Introducing Solubility Control for Improved Organic P-Type Dopants
Abstract
To overcome the poor solubility of the widely used p-type dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), we have synthesized a series of structure-modified, organic p-type dopants to include alkyl ester groups designed to enable solubility and miscibility control. UV–vis–NIR and cyclic voltammetry measurements show increased solubility of mono- and diester substituted dopants with only modest changes to acceptor strength. Using absorption spectroscopy, photoluminescence, and in-plane conductivity measurements, we demonstrate that the new dopants can successfully p-type dope poly(3-hexylthiophene- 2,5-diyl) (P3HT). Monoester substituted dopants are characterized by only slightly reduced electron affinity relative to F4TCNQ, but greater doping effectiveness due to increased miscibility with P3HT. Diester substituted dopants undergo a dimerization reaction before assuming their doped states, which may help anchor dopants into position post deposition, thus decreasing the negative effect of dopant drift and diffusion. Here, we conclude that increased dopant solubility/miscibility increases the overall effectiveness of doping in solution-cast polymer films and that ester modification is a practical approach to achieving solubility/miscibility control in TCNQ-type dopants.
- Publication Date:
- Research Org.:
- Univ. of California, Davis, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1924290
- Grant/Contract Number:
- SC0010419
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 27; Journal Issue: 16; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Doping; Electrical conductivity; Impurities; Organic compounds; Organic polymers
Citation Formats
Li, Jun, Zhang, Guangwu, Holm, Daniella M., Jacobs, Ian E., Yin, Bin, Stroeve, Pieter, Mascal, Mark, and Moulé, Adam J. Introducing Solubility Control for Improved Organic P-Type Dopants. United States: N. p., 2015.
Web. doi:10.1021/acs.chemmater.5b02340.
Li, Jun, Zhang, Guangwu, Holm, Daniella M., Jacobs, Ian E., Yin, Bin, Stroeve, Pieter, Mascal, Mark, & Moulé, Adam J. Introducing Solubility Control for Improved Organic P-Type Dopants. United States. https://doi.org/10.1021/acs.chemmater.5b02340
Li, Jun, Zhang, Guangwu, Holm, Daniella M., Jacobs, Ian E., Yin, Bin, Stroeve, Pieter, Mascal, Mark, and Moulé, Adam J. Fri .
"Introducing Solubility Control for Improved Organic P-Type Dopants". United States. https://doi.org/10.1021/acs.chemmater.5b02340. https://www.osti.gov/servlets/purl/1924290.
@article{osti_1924290,
title = {Introducing Solubility Control for Improved Organic P-Type Dopants},
author = {Li, Jun and Zhang, Guangwu and Holm, Daniella M. and Jacobs, Ian E. and Yin, Bin and Stroeve, Pieter and Mascal, Mark and Moulé, Adam J.},
abstractNote = {To overcome the poor solubility of the widely used p-type dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), we have synthesized a series of structure-modified, organic p-type dopants to include alkyl ester groups designed to enable solubility and miscibility control. UV–vis–NIR and cyclic voltammetry measurements show increased solubility of mono- and diester substituted dopants with only modest changes to acceptor strength. Using absorption spectroscopy, photoluminescence, and in-plane conductivity measurements, we demonstrate that the new dopants can successfully p-type dope poly(3-hexylthiophene- 2,5-diyl) (P3HT). Monoester substituted dopants are characterized by only slightly reduced electron affinity relative to F4TCNQ, but greater doping effectiveness due to increased miscibility with P3HT. Diester substituted dopants undergo a dimerization reaction before assuming their doped states, which may help anchor dopants into position post deposition, thus decreasing the negative effect of dopant drift and diffusion. Here, we conclude that increased dopant solubility/miscibility increases the overall effectiveness of doping in solution-cast polymer films and that ester modification is a practical approach to achieving solubility/miscibility control in TCNQ-type dopants.},
doi = {10.1021/acs.chemmater.5b02340},
journal = {Chemistry of Materials},
number = 16,
volume = 27,
place = {United States},
year = {Fri Jul 24 00:00:00 EDT 2015},
month = {Fri Jul 24 00:00:00 EDT 2015}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
The path to ubiquitous and low-cost organic electronic appliances on plastic
journal, April 2004
- Forrest, Stephen R.
- Nature, Vol. 428, Issue 6986, p. 911-918
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
Synthesis of Conjugated Polymers for Organic Solar Cell Applications
journal, November 2009
- Cheng, Yen-Ju; Yang, Sheng-Hsiung; Hsu, Chain-Shu
- Chemical Reviews, Vol. 109, Issue 11
Doping of organic semiconductors
journal, December 2012
- Lüssem, B.; Riede, M.; Leo, K.
