Polymorphism controls the degree of charge transfer in a molecularly doped semiconducting polymer
Abstract
When an organic semiconductor (OSC) is blended with an electron acceptor molecule that can act as a p-type dopant, there should ideally be complete (integer) transfer of charge from the OSC to the dopant. However, some dopant–OSC blends instead form charge transfer complexes (CTCs), characterized by fractional charge transfer (CT) and strong orbital hybridization between the two molecules. Fractional CT doping does not efficiently generate free charge carriers, but it is unclear what conditions lead to incomplete charge transfer. Here we show that by modifying film processing conditions in the semiconductor–dopant couple poly(3-hexylthiophene):2,3,5,6-tetrafluoro-7,7,8,8,-tetracyanoquinodimethane (P3HT:F4TCNQ), we can selectively obtain nearly pure integer or fractional CT phases. Fractional CT films show electrical conductivities approximately 2 orders of magnitude lower than corresponding integer CT films, and remarkably different optical absorption spectra. Grazing incidence wide-angle X-ray diffraction (GIXD) reveals that fractional CT films display an unusually dense and well-ordered crystal structure. These films show lower paracrystallinity and shorter lamellar and π-stacking distances than undoped films processed under similar conditions. Using plane-wave DFT we obtain a structure with unit cell parameters closely matching those observed by GIXD. This first-ever observation of both fractional and integer CT in a single OSC–dopant system demonstrates the importance ofmore »
- Authors:
-
[1];
[1];
[1];
[1]
- Univ. of California, Davis, CA (United States)
- Stanford Univ., CA (United States)
- Publication Date:
- Research Org.:
- Univ. of California, Davis, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1540056
- Alternate Identifier(s):
- OSTI ID: 1434112
- Grant/Contract Number:
- SC0010419; CMMI-1636385; CBET-1510481; ECCS-1542152
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Materials Horizons
- Additional Journal Information:
- Journal Volume: 5; Journal Issue: 4; Journal ID: ISSN 2051-6347
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
Citation Formats
Jacobs, Ian E., Cendra, Camila, Harrelson, Thomas F., Bedolla Valdez, Zaira I., Faller, Roland, Salleo, Alberto, and Moulé, Adam J. Polymorphism controls the degree of charge transfer in a molecularly doped semiconducting polymer. United States: N. p., 2018.
Web. doi:10.1039/c8mh00223a.
Jacobs, Ian E., Cendra, Camila, Harrelson, Thomas F., Bedolla Valdez, Zaira I., Faller, Roland, Salleo, Alberto, & Moulé, Adam J. Polymorphism controls the degree of charge transfer in a molecularly doped semiconducting polymer. United States. https://doi.org/10.1039/c8mh00223a
Jacobs, Ian E., Cendra, Camila, Harrelson, Thomas F., Bedolla Valdez, Zaira I., Faller, Roland, Salleo, Alberto, and Moulé, Adam J. Mon .
"Polymorphism controls the degree of charge transfer in a molecularly doped semiconducting polymer". United States. https://doi.org/10.1039/c8mh00223a. https://www.osti.gov/servlets/purl/1540056.
@article{osti_1540056,
title = {Polymorphism controls the degree of charge transfer in a molecularly doped semiconducting polymer},
author = {Jacobs, Ian E. and Cendra, Camila and Harrelson, Thomas F. and Bedolla Valdez, Zaira I. and Faller, Roland and Salleo, Alberto and Moulé, Adam J.},
abstractNote = {When an organic semiconductor (OSC) is blended with an electron acceptor molecule that can act as a p-type dopant, there should ideally be complete (integer) transfer of charge from the OSC to the dopant. However, some dopant–OSC blends instead form charge transfer complexes (CTCs), characterized by fractional charge transfer (CT) and strong orbital hybridization between the two molecules. Fractional CT doping does not efficiently generate free charge carriers, but it is unclear what conditions lead to incomplete charge transfer. Here we show that by modifying film processing conditions in the semiconductor–dopant couple poly(3-hexylthiophene):2,3,5,6-tetrafluoro-7,7,8,8,-tetracyanoquinodimethane (P3HT:F4TCNQ), we can selectively obtain nearly pure integer or fractional CT phases. Fractional CT films show electrical conductivities approximately 2 orders of magnitude lower than corresponding integer CT films, and remarkably different optical absorption spectra. Grazing incidence wide-angle X-ray diffraction (GIXD) reveals that fractional CT films display an unusually dense and well-ordered crystal structure. These films show lower paracrystallinity and shorter lamellar and π-stacking distances than undoped films processed under similar conditions. Using plane-wave DFT we obtain a structure with unit cell parameters closely matching those observed by GIXD. This first-ever observation of both fractional and integer CT in a single OSC–dopant system demonstrates the importance of structural effects on OSC doping and opens the door to further studies.},
doi = {10.1039/c8mh00223a},
journal = {Materials Horizons},
number = 4,
volume = 5,
place = {United States},
year = {Mon Mar 26 00:00:00 EDT 2018},
month = {Mon Mar 26 00:00:00 EDT 2018}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 83 works
Citation information provided by
Web of Science
Web of Science
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:
Identifying Atomic Scale Structure in Undoped/Doped Semicrystalline P3HT Using Inelastic Neutron Scattering
journal, March 2017
- Harrelson, Thomas F.; Cheng, Yongqiang Q.; Li, Jun
- Macromolecules, Vol. 50, Issue 6
Aggregates Promote Efficient Charge Transfer Doping of Poly(3-hexylthiophene)
journal, August 2013
- Gao, Jian; Niles, Edwards T.; Grey, John K.
