Competition between Exceptionally Long‐Range Alkyl Sidechain Ordering and Backbone Ordering in Semiconducting Polymers and Its Impact on Electronic and Optoelectronic Properties
Abstract
Abstract Intra‐ and intermolecular ordering greatly impacts the electronic and optoelectronic properties of semiconducting polymers. The interrelationship between ordering of alkyl sidechains and conjugated backbones has yet to be fully detailed, despite much prior effort. Here, the discovery of a highly ordered alkyl sidechain phase in six representative semiconducting polymers, determined from distinct spectroscopic and diffraction signatures, is reported. The sidechain ordering exhibits unusually large coherence lengths (≥70 nm), induces torsional/twisting backbone disorder, and results in a vertically multilayered nanostructure with ordered sidechain layers alternating with disordered backbone layers. Calorimetry and in situ variable temperature scattering measurements in a model system poly{4‐(5‐(4,8‐bis(3‐butylnonyl)‐6‐methylbenzo[1,2‐b:4,5‐b′]dithiophen‐2‐yl)thiophen‐2‐yl)‐2‐(2‐butyloctyl)‐5,6‐difluoro‐7‐(5‐methylthiophen‐2‐yl)‐2H‐benzo[d][1,2,3]triazole} (PBnDT‐FTAZ) clearly delineate this competition of ordering that prevents simultaneous long‐range order of both moieties. The long‐range sidechain ordering can be exploited as a transient state to fabricate PBnDT‐FTAZ films with an atypical edge‐on texture and 2.5× improved field‐effect transistor mobility. The observed influence of ordering between the moieties implies that improved molecular design can produce synergistic rather than destructive ordering effects. Given the large sidechain coherence lengths observed, such synergistic ordering should greatly improve the coherence length of backbone ordering and thereby improve electronic and optoelectronic properties such as charge transport and exciton diffusion lengths.
- Authors:
-
- Department of Physics and Organic and Carbon Electronics Lab (ORaCEL) North Carolina State University Raleigh NC 27695 USA
- Materials Science and Engineering Division National Institute of Standards and Technology 100 Bureau Drive Gaithersburg MD 20899 USA
- Department of Chemistry University of North Carolina at Chapel Hill Chapel Hill NC 27599‐3290 USA
- Department of Mechanical and Aerospace Engineering and ORaCEL North Carolina State University Raleigh NC 27695 USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1485503
- Grant/Contract Number:
- DE‐AC02‐05CH11231
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Advanced Functional Materials
- Additional Journal Information:
- Journal Name: Advanced Functional Materials Journal Volume: 29 Journal Issue: 5; Journal ID: ISSN 1616-301X
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Carpenter, Joshua H., Ghasemi, Masoud, Gann, Eliot, Angunawela, Indunil, Stuard, Samuel J., Rech, Jeromy James, Ritchie, Earl, O'Connor, Brendan T., Atkin, Joanna, You, Wei, DeLongchamp, Dean M., and Ade, Harald. Competition between Exceptionally Long‐Range Alkyl Sidechain Ordering and Backbone Ordering in Semiconducting Polymers and Its Impact on Electronic and Optoelectronic Properties. Germany: N. p., 2018.
Web. doi:10.1002/adfm.201806977.
Carpenter, Joshua H., Ghasemi, Masoud, Gann, Eliot, Angunawela, Indunil, Stuard, Samuel J., Rech, Jeromy James, Ritchie, Earl, O'Connor, Brendan T., Atkin, Joanna, You, Wei, DeLongchamp, Dean M., & Ade, Harald. Competition between Exceptionally Long‐Range Alkyl Sidechain Ordering and Backbone Ordering in Semiconducting Polymers and Its Impact on Electronic and Optoelectronic Properties. Germany. https://doi.org/10.1002/adfm.201806977
Carpenter, Joshua H., Ghasemi, Masoud, Gann, Eliot, Angunawela, Indunil, Stuard, Samuel J., Rech, Jeromy James, Ritchie, Earl, O'Connor, Brendan T., Atkin, Joanna, You, Wei, DeLongchamp, Dean M., and Ade, Harald. Wed .
"Competition between Exceptionally Long‐Range Alkyl Sidechain Ordering and Backbone Ordering in Semiconducting Polymers and Its Impact on Electronic and Optoelectronic Properties". Germany. https://doi.org/10.1002/adfm.201806977.
