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Title: Charge delocalization characteristics of regioregular high mobility polymers

Abstract

Controlling the regioregularity among the structural units of narrow bandgap conjugated polymer backbones has led to improvements in optoelectronic properties, for example in the mobilities observed in field effect transistor devices. To investigate how the regioregularity affects quantities relevant to hole transport, regioregular and regiorandom oligomers representative of polymeric structures were studied using density functional theory. Several structural and electronic characteristics of the oligomers were compared, including chain planarity, cation spin density, excess charges on molecular units and internal reorganizational energy. The main difference between the regioregular and regiorandom oligomers is found to be the conjugated backbone planarity, while the reorganizational energies calculated are quite similar across the molecular family. Lastly, this work constitutes the first step on understanding the complex interplay of atomistic changes and an oligomer backbone structure toward modeling the charge transport properties.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1338770
Report Number(s):
LA-UR-16-21115
Journal ID: ISSN 2041-6520; CSHCBM
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 8; Journal Issue: 2; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Material Science

Citation Formats

Coughlin, J. E., Zhugayevych, A., Wang, M., Bazan, G. C., and Tretiak, S. Charge delocalization characteristics of regioregular high mobility polymers. United States: N. p., 2017. Web. doi:10.1039/C6SC01599A.
Coughlin, J. E., Zhugayevych, A., Wang, M., Bazan, G. C., & Tretiak, S. Charge delocalization characteristics of regioregular high mobility polymers. United States. doi:10.1039/C6SC01599A.
Coughlin, J. E., Zhugayevych, A., Wang, M., Bazan, G. C., and Tretiak, S. Sun . "Charge delocalization characteristics of regioregular high mobility polymers". United States. doi:10.1039/C6SC01599A. https://www.osti.gov/servlets/purl/1338770.
@article{osti_1338770,
title = {Charge delocalization characteristics of regioregular high mobility polymers},
author = {Coughlin, J. E. and Zhugayevych, A. and Wang, M. and Bazan, G. C. and Tretiak, S.},
abstractNote = {Controlling the regioregularity among the structural units of narrow bandgap conjugated polymer backbones has led to improvements in optoelectronic properties, for example in the mobilities observed in field effect transistor devices. To investigate how the regioregularity affects quantities relevant to hole transport, regioregular and regiorandom oligomers representative of polymeric structures were studied using density functional theory. Several structural and electronic characteristics of the oligomers were compared, including chain planarity, cation spin density, excess charges on molecular units and internal reorganizational energy. The main difference between the regioregular and regiorandom oligomers is found to be the conjugated backbone planarity, while the reorganizational energies calculated are quite similar across the molecular family. Lastly, this work constitutes the first step on understanding the complex interplay of atomistic changes and an oligomer backbone structure toward modeling the charge transport properties.},
doi = {10.1039/C6SC01599A},
journal = {Chemical Science},
number = 2,
volume = 8,
place = {United States},
year = {2017},
month = {1}
}

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Works referenced in this record:

The path to ubiquitous and low-cost organic electronic appliances on plastic
journal, April 2004


Organic Transistors in Optical Displays and Microelectronic Applications
journal, June 2010

  • Gelinck, Gerwin; Heremans, Paul; Nomoto, Kazumasa
  • Advanced Materials, Vol. 22, Issue 34
  • DOI: 10.1002/adma.200903559

A stable solution-processed polymer semiconductor with record high-mobility for printed transistors
journal, October 2012

  • Li, Jun; Zhao, Yan; Tan, Huei Shuan
  • Scientific Reports, Vol. 2, Issue 1
  • DOI: 10.1038/srep00754

Toward high-mobility organic field-effect transistors: Control of molecular packing and large-area fabrication of single-crystal-based devices
journal, January 2013

  • Li, Hanying; Giri, Gaurav; Tok, Jeffrey B. -H.
  • MRS Bulletin, Vol. 38, Issue 1
  • DOI: 10.1557/mrs.2012.309

Elastomeric Transistor Stamps: Reversible Probing of Charge Transport in Organic Crystals
journal, March 2004

  • Sundar, Vikram C.; Zaumseil, Jana; Podzorov, Vitaly
  • Science, Vol. 303, Issue 5664, p. 1644-1646
  • DOI: 10.1126/science.1094196

Quantifying the Energy Barriers and Elucidating the Charge Transport Mechanisms across Interspherulite Boundaries in Solution-Processed Organic Semiconductor Thin Films
journal, August 2015

  • Hailey, Anna K.; Wang, Szu-Ying; Chen, Yuanzhen
  • Advanced Functional Materials, Vol. 25, Issue 35
  • DOI: 10.1002/adfm.201501666

Materials and Applications for Large Area Electronics: Solution-Based Approaches
journal, January 2010

  • Arias, Ana Claudia; MacKenzie, J. Devin; McCulloch, Iain
  • Chemical Reviews, Vol. 110, Issue 1
  • DOI: 10.1021/cr900150b

High-Mobility Field-Effect Transistors Fabricated with Macroscopic Aligned Semiconducting Polymers
journal, February 2014


High Mobility Field Effect Transistors Based on Macroscopically Oriented Regioregular Copolymers
journal, February 2012

  • Tseng, Hsin-Rong; Ying, Lei; Hsu, Ben B. Y.
  • Nano Letters, Vol. 12, Issue 12
  • DOI: 10.1021/nl303612z

Regioregular Pyridal[2,1,3]thiadiazole π-Conjugated Copolymers
journal, November 2011

  • Ying, Lei; Hsu, Ben B. Y.; Zhan, Hongmei
  • Journal of the American Chemical Society, Vol. 133, Issue 46
  • DOI: 10.1021/ja207543g

