03204

The Structure and Characterization of 3,4,5-Triiodo-2-Methylthiophene: An Unexpected Iodination Product of 2-Methylthiophene
journal, January 2019

  • Patel, Dinesh G.; Sylvester, Eric D.; LeValley, Nicholas R.
  • Journal of Chemical Crystallography, Vol. 49, Issue 3
  • DOI: 10.1007/s10870-019-00770-z

Power Factor of One Molecule Thick Films and Length Dependence
journal, December 2019