@article{osti_1485503,
title = {Competition between Exceptionally Long‐Range Alkyl Sidechain Ordering and Backbone Ordering in Semiconducting Polymers and Its Impact on Electronic and Optoelectronic Properties},
author = {Carpenter, Joshua H. and Ghasemi, Masoud and Gann, Eliot and Angunawela, Indunil and Stuard, Samuel J. and Rech, Jeromy James and Ritchie, Earl and O'Connor, Brendan T. and Atkin, Joanna and You, Wei and DeLongchamp, Dean M. and Ade, Harald},
abstractNote = {Abstract Intra‐ and intermolecular ordering greatly impacts the electronic and optoelectronic properties of semiconducting polymers. The interrelationship between ordering of alkyl sidechains and conjugated backbones has yet to be fully detailed, despite much prior effort. Here, the discovery of a highly ordered alkyl sidechain phase in six representative semiconducting polymers, determined from distinct spectroscopic and diffraction signatures, is reported. The sidechain ordering exhibits unusually large coherence lengths (≥70 nm), induces torsional/twisting backbone disorder, and results in a vertically multilayered nanostructure with ordered sidechain layers alternating with disordered backbone layers. Calorimetry and in situ variable temperature scattering measurements in a model system poly{4‐(5‐(4,8‐bis(3‐butylnonyl)‐6‐methylbenzo[1,2‐b:4,5‐b′]dithiophen‐2‐yl)thiophen‐2‐yl)‐2‐(2‐butyloctyl)‐5,6‐difluoro‐7‐(5‐methylthiophen‐2‐yl)‐2H‐benzo[d][1,2,3]triazole} (PBnDT‐FTAZ) clearly delineate this competition of ordering that prevents simultaneous long‐range order of both moieties. The long‐range sidechain ordering can be exploited as a transient state to fabricate PBnDT‐FTAZ films with an atypical edge‐on texture and 2.5× improved field‐effect transistor mobility. The observed influence of ordering between the moieties implies that improved molecular design can produce synergistic rather than destructive ordering effects. Given the large sidechain coherence lengths observed, such synergistic ordering should greatly improve the coherence length of backbone ordering and thereby improve electronic and optoelectronic properties such as charge transport and exciton diffusion lengths.},
doi = {10.1002/adfm.201806977},
journal = {Advanced Functional Materials},
number = 5,
volume = 29,
place = {Germany},
year = {2018},
month = {12}
}
https://doi.org/10.1002/adfm.201806977
Web of Science
Works referenced in this record:
A Study on the Correlation Between Structure and Hole Transport in Semi-Crystalline Regioregular P3HT
journal, September 2012
- Shen, Xiaobo; Duzhko, Volodimyr V.; Russell, Thomas P.
- Advanced Energy Materials, Vol. 3, Issue 2
Charge Mobility and Transport Behavior in the Ordered and Disordered States of the Regioregular Poly(3-hexylthiophene)
journal, November 2009
- Lan, Yi-Kang; Huang, Ching-I
- The Journal of Physical Chemistry B, Vol. 113, Issue 44
A Near Edge X-ray Absorption Fine Structure Spectroscopy Investigation of the Structure of Self-Assembled Films of Octadecyltrichlorosilane
journal, February 2002
- Peters, Richard D.; Nealey, Paul F.; Crain, Jason N.
- Langmuir, Vol. 18, Issue 4
Towards a detailed understanding of the NEXAFS spectra of bulk polyethylene copolymers and related alkanes
journal, March 2003
- Schöll, A.; Fink, R.; Umbach, E.
- Chemical Physics Letters, Vol. 370, Issue 5-6
Poly(diketopyrrolopyrrole−terthiophene) for Ambipolar Logic and Photovoltaics
journal, November 2009
- Bijleveld, Johan C.; Zoombelt, Arjan P.; Mathijssen, Simon G. J.
- Journal of the American Chemical Society, Vol. 131, Issue 46
A high-mobility electron-transporting polymer for printed transistors
journal, January 2009
- Yan, He; Chen, Zhihua; Zheng, Yan
- Nature, Vol. 457, Issue 7230, p. 679-686
Fluorination of Donor–Acceptor Copolymer Active Layers Enhances Charge Mobilities in Thin-Film Transistors
journal, September 2017
- Smith, Brandon H.; Zhang, Qianqian; Kelly, Mary Allison
- ACS Macro Letters, Vol. 6, Issue 10
The Impact of Polymer Regioregularity on Charge Transport and Efficiency of P3HT:PCBM Photovoltaic Devices
journal, May 2010
- Mauer, Ralf; Kastler, Marcel; Laquai, Frédéric
- Advanced Functional Materials, Vol. 20, Issue 13
Calibrated NEXAFS spectra of common conjugated polymers
journal, January 2011
- Watts, B.; Swaraj, S.; Nordlund, D.
- The Journal of Chemical Physics, Vol. 134, Issue 2
Two-dimensional charge transport in self-organized, high-mobility conjugated polymers
journal, October 1999
- Sirringhaus, H.; Brown, P. J.; Friend, R. H.