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 17
Structural phase transition in pentacene caused by molecular doping and its effect on charge carrier mobility
journal, January 2012
- Kleemann, Hans; Schuenemann, Christoph; Zakhidov, Alexander A.
- Organic Electronics, Vol. 13, Issue 1
Neutral-ionic interface in organic charge-transfer salts
journal, August 1978
- Soos, Z. G.; Mazumdar, S.
- Physical Review B, Vol. 18, Issue 4
Organic thermoelectric materials for energy harvesting and temperature control
journal, August 2016
- Russ, Boris; Glaudell, Anne; Urban, Jeffrey J.
- Nature Reviews Materials, Vol. 1, Issue 10
Behavior of charge‐transfer absorption upon passing through the neutral‐ionic phase transition
journal, January 1983
- Jacobsen, C. S.; Torrance, J. B.
- The Journal of Chemical Physics, Vol. 78, Issue 1
The difference between metallic and insulating salts of tetracyanoquinodimethone (TCNQ): how to design an organic metal
journal, March 1979
- Torrance, Jerry B.
- Accounts of Chemical Research, Vol. 12, Issue 3
Enhanced Electrical Conductivity of Molecularly p-Doped Poly(3-hexylthiophene) through Understanding the Correlation with Solid-State Order
journal, October 2017
- Hynynen, Jonna; Kiefer, David; Yu, Liyang
- Macromolecules, Vol. 50, Issue 20
Enhanced Charge Transfer Doping Efficiency in J-Aggregate Poly(3-hexylthiophene) Nanofibers
journal, June 2015
- Gao, Jian; Stein, Benjamin W.; Thomas, Alan K.
- The Journal of Physical Chemistry C, Vol. 119, Issue 28
Controlling Molecular Doping in Organic Semiconductors
journal, September 2017
- Jacobs, Ian E.; Moulé, Adam J.
- Advanced Materials, Vol. 29, Issue 42
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
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
Modeling the Neutral-Ionic Transition with Correlated Electrons Coupled to Soft Lattices and Molecules
journal, May 2017
- D’Avino, Gabriele; Painelli, Anna; Soos, Zoltán
- Crystals, Vol. 7, Issue 5
Molecular Electrical Doping of Organic Semiconductors: Fundamental Mechanisms and Emerging Dopant Design Rules
journal, February 2016
- Salzmann, Ingo; Heimel, Georg; Oehzelt, Martin
- Accounts of Chemical Research, Vol. 49, Issue 3
Direct Observation of Doping Sites in Temperature-Controlled, p-Doped P3HT Thin Films by Conducting Atomic Force Microscopy
journal, July 2014
- Duong, Duc T.; Phan, Hung; Hanifi, David
- Advanced Materials, Vol. 26, Issue 35
Doped Organic Transistors
journal, October 2016
- Lüssem, Björn; Keum, Chang-Min; Kasemann, Daniel
- Chemical Reviews, Vol. 116, Issue 22
Far-Infrared Optical Response of Neutral-Ionic Phase Transition in an Organic Charge-Transfer Complex
journal, October 2001
- Okimoto, Y.; Horiuchi, S.; Saitoh, E.
- Physical Review Letters, Vol. 87, Issue 18
Discovery of a Neutral-to-Ionic Phase Transition in Organic Materials
journal, January 1981
- Torrance, J. B.; Vazquez, J. E.; Mayerle, J. J.
- Physical Review Letters, Vol. 46, Issue 4
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
Charge-transfer crystallites as molecular electrical dopants
journal, October 2015
- Méndez, Henry; Heimel, Georg; Winkler, Stefanie
- Nature Communications, Vol. 6, Issue 1
How intermolecular geometrical disorder affects the molecular doping of donor–acceptor copolymers
journal, March 2015
- Di Nuzzo, Daniele; Fontanesi, Claudio; Jones, Rebecca
- Nature Communications, Vol. 6, Issue 1
Charge-Transfer–Solvent Interaction Predefines Doping Efficiency in p-Doped P3HT Films
journal, June 2016
- Müller, Lars; Nanova, Diana; Glaser, Tobias
- Chemistry of Materials, Vol. 28, Issue 12
Neutral-ionic transition and dimerization in organic mixed-stack compounds
journal, January 1986
- Avignon, M.; Balseiro, C. A.; Proetto, C. R.