Organic semiconductors: A theoretical characterization of the basic parameters governing charge transport
journal, April 2002

  • Bredas, J. L.; Calbert, J. P.; da Silva Filho, D. A.
  • Proceedings of the National Academy of Sciences, Vol. 99, Issue 9
  • DOI: 10.1073/pnas.092143399

Theoretical Description of Structural and Electronic Properties of Organic Photovoltaic Materials
journal, April 2015


A general relationship between disorder, aggregation and charge transport in conjugated polymers
journal, August 2013

  • Noriega, Rodrigo; Rivnay, Jonathan; Vandewal, Koen
  • Nature Materials, Vol. 12, Issue 11
  • DOI: 10.1038/nmat3722

Percolation, Tie-Molecules, and the Microstructural Determinants of Charge Transport in Semicrystalline Conjugated Polymers
journal, June 2015


Chain-Assisted Charge Transport in Semicrystalline Conjugated Polymers
journal, June 2016

  • Conchuir, B. O.; Tarantini, C.; McNeill, C. R.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 27
  • DOI: 10.1021/acs.jpcc.6b04714

Quantum Mechanical Continuum Solvation Models
journal, August 2005

  • Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto
  • Chemical Reviews, Vol. 105, Issue 8
  • DOI: 10.1021/cr9904009

Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model
journal, April 2003

  • Cossi, Maurizio; Rega, Nadia; Scalmani, Giovanni
  • Journal of Computational Chemistry, Vol. 24, Issue 6
  • DOI: 10.1002/jcc.10189

A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
journal, July 2004

  • Yanai, Takeshi; Tew, David P.; Handy, Nicholas C.
  • Chemical Physics Letters, Vol. 393, Issue 1-3, p. 51-57
  • DOI: 10.1016/j.cplett.2004.06.011

Semicrystalline D–A Copolymers with Different Chain Curvature for Applications in Polymer Optoelectronic Devices
journal, February 2014

  • Lee, Wonho; Kim, Gi-Hwan; Ko, Seo-Jin
  • Macromolecules, Vol. 47, Issue 5
  • DOI: 10.1021/ma402588m

Combining Electron-Neutral Building Blocks with Intramolecular “Conformational Locks” Affords Stable, High-Mobility P- and N-Channel Polymer Semiconductors
journal, June 2012

  • Huang, Hui; Chen, Zhihua; Ortiz, Rocio Ponce
  • Journal of the American Chemical Society, Vol. 134, Issue 26
  • DOI: 10.1021/ja303401s

Noncovalent Intramolecular Interactions in the Monomers and Oligomers of the Acceptor and Donor Type of Low Band Gap Conducting Polymers
journal, November 2007

  • Özen, Alimet Sema; Atilgan, Canan; Sonmez, Gursel
  • The Journal of Physical Chemistry C, Vol. 111, Issue 44
  • DOI: 10.1021/jp074380n

Controlling Conformations of Conjugated Polymers and Small Molecules: The Role of Nonbonding Interactions
journal, May 2013

  • Jackson, Nicholas E.; Savoie, Brett M.; Kohlstedt, Kevin L.
  • Journal of the American Chemical Society, Vol. 135, Issue 28
  • DOI: 10.1021/ja403667s

A Combined Experimental and Theoretical Study of Conformational Preferences of Molecular Semiconductors
journal, July 2014

  • Coughlin, Jessica E.; Zhugayevych, Andriy; Bakus, Ronald C.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 29
  • DOI: 10.1021/jp506172a

Impact of the Computational Method on the Geometric and Electronic Properties of Oligo(phenylene vinylene) Radical Cations
journal, November 2005

  • Geskin, V. M.; Grozema, F. C.; Siebbeles, L. D. A.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 43
  • DOI: 10.1021/jp0519417

Role of Geometric Distortion and Polarization in Localizing Electronic Excitations in Conjugated Polymers
journal, December 2012

  • Nayyar, Iffat H.; Batista, Enrique R.; Tretiak, Sergei
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 2
  • DOI: 10.1021/ct300837d

Effect of trans - and cis -isomeric defects on the localization of the charged excitations in π-conjugated organic polymers
journal, April 2013

  • Nayyar, Iffat H.; Batista, Enrique R.; Tretiak, Sergei
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 51, Issue 12
  • DOI: 10.1002/polb.23291

Localization of Electronic Excitations in Conjugated Polymers Studied by DFT
journal, February 2011

  • Nayyar, Iffat H.; Batista, Enrique R.; Tretiak, Sergei
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 6
  • DOI: 10.1021/jz101740w

Study of Hopping Transport in Long Oligothiophenes and Oligoselenophenes: Dependence of Reorganization Energy on Chain Length
journal, July 2008

  • Zade, Sanjio S.; Bendikov, Michael
  • Chemistry - A European Journal, Vol. 14, Issue 22
  • DOI: 10.1002/chem.200701182

Recent development of push–pull conjugated polymers for bulk-heterojunction photovoltaics: rational design and fine tailoring of molecular structures
journal, January 2012

  • Duan, Chunhui; Huang, Fei; Cao, Yong
  • Journal of Materials Chemistry, Vol. 22, Issue 21
  • DOI: 10.1039/c2jm30470h

Chemical and Electrochemical Electron-Transfer Theory
journal, October 1964


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    • Kang, So-Huei; Lee, Junghoon; Yoo, Dahyeon
    • Journal of Materials Chemistry C, Vol. 7, Issue 28
    • DOI: 10.1039/c9tc02414j