- Nature, Vol. 401, Issue 6754, p. 685-688
Polymorphism and Structural Transition around 54 °C in Regioregular Poly(3-hexylthiophene) with High Crystallinity As Revealed by Infrared Spectroscopy
journal, December 2011
- Yuan, Yuan; Zhang, Jianming; Sun, Jiaqian
- Macromolecules, Vol. 44, Issue 23
Long-range exciton transport in conjugated polymer nanofibers prepared by seeded growth
journal, May 2018
- Jin, Xu-Hui; Price, Michael B.; Finnegan, John R.
- Science, Vol. 360, Issue 6391
Enthalpies of fusion and solid-solid transition of even-numbered paraffins C22H46, C24H50, C26H54 and C28H58
journal, April 1991
- Domanska, U.; Wyrzykowska-Stankiewicz, D.
- Thermochimica Acta, Vol. 179
A SAXS/WAXS/GISAXS Beamline with Multilayer Monochromator
journal, October 2010
- Hexemer, Alexander; Bras, Wim; Glossinger, James
- Journal of Physics: Conference Series, Vol. 247
Differences in NEXAFS of odd/even long chain n-alkane crystals
journal, December 2013
- Swaraj, Sufal; Ade, Harald
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 191
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
A Thienoisoindigo-Naphthalene Polymer with Ultrahigh Mobility of 14.4 cm 2 /V·s That Substantially Exceeds Benchmark Values for Amorphous Silicon Semiconductors
journal, June 2014
- Kim, Gyoungsik; Kang, Seok-Ju; Dutta, Gitish K.
- Journal of the American Chemical Society, Vol. 136, Issue 26
Growth and Characterization of Sexithiophene Single Crystals
journal, July 1995
- Horowitz, Gilles; Bachet, Bernard; Yassar, Abderrahim
- Chemistry of Materials, Vol. 7, Issue 7
A Low-Bandgap Poly(2,7-Carbazole) Derivative for Use in High-Performance Solar Cells
journal, September 2007
- Blouin, N.; Michaud, A.; Leclerc, M.
- Advanced Materials, Vol. 19, Issue 17, p. 2295-2300
Thermodynamic properties of organic compounds: enthalpy of fusion and melting point temperature compilation
journal, October 1991
- Acree, William E.
- Thermochimica Acta, Vol. 189, Issue 1
Glass Transition Temperature of Conjugated Polymers by Oscillatory Shear Rheometry
journal, June 2017
- Xie, Renxuan; Lee, Youngmin; Aplan, Melissa P.
- Macromolecules, Vol. 50, Issue 13
Highly Disordered Polymer Field Effect Transistors: N -Alkyl Dithieno[3,2- b :2′,3′- d ]pyrrole-Based Copolymers with Surprisingly High Charge Carrier Mobilities
journal, October 2008
- Liu, Junying; Zhang, Rui; Sauvé, Geneviève
- Journal of the American Chemical Society, Vol. 130, Issue 39
Regio-Regular Oligo and Poly(3-hexyl thiophene): Precise Structural Markers from the Vibrational Spectra of Oligomer Single Crystals.
journal, October 2014
- Brambilla, Luigi; Tommasini, Matteo; Botiz, Ioan
- Macromolecules, Vol. 47, Issue 19
Effect of Solvent Evaporation Rate on Order-to-Disorder Phase Transition Behavior of Regioregular Poly(3-butylthiophene)
journal, August 2011
- Yuan, Yuan; Zhang, Jianming; Sun, Jiaqian
- Macromolecules, Vol. 44, Issue 15
Side-Chain Dynamics and Crystallization in a Series of Regiorandom Poly(3-alkylthiophenes)
journal, February 2009
- Pankaj, Shireesh; Hempel, Elke; Beiner, Mario
- Macromolecules, Vol. 42, Issue 3
Excitons and Davydov splitting in sexithiophene from first-principles many-body Green’s function theory
journal, September 2015
- Leng, Xia; Yin, Huabing; Liang, Dongmei
- The Journal of Chemical Physics, Vol. 143, Issue 11
Structure of P3HT crystals, thin films, and solutions by UV/Vis spectral analysis
journal, January 2015
- Böckmann, Marcus; Schemme, Thomas; de Jong, Djurre H.
- Physical Chemistry Chemical Physics, Vol. 17, Issue 43
Fluorine Substituted Conjugated Polymer of Medium Band Gap Yields 7% Efficiency in Polymer−Fullerene Solar Cells
journal, March 2011
- Price, Samuel C.; Stuart, Andrew C.; Yang, Liqiang
- Journal of the American Chemical Society, Vol. 133, Issue 12
Approaching disorder-free transport in high-mobility conjugated polymers
journal, November 2014
- Venkateshvaran, Deepak; Nikolka, Mark; Sadhanala, Aditya
- Nature, Vol. 515, Issue 7527
Integrated Optoelectronic Devices Based on Conjugated Polymers
journal, June 1998
- Sirringhaus, H.
- Science, Vol. 280, Issue 5370
Side-Chain-Induced Rigid Backