skip to main content
OSTI.GOV 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 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 dopantmore » 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)
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:
Journal Article: 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. https://doi.org/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. 2018. "Influence of dopant size and electron affinity on the electrical conductivity and thermoelectric properties of a series of conjugated polymers". United States. https://doi.org/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},
url = {https://www.osti.gov/biblio/1482091}, journal = {Journal of Materials Chemistry. A},
issn = {2050-7488},
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


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


Charge-transport model for conducting polymers
journal, November 2016


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


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


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


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


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


Mössbauer spectroscopy studies of selected conducting polypyrroles
journal, December 1985


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


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


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


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


Conjugated Polymer-Based Organic Solar Cells
journal, April 2007


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


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


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


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


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


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


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


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


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


Polaron Delocalization in Conjugated Polymer Films
journal, May 2016


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


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


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


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


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


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


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


Flexible organic semiconductor thin films
journal, January 2015


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


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


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


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


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


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


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


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


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


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


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


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


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


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


Conjugated Polymer-Based Organic Solar Cells
journal, July 2007


Works referencing / citing this record:

Dodecaborane‐Based Dopants Designed to Shield Anion Electrostatics Lead to Increased Carrier Mobility in a Doped Conjugated Polymer
journal, January 2019


Effect of Heteroatom and Doping on the Thermoelectric Properties of Poly(3-alkylchalcogenophenes)
journal, October 2018


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


Interfacial charge-transfer doping of metal halide perovskites for high performance photovoltaics
journal, January 2019


Designing π-conjugated polymer blends with improved thermoelectric power factors
journal, January 2019