- physica status solidi (a), Vol. 210, Issue 1
Enhanced Hole Injection into Amorphous Hole-Transport Layers of Organic Light-Emitting Diodes Using Controlled p-Type Doping
journal, August 2001
- Zhou, X.; Blochwitz, J.; Pfeiffer, M.
- Advanced Functional Materials, Vol. 11, Issue 4
White organic light-emitting diodes: Status and perspective
journal, July 2013
- Reineke, Sebastian; Thomschke, Michael; Lüssem, Björn
- Reviews of Modern Physics, Vol. 85, Issue 3
Doping effects for organic photovoltaic cells based on small-molecular-weight semiconductors
journal, June 2009
- Taima, Tetsuya; Sakai, Jun; Yamanari, Toshihiro
- Solar Energy Materials and Solar Cells, Vol. 93, Issue 6-7
Molecular Semiconductors in Organic Photovoltaic Cells
journal, November 2010
- Hains, Alexander W.; Liang, Ziqi; Woodhouse, Michael A.
- Chemical Reviews, Vol. 110, Issue 11
High-Performance Organic Field-Effect Transistors
journal, April 2009
- Braga, Daniele; Horowitz, Gilles
- Advanced Materials, Vol. 21, Issue 14-15
Moderate doping leads to high performance of semiconductor/insulator polymer blend transistors
journal, March 2013
- Lu, Guanghao; Blakesley, James; Himmelberger, Scott
- Nature Communications, Vol. 4, Issue 1
The effects of solvents on the morphology and sheet resistance in poly(3,4-ethylenedioxythiophene)–polystyrenesulfonic acid (PEDOT–PSS) films
journal, August 2003
- Jönsson, S. K. M.; Birgerson, J.; Crispin, X.
- Synthetic Metals, Vol. 139, Issue 1
PEDOT-Type Materials in Organic Solar Cells
book, June 2008
- Eischner, Andreas; Kirchmeyer, Stephan
- Organic Photovoltaics
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
Polarons and bipolarons in doped polythiophene: A theoretical investigation
journal, August 1987
- Brédas, J. L.; Wudl, F.; Heeger, A. J.
- Solid State Communications, Vol. 63, Issue 7
Bipolarons in poly(3-methylthiophene): Spectroscopic, magnetic, and electrochemical measurements
journal, November 1987
- Colaneri, N.; Nowak, M.; Spiegel, D.
- Physical Review B, Vol. 36, Issue 15
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
Charge Transfer Absorption for π-Conjugated Polymers and Oligomers Mixed with Electron Acceptors
journal, May 2007
- Panda, Priyadarshi; Veldman, Dirk; Sweelssen, Jörgen
- The Journal of Physical Chemistry B, Vol. 111, Issue 19
Charge Transfer in Molecular Complexes with 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 -TCNQ): A Density Functional Theory Study
journal, December 2011
- Zhu, Lingyun; Kim, Eung-Gun; Yi, Yuanping
- Chemistry of Materials, Vol. 23, Issue 23
The effect of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane charge transfer dopants on the conformation and aggregation of poly(3-hexylthiophene)
journal, January 2013
- Gao, Jian; Roehling, John D.; Li, Yongle
- Journal of Materials Chemistry C, Vol. 1, Issue 36
Electrical Properties of Organic Solids. II. Effects of Added Electron Acceptor on Metal‐Free Phthalocyanine
journal, April 1960
- Kearns, David R.; Tollin, Gordon; Calvin, Melvin
- The Journal of Chemical Physics, Vol. 32, Issue 4
A comparison of experimental determinations of electron affinities of pi charge transfer complex acceptors
journal, October 1975
- Chen, E. C. M.; Wentworth, W. E.
- The Journal of Chemical Physics, Vol. 63, Issue 8
Negative ion properties of fluoranil, chloranil, and bromanil: Electron affinities
journal, January 1978
- Cooper, C. D.; Frey, W. F.; Compton, R. N.
- The Journal of Chemical Physics, Vol. 69, Issue 6
Electron transfer in a new highly conducting donor-acceptor complex
journal, February 1973
- Ferraris, John.; Cowan, D. O.; Walatka, V.
- Journal of the American Chemical Society, Vol. 95, Issue 3
Negative ion properties of tetracyanoquinodimethan: Electron affinity and compound states
journal, May 1977
- Compton, R. N.; Cooper, C. D.
- The Journal of Chemical Physics, Vol. 66, Issue 10
Molecular material‐based junctions: Formation of a Schottky contact with metallophthalocyanine thin films doped by the cosublimation method
journal, October 1986
- Maitrot, M.; Guillaud, G.; Boudjema, B.
