skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Influence of dopant size and electron affinity on the electrical conductivity and thermoelectric properties of a series of conjugated polymers

Abstract

Here, chemical doping is widely used to manipulate the electrical and thermoelectric properties of organic semiconductors, yet intelligent design of polymer–dopant systems remains elusive. It is challenging to predict the electrical and thermoelectric properties of doped organic semiconductors due to the large number of variables impacting these properties, including film morphology, dopant and polymer energetics, dopant size, and degree of polaron delocalization. Herein, a series of dopants with varying sizes and electron affinities (EAs) are combined with polymers of differing ionization energies (IEs) to investigate how the difference between polymer IE and dopant EA influences the doping efficiency and electrical conductivity, and how the dopant size influences the thermoelectric properties. Our experiments demonstrate that at low doping levels the doping efficiency strongly depends on the difference between the polymer IE and dopant EA; the effectiveness of doping on increasing electrical conductivity drastically decreases at high loadings for the molybdenum dithiolene complexes, while FeCl 3 remains effective at high loadings; and the large molybdenum complexes lead to more delocalized polarons as compared to FeCl 3. To take advantage of the complementary doping characteristics of the molybdenum complexes and FeCl 3, both dopants are employed simultaneously to reach high power factors atmore » relatively low dopant concentrations.« less

Authors:
 [1];  [2];  [1];  [3];  [1];  [4];  [1];  [5]; ORCiD logo [1]; ORCiD logo [3];  [2]; ORCiD logo [1]
  1. Univ. of Kentucky, Lexington, KY (United States)
  2. Georgia Inst. of Technology, Atlanta, GA (United States)
  3. Purdue Univ., West Lafayette, IN (United States)
  4. Brookhaven National Lab. (BNL), Shirley, NY (United States)
  5. South China Normal Univ. (People's Republic of China)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1482091
Alternate Identifier(s):
OSTI ID: 1464569
Report Number(s):
BNL-209436-2018-JAAM
Journal ID: ISSN 2050-7488; JMCAET
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 6; Journal Issue: 34; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Liang, Zhiming, Zhang, Yadong, Souri, Maryam, Luo, Xuyi, Boehm, Alex M., Li, Ruipeng, Zhang, Yan, Wang, Tairan, Kim, Doo -Young, Mei, Jianguo, Marder, Seth R., and Graham, Kenneth R. Influence of dopant size and electron affinity on the electrical conductivity and thermoelectric properties of a series of conjugated polymers. United States: N. p., 2018. Web. doi:10.1039/C8TA05922E.
Liang, Zhiming, Zhang, Yadong, Souri, Maryam, Luo, Xuyi, Boehm, Alex M., Li, Ruipeng, Zhang, Yan, Wang, Tairan, Kim, Doo -Young, Mei, Jianguo, Marder, Seth R., & Graham, Kenneth R. Influence of dopant size and electron affinity on the electrical conductivity and thermoelectric properties of a series of conjugated polymers. United States. doi:10.1039/C8TA05922E.
Liang, Zhiming, Zhang, Yadong, Souri, Maryam, Luo, Xuyi, Boehm, Alex M., Li, Ruipeng, Zhang, Yan, Wang, Tairan, Kim, Doo -Young, Mei, Jianguo, Marder, Seth R., and Graham, Kenneth R. Mon . "Influence of dopant size and electron affinity on the electrical conductivity and thermoelectric properties of a series of conjugated polymers". United States. doi:10.1039/C8TA05922E. https://www.osti.gov/servlets/purl/1482091.
@article{osti_1482091,
title = {Influence of dopant size and electron affinity on the electrical conductivity and thermoelectric properties of a series of conjugated polymers},
author = {Liang, Zhiming and Zhang, Yadong and Souri, Maryam and Luo, Xuyi and Boehm, Alex M. and Li, Ruipeng and Zhang, Yan and Wang, Tairan and Kim, Doo -Young and Mei, Jianguo and Marder, Seth R. and Graham, Kenneth R.},
abstractNote = {Here, chemical doping is widely used to manipulate the electrical and thermoelectric properties of organic semiconductors, yet intelligent design of polymer–dopant systems remains elusive. It is challenging to predict the electrical and thermoelectric properties of doped organic semiconductors due to the large number of variables impacting these properties, including film morphology, dopant and polymer energetics, dopant size, and degree of polaron delocalization. Herein, a series of dopants with varying sizes and electron affinities (EAs) are combined with polymers of differing ionization energies (IEs) to investigate how the difference between polymer IE and dopant EA influences the doping efficiency and electrical conductivity, and how the dopant size influences the thermoelectric properties. Our experiments demonstrate that at low doping levels the doping efficiency strongly depends on the difference between the polymer IE and dopant EA; the effectiveness of doping on increasing electrical conductivity drastically decreases at high loadings for the molybdenum dithiolene complexes, while FeCl3 remains effective at high loadings; and the large molybdenum complexes lead to more delocalized polarons as compared to FeCl3. To take advantage of the complementary doping characteristics of the molybdenum complexes and FeCl3, both dopants are employed simultaneously to reach high power factors at relatively low dopant concentrations.},
doi = {10.1039/C8TA05922E},
journal = {Journal of Materials Chemistry. A},
number = 34,
volume = 6,
place = {United States},
year = {2018},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