- Physical Review B, Vol. 33, Issue 1
Intermolecular Hybridization Governs Molecular Electrical Doping
journal, January 2012
- Salzmann, Ingo; Heimel, Georg; Duhm, Steffen
- Physical Review Letters, Vol. 108, Issue 3
Introducing Solubility Control for Improved Organic P-Type Dopants
journal, August 2015
- Li, Jun; Zhang, Guangwu; Holm, Daniella M.
- Chemistry of Materials, Vol. 27, Issue 16
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
Model of the Neutral-Ionic Phase Transformation
journal, December 1981
- Hubbard, J.; Torrance, J. B.
- Physical Review Letters, Vol. 47, Issue 24
Charge-Transfer Localization in Molecularly Doped Thiophene-Based Donor Polymers
journal, June 2010
- Pingel, Patrick; Zhu, Lingyun; Park, Kue Surk
- The Journal of Physical Chemistry Letters, Vol. 1, Issue 13
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
Molecular Interactions and Ordering in Electrically Doped Polymers: Blends of PBTTT and F 4 TCNQ
journal, September 2014
- Cochran, Justin E.; Junk, Matthias J. N.; Glaudell, A. M.
- Macromolecules, Vol. 47, Issue 19
Localization and Delocalization Errors in Density Functional Theory and Implications for Band-Gap Prediction
journal, April 2008
- Mori-Sánchez, Paula; Cohen, Aron J.; Yang, Weitao
- Physical Review Letters, Vol. 100, Issue 14
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
Charge transfer in and conductivity of molecularly doped thiophene-based copolymers
journal, November 2014
- Ghani, Fatemeh; Opitz, Andreas; Pingel, Patrick
- Journal of Polymer Science Part B: Polymer Physics, Vol. 53, Issue 1
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
Dielectric response of modified Hubbard models with neutral-ionic and Peierls transitions
journal, April 2004
- Soos, Zoltan G.; Bewick, Sharon A.; Peri, Andrea
- The Journal of Chemical Physics, Vol. 120, Issue 14
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
Toward a comprehensive understanding of molecular doping organic semiconductors (review)
journal, October 2015
- Salzmann, Ingo; Heimel, Georg
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 204
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
Impact of mesoscale order on open-circuit voltage in organic solar cells
journal, December 2014
- Poelking, Carl; Tietze, Max; Elschner, Chris
- Nature Materials, Vol. 14, Issue 4
Charge–transfer organic crystals: Molecular vibrations and spectroscopic effects of electron–molecular vibration coupling of the strong electron acceptor TCNQF 4
journal, April 1986
- Meneghetti, Moreno; Pecile, Cesare
- The Journal of Chemical Physics, Vol. 84, Issue 8
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
Doping of Organic Semiconductors: Impact of Dopant Strength and Electronic Coupling
journal, June 2013
- Méndez, Henry; Heimel, Georg; Opitz, Andreas
- Angewandte Chemie, Vol. 125, Issue 30
Highly Efficient Organic Devices Based on Electrically Doped Transport Layers
journal, July 2007
- Walzer, K.; Maennig, B.; Pfeiffer, M.
- ChemInform, Vol. 38, Issue 31
Works referencing / citing this record:
Energetics and Escape of Interchain‐Delocalized Ion Pairs in Nonpolar Media
journal, January 2019
- Burke, John H.; Bird, Matthew J.
- Advanced Materials, Vol. 31, Issue 12
Electronic-reconstruction-enhanced hydrogen evolution catalysis in oxide polymorphs
journal, July 2019
- Li, Yangyang; Yu, Zhi Gen; Wang, Ling
- Nature Communications, Vol. 10, Issue 1
Double doping of conjugated polymers with monomer molecular dopants
journal, January 2019
- Kiefer, David; Kroon, Renee; Hofmann, Anna I.
- Nature Materials, Vol. 18, Issue 2
Ground-state electron transfer in all-polymer donor–acceptor heterojunctions
journal, March 2020
- Xu, Kai; Sun, Hengda; Ruoko, Tero-Petri
- Nature Materials, Vol. 19, Issue 7
Ab initio modelling of local interfaces in doped organic semiconductors
journal, January 2020
- Valencia, Ana M.; Guerrini, Michele; Cocchi, Caterina
- Physical Chemistry Chemical Physics, Vol. 22, Issue 6
Sequential molecular doping of non-fullerene organic solar cells without hole transport layers
journal, January 2020
- Zhang, Dongyang; Wang, Jianqiu; Zhang, Xuning
- Journal of Materials Chemistry C, Vol. 8, Issue 1
Will organic thermoelectrics get hot?
journal, July 2019
- Campoy-Quiles, Mariano
- Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 377, Issue 2152