- Journal of Applied Physics, Vol. 60, Issue 7
Structural characterization and electrical conductivity of poly(phenylethynyl) copper doped with iodine and 2,3-dichloro-5,6-dicyano-p-benzoquinone
journal, March 1989
- Krikor, H.; Nagels, P.
- Synthetic Metals, Vol. 29, Issue 2-3
Charge-transfer doping of poly(3-alkyl-2,2′-bithiophene)
journal, May 1999
- Tolbert, Laren; Edmond, Christine; Kowalik, Janusz
- Synthetic Metals, Vol. 101, Issue 1-3
Effect of molecular p-doping on hole density and mobility in poly(3-hexylthiophene)
journal, April 2012
- Pingel, P.; Schwarzl, R.; Neher, D.
- Applied Physics Letters, Vol. 100, Issue 14
Optical measurement of doping efficiency in poly(3-hexylthiophene) solutions and thin films
journal, February 2015
- Wang, Chenchen; Duong, Duc T.; Vandewal, Koen
- Physical Review B, Vol. 91, Issue 8
Synthesis and Application of 1,3,4,5,7,8-Hexafluorotetracyanonaphthoquinodimethane (F6-TNAP): A Conductivity Dopant for Organic Light-Emitting Devices
journal, July 2010
- Koech, Phillip K.; Padmaperuma, Asanga B.; Wang, Liang
- Chemistry of Materials, Vol. 22, Issue 13
Fermi level shift and doping efficiency in -doped small molecule organic semiconductors: A photoelectron spectroscopy and theoretical study
journal, July 2012
- Tietze, Max L.; Burtone, Lorenzo; Riede, Moritz
- Physical Review B, Vol. 86, Issue 3
An organic p-type dopant with high thermal stability for an organic semiconductor
journal, January 2008
- Gao, Zhi Qiang; Mi, Bao Xiu; Xu, Gui Zhen
- Chem. Commun., Issue 1
Efficient Vacuum-Deposited Organic Solar Cells Based on a New Low-Bandgap Oligothiophene and Fullerene C60
journal, November 2006
- Schulze, K.; Uhrich, C.; Schüppel, R.
- Advanced Materials, Vol. 18, Issue 21
Investigation of C 60 F 36 as low-volatility p -dopant in organic optoelectronic devices
journal, May 2011
- Meerheim, Rico; Olthof, Selina; Hermenau, Martin
- Journal of Applied Physics, Vol. 109, Issue 10
Ground-State Interaction and Electrical Doping of Fluorinated C 60 in Conjugated Polymers
journal, November 2009
- Solomeshch, Olga; Yu, Young Jun; Goryunkov, Alexey A.
- Advanced Materials, Vol. 21, Issue 44
The role of energy level matching in organic solar cells—Hexaazatriphenylene hexacarbonitrile as transparent electron transport material
journal, March 2011
- Falkenberg, Christiane; Olthof, Selina; Rieger, Ralph
- Solar Energy Materials and Solar Cells, Vol. 95, Issue 3
High hole mobility through charge recombination interface in organic light-emitting diodes
journal, October 2011
- Diouf, Baye Boucar; Jeon, Woo Sik; Park, Jung Soo
- Synthetic Metals, Vol. 161, Issue 19-20
Solution-processed hexaazatriphenylene hexacarbonitrile as a universal hole-injection layer for organic light-emitting diodes
journal, April 2013
- Lin, Hao-Wu; Lin, Wei-Chieh; Chang, Jung-Hung
- Organic Electronics, Vol. 14, Issue 4
Molecular doping of low-bandgap-polymer:fullerene solar cells: Effects on transport and solar cells
journal, February 2012
- Veysel Tunc, Ali; De Sio, Antonietta; Riedel, Daniel
- Organic Electronics, Vol. 13, Issue 2
Synthesis and characterization of p-type conductivity dopant 2-(3-(adamantan-1-yl)propyl)-3,5,6-trifluoro-7,7,8,8-tetracyanoquinodimethane
journal, January 2013
- Rainbolt, James E.; Koech, Phillip K.; Polikarpov, Evgueni
- Journal of Materials Chemistry C, Vol. 1, Issue 9
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
Effect of molecular symmetry on melting temperature and solubility
journal, January 2004
- Pinal, Rodolfo
- Organic & Biomolecular Chemistry, Vol. 2, Issue 18
Electroluminescence from Substituted Poly(thiophenes): From Blue to Near-Infrared
journal, October 1995
- Andersson, M. R.; Berggren, M.; Inganaes, O.