A High Mobility P-Type DPP-Thieno[3,2-b]thiophene Copolymer for Organic Thin-Film Transistors
journal, August 2010

  • Li, Yuning; Singh, Samarendra P.; Sonar, Prashant
  • Advanced Materials, Vol. 22, Issue 43
  • DOI: 10.1002/adma.201002313

Increased power factors of organic–inorganic nanocomposite thermoelectric materials and the role of energy filtering
journal, January 2017

  • Liang, Zhiming; Boland, Mathias J.; Butrouna, Kamal
  • Journal of Materials Chemistry A, Vol. 5, Issue 30
  • DOI: 10.1039/C7TA02307C

Charge-transport model for conducting polymers
journal, November 2016

  • Kang, Stephen Dongmin; Snyder, G. Jeffrey
  • Nature Materials, Vol. 16, Issue 2
  • DOI: 10.1038/nmat4784

Raman Spectroscopic Studies of Regioregular Poly(3-alkylthiophenes)
journal, January 1996

  • Louarn, Guy; Trznadel, Miroslaw; Buisson, J. P.
  • The Journal of Physical Chemistry, Vol. 100, Issue 30
  • DOI: 10.1021/jp960104p

Localized Charge Transfer in a Molecularly Doped Conducting Polymer
journal, September 2007

  • Aziz, E. F.; Vollmer, A.; Eisebitt, S.
  • Advanced Materials, Vol. 19, Issue 20, p. 3257-3260
  • DOI: 10.1002/adma.200700926

Organic thermoelectric materials for energy harvesting and temperature control
journal, August 2016


Flexible light-emitting diodes made from soluble conducting polymers
journal, June 1992

  • Gustafsson, G.; Cao, Y.; Treacy, G. M.
  • Nature, Vol. 357, Issue 6378
  • DOI: 10.1038/357477a0

Side Chain Engineering in Solution-Processable Conjugated Polymers
journal, September 2013

  • Mei, Jianguo; Bao, Zhenan
  • Chemistry of Materials, Vol. 26, Issue 1
  • DOI: 10.1021/cm4020805

Electronic and Vibrational Spectra of Positive Polarons and Bipolarons in Regioregular Poly(3-hexylthiophene) Doped with Ferric Chloride
journal, March 2015

  • Yamamoto, Jun; Furukawa, Yukio
  • The Journal of Physical Chemistry B, Vol. 119, Issue 13
  • DOI: 10.1021/jp512654b

Mössbauer spectroscopy studies of selected conducting polypyrroles
journal, December 1985

  • Proń, A.; Kucharski, Z.; Budrowski, C.
  • The Journal of Chemical Physics, Vol. 83, Issue 11
  • DOI: 10.1063/1.449624

Controlling Electrical Properties of Conjugated Polymers via a Solution-Based p-Type Doping
journal, September 2008

  • Yim, Keng-Hoong; Whiting, Gregory L.; Murphy, Craig E.
  • Advanced Materials, Vol. 20, Issue 17, p. 3319-3324
  • DOI: 10.1002/adma.200800735

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

Sequential Doping Reveals the Importance of Amorphous Chain Rigidity in Charge Transport of Semi-Crystalline Polymers
journal, September 2017

  • Chew, Annabel R.; Ghosh, Raja; Shang, Zhengrong
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 20
  • DOI: 10.1021/acs.jpclett.7b01989

Observation of Anderson Localization in an Electron Gas
journal, May 1969


Conjugated Polymer-Based Organic Solar Cells
journal, April 2007

  • Günes, Serap; Neugebauer, Helmut; Sariciftci, Niyazi Serdar
  • Chemical Reviews, Vol. 107, Issue 4, p. 1324-1338
  • DOI: 10.1021/cr050149z

Molecular Electrical Doping of Organic Semiconductors: Fundamental Mechanisms and Emerging Dopant Design Rules
journal, February 2016


Doping of Fullerenes via Anion-Induced Electron Transfer and Its Implication for Surfactant Facilitated High Performance Polymer Solar Cells
journal, June 2013

  • Li, Chang-Zhi; Chueh, Chu-Chen; Ding, Feizhi
  • Advanced Materials, Vol. 25, Issue 32
  • DOI: 10.1002/adma.201300580

Probing the energy levels in hole-doped molecular semiconductors
journal, January 2015

  • Winkler, Stefanie; Amsalem, Patrick; Frisch, Johannes
  • Materials Horizons, Vol. 2, Issue 4
  • DOI: 10.1039/C5MH00023H

Direct Observation of Doping Sites in Temperature-Controlled, p-Doped P3HT Thin Films by Conducting Atomic Force Microscopy
journal, July 2014


Mechanism of Dedoping Processes of Conducting Poly(3-alkylthiophenes)
journal, August 2005

  • Koizumi, Hitoshi; Dougauchi, Hiroshi; Ichikawa, Tsuneki
  • The Journal of Physical Chemistry B, Vol. 109, Issue 32
  • DOI: 10.1021/jp051989k

Enhanced Charge-Carrier Injection and Collection Via Lamination of Doped Polymer Layers p-Doped with a Solution-Processible Molybdenum Complex
journal, December 2013

  • Dai, An; Zhou, Yinhua; Shu, Andrew L.
  • Advanced Functional Materials, Vol. 24, Issue 15
  • DOI: 10.1002/adfm.201303232

An iodine-doped polymer light-emitting diode
journal, October 1997

  • Huang, F.; MacDiarmid, A. G.; Hsieh, B. R.
  • Applied Physics Letters, Vol. 71, Issue 17
  • DOI: 10.1063/1.120078

A general expression for the thermoelectric power
journal, November 1971


Optimization of the thermoelectric figure of merit in the conducting polymer poly(3,4-ethylenedioxythiophene)
journal, May 2011

  • Bubnova, Olga; Khan, Zia Ullah; Malti, Abdellah
  • Nature Materials, Vol. 10, Issue 6, p. 429-433
  • DOI: 10.1038/nmat3012

Comparison of solution-mixed and sequentially processed P3HT:F4TCNQ films: effect of doping-induced aggregation on film morphology
journal, January 2016

  • Jacobs, Ian E.; Aasen, Erik W.; Oliveira, Julia L.
  • J. Mater. Chem. C, Vol. 4, Issue 16
  • DOI: 10.1039/C5TC04207K

Electronic Conduction in Polymers. II. The Electrochemical Reduction of Polypyrrole at Controlled Potential
journal, January 1963

  • Bolto, Ba; Weiss, De
  • Australian Journal of Chemistry, Vol. 16, Issue 6
  • DOI: 10.1071/CH9631076

Charge-transfer crystallites as molecular electrical dopants
journal, October 2015

  • Méndez, Henry; Heimel, Georg; Winkler, Stefanie
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9560

Solubility-Limited Extrinsic n-Type Doping of a High Electron Mobility Polymer for Thermoelectric Applications
journal, January 2014

  • Schlitz, Ruth A.; Brunetti, Fulvio G.; Glaudell, Anne M.
  • Advanced Materials, Vol. 26, Issue 18
  • DOI: 10.1002/adma.201304866

Polaron Delocalization in Conjugated Polymer Films
journal, May 2016

  • Ghosh, Raja; Pochas, Christopher M.; Spano, Frank C.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 21
  • DOI: 10.1021/acs.jpcc.6b02917

Impact of the Doping Method on Conductivity and Thermopower in Semiconducting Polythiophenes
journal, October 2014

  • Glaudell, Anne M.; Cochran, Justin E.; Patel, Shrayesh N.
  • Advanced Energy Materials, Vol. 5, Issue 4
  • DOI: 10.1002/aenm.201401072

A Molybdenum Dithiolene Complex as p -Dopant for Hole-Transport Materials: A Multitechnique Experimental and Theoretical Investigation
journal, January 2010

  • Qi, Yabing; Sajoto, Tissa; Kröger, Michael
  • Chemistry of Materials, Vol. 22, Issue 2
  • DOI: 10.1021/cm9031623

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


The Effects of Crystallinity on Charge Transport and the Structure of Sequentially Processed F 4 TCNQ-Doped Conjugated Polymer Films
journal, September 2017

  • Scholes, D. Tyler; Yee, Patrick Y.; Lindemuth, Jeffrey R.
  • Advanced Functional Materials, Vol. 27, Issue 44
  • DOI: 10.1002/adfm.201702654

Fermi level shift and doping efficiency in p -doped small molecule organic semiconductors: A photoelectron spectroscopy and theoretical study
journal, July 2012


Complementary Semiconducting Polymer Blends: The Influence of Conjugation-Break Spacer Length in Matrix Polymers
journal, March 2016


Solution-processed organic tandem solar cells with power conversion efficiencies >12%
journal, December 2016


Hall-Effect Measurements Probing the Degree of Charge-Carrier Delocalization in Solution-Processed Crystalline Molecular Semiconductors
journal, August 2011


Organic electrochemical transistors
journal, January 2018


Doping of organic semiconductors
journal, December 2012


Enhanced n-Doping Efficiency of a Naphthalenediimide-Based Copolymer through Polar Side Chains for Organic Thermoelectrics
journal, January 2018


Microstructural Characterization and Charge Transport in Thin Films of Conjugated Polymers
journal, July 2010

  • Salleo, Alberto; Kline, R. Joseph; DeLongchamp, Dean M.
  • Advanced Materials, Vol. 22, Issue 34
  • DOI: 10.1002/adma.200903712

Enhancing doping efficiency by improving host-dopant miscibility for fullerene-based n-type thermoelectrics
journal, January 2017

  • Qiu, Li; Liu, Jian; Alessandri, Riccardo
  • J. Mater. Chem. A, Vol. 5, Issue 40
  • DOI: 10.1039/C7TA06609K

Importance of the Donor:Fullerene Intermolecular Arrangement for High-Efficiency Organic Photovoltaics
journal, June 2014

  • Graham, Kenneth R.; Cabanetos, Clement; Jahnke, Justin P.
  • Journal of the American Chemical Society, Vol. 136, Issue 27
  • DOI: 10.1021/ja502985g

Flexible organic semiconductor thin films
journal, January 2015

  • Gupta, Shiv K.; Jha, Purushottam; Singh, Ajay
  • Journal of Materials Chemistry C, Vol. 3, Issue 33
  • DOI: 10.1039/C5TC00901D

Highly Efficient Organic Devices Based on Electrically Doped Transport Layers
journal, April 2007

  • Walzer, K.; Maennig, B.; Pfeiffer, M.
  • Chemical Reviews, Vol. 107, Issue 4
  • DOI: 10.1021/cr050156n

Influence of crystallinity on the thermoelectric power factor of P3HT vapour-doped with F4TCNQ
journal, January 2018

  • Hynynen, Jonna; Kiefer, David; Müller, Christian
  • RSC Advances, Vol. 8, Issue 3
  • DOI: 10.1039/C7RA11912G

A new photon source for ultraviolet photoelectron spectroscopy of organic and other damage-prone materials
journal, February 2017


Synthesis of electrically conducting organic polymers: halogen derivatives of polyacetylene, (CH) x
journal, January 1977

  • Shirakawa, Hideki; Louis, Edwin J.; MacDiarmid, Alan G.
  • Journal of the Chemical Society, Chemical Communications, Issue 16
  • DOI: 10.1039/c39770000578

Electrochemical Considerations for Determining Absolute Frontier Orbital Energy Levels of Conjugated Polymers for Solar Cell Applications
journal, April 2011

  • Cardona, Claudia M.; Li, Wei; Kaifer, Angel E.
  • Advanced Materials, Vol. 23, Issue 20
  • DOI: 10.1002/adma.201004554