- Macromolecules, Vol. 28, Issue 22
Relationship between the ionization and oxidation potentials of molecular organic semiconductors
journal, February 2005
- D’Andrade, Brian W.; Datta, Shubhashish; Forrest, Stephen R.
- Organic Electronics, Vol. 6, Issue 1, p. 11-20
Controlled p -doping of zinc phthalocyanine by coevaporation with tetrafluorotetracyanoquinodimethane: A direct and inverse photoemission study
journal, December 2001
- Gao, Weiying; Kahn, Antoine
- Applied Physics Letters, Vol. 79, Issue 24
Two-Dimensional Electronic Excitations in Self-Assembled Conjugated Polymer Nanocrystals
journal, February 2000
- Österbacka, R.
- Science, Vol. 287, Issue 5454
Photoinduced Carrier Generation in P3HT/PCBM Bulk Heterojunction Materials
journal, February 2008
- Hwang, In-Wook; Moses, Daniel; Heeger, Alan J.
- The Journal of Physical Chemistry C, Vol. 112, Issue 11
Impact of interfacial polymer morphology on photoexcitation dynamics and device performance in P3HT/ZnO heterojunctions
journal, January 2009
- Lloyd, Matthew T.; Prasankumar, Rohit P.; Sinclair, Michael B.
- Journal of Materials Chemistry, Vol. 19, Issue 26
Chiroptical Properties of Regioregular Chiral Polythiophenes
journal, November 1994
- Bouman, M. M.; Havinga, E. E.; Janssen, R. A. J.
- Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals, Vol. 256, Issue 1
Controlling Morphology in Polymer–Fullerene Mixtures
journal, January 2008
- Moulé, A. J.; Meerholz, K.
- Advanced Materials, Vol. 20, Issue 2
The chemical and structural origin of efficient p-type doping in P3HT
journal, May 2013
- Duong, Duc T.; Wang, Chenchen; Antono, Erin
- Organic Electronics, Vol. 14, Issue 5
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
Comprehensive picture of -type doping of P3HT with the molecular acceptor F TCNQ
journal, March 2013
- Pingel, P.; Neher, D.
- Physical Review B, Vol. 87, Issue 11
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
The impact of molecular weight on microstructure and charge transport in semicrystalline polymer semiconductors–poly(3-hexylthiophene), a model study
journal, December 2013
- Koch, Felix Peter Vinzenz; Rivnay, Jonathan; Foster, Sam
- Progress in Polymer Science, Vol. 38, Issue 12
Role of Intermolecular Coupling in the Photophysics of Disordered Organic Semiconductors: Aggregate Emission in Regioregular Polythiophene
journal, May 2007
- Clark, Jenny; Silva, Carlos; Friend, Richard H.
- Physical Review Letters, Vol. 98, Issue 20
Effect of Trace Solvent on the Morphology of P3HT:PCBM Bulk Heterojunction Solar Cells
journal, March 2011
- Chang, Lilian; Lademann, Hans W. A.; Bonekamp, Jörg-Bernd
- Advanced Functional Materials, Vol. 21, Issue 10
Controlling microstructure in poly(3-hexylthiophene) nanofibers
journal, January 2012
- Roehling, John D.; Arslan, Ilke; Moulé, Adam J.
- J. Mater. Chem., Vol. 22, Issue 6
Reversible Optical Control of Conjugated Polymer Solubility with Sub-micrometer Resolution
journal, January 2015
- Jacobs, Ian E.; Li, Jun; Burg, Stephanie L.
- ACS Nano, Vol. 9, Issue 2
Effect of Crystallization on the Electronic Energy Levels and Thin Film Morphology of P3HT:PCBM Blends
journal, April 2011
- Tsoi, Wing C.; Spencer, Steve J.; Yang, Li
- Macromolecules, Vol. 44, Issue 8
Quenching of Excitons by Holes in Poly(3-hexylthiophene) Films
journal, May 2008
- Ferguson, Andrew J.; Kopidakis, Nikos; Shaheen, Sean E.
- The Journal of Physical Chemistry C, Vol. 112, Issue 26
High work-function hole transport layers by self-assembly using a fluorinated additive
journal, January 2014
- Mauger, Scott A.; Li, Jun; Özmen, Özge Tüzün
- J. Mater. Chem. C, Vol. 2, Issue 1
Microscopic Understanding of the Anisotropic Conductivity of PEDOT:PSS Thin Films
journal, May 2007
- Nardes, A. M.; Kemerink, M.; Janssen, R. A. J.
- Advanced Materials, Vol. 19, Issue 9
Works referencing / citing this record:
High-mobility, trap-free charge transport in conjugated polymer diodes
text, January 2019
- Nikolka, Mark; Broch, Katharina; Armitage, John
- Apollo - University of Cambridge Repository