Complementary Semiconducting Polymer Blends for Efficient Charge Transport
journal, October 2015


Doping of Organic Semiconductors: Impact of Dopant Strength and Electronic Coupling
journal, June 2013

  • Méndez, Henry; Heimel, Georg; Opitz, Andreas
  • Angewandte Chemie International Edition, Vol. 52, Issue 30
  • DOI: 10.1002/anie.201302396

Morphology controls the thermoelectric power factor of a doped semiconducting polymer
journal, June 2017

  • Patel, Shrayesh N.; Glaudell, Anne M.; Peterson, Kelly A.
  • Science Advances, Vol. 3, Issue 6
  • DOI: 10.1126/sciadv.1700434

Synthetic and Electron Spin Resonance Studies of Six-Coordinate Complexes Related by Electron-Transfer Reactions
journal, July 1964

  • Davison, A.; Edelstein, N.; Holm, R. H.
  • Journal of the American Chemical Society, Vol. 86, Issue 14
  • DOI: 10.1021/ja01068a010

Direct determination of the electronic structure of the poly(3-hexylthiophene):phenyl-[6,6]-C61 butyric acid methyl ester blend
journal, November 2010


Comprehensive picture of p -type doping of P3HT with the molecular acceptor F 4 TCNQ
journal, March 2013


Organic Thermoelectric Materials: Emerging Green Energy Materials Converting Heat to Electricity Directly and Efficiently
journal, March 2014


Near-ultraviolet inverse photoemission spectroscopy using ultra-low energy electrons
journal, June 2012


Use of a High Electron-Affinity Molybdenum Dithiolene Complex to p-Dope Hole-Transport Layers
journal, September 2009

  • Qi, Yabing; Sajoto, Tissa; Barlow, Stephen
  • Journal of the American Chemical Society, Vol. 131, Issue 35
  • DOI: 10.1021/ja904939g

Confined and delocalized polarons in π -conjugated oligomers and polymers: A study of the effective conjugation length
journal, June 2004


Semiconducting π-Conjugated Systems in Field-Effect Transistors: A Material Odyssey of Organic Electronics
journal, November 2011

  • Wang, Chengliang; Dong, Huanli; Hu, Wenping
  • Chemical Reviews, Vol. 112, Issue 4
  • DOI: 10.1021/cr100380z

Electronic Conduction in Polymers. III. Electronic Properties of Polypyrrole
journal, January 1963

  • Bolto, Ba; McNeill, R.; Weiss, De
  • Australian Journal of Chemistry, Vol. 16, Issue 6
  • DOI: 10.1071/CH9631090

High Conductivity in Molecularly p-Doped Diketopyrrolopyrrole-Based Polymer: The Impact of a High Dopant Strength and Good Structural Order
journal, May 2016

  • Karpov, Yevhen; Erdmann, Tim; Raguzin, Ivan
  • Advanced Materials, Vol. 28, Issue 28
  • DOI: 10.1002/adma.201506295

Effective Approaches to Improve the Electrical Conductivity of PEDOT:PSS: A Review
journal, March 2015

  • Shi, Hui; Liu, Congcong; Jiang, Qinglin
  • Advanced Electronic Materials, Vol. 1, Issue 4
  • DOI: 10.1002/aelm.201500017

Integrated Materials Design of Organic Semiconductors for Field-Effect Transistors
journal, April 2013

  • Mei, Jianguo; Diao, Ying; Appleton, Anthony L.
  • Journal of the American Chemical Society, Vol. 135, Issue 18
  • DOI: 10.1021/ja400881n

The chemical and structural origin of efficient p-type doping in P3HT
journal, May 2013


    Works referencing / citing this record:

    Ultrafast transient absorption spectroscopy of doped P3HT films: distinguishing free and trapped polarons
    journal, January 2019

    • Voss, Matthew G.; Scholes, D. Tyler; Challa, J. Reddy
    • Faraday Discussions, Vol. 216
    • DOI: 10.1039/c8fd00210j

    Ultrafast transient absorption spectroscopy of doped P3HT films: distinguishing free and trapped polarons
    journal, January 2019

    • Voss, Matthew G.; Scholes, D. Tyler; Challa, J. Reddy
    • Faraday Discussions, Vol. 216
    • DOI: 10.1039/c8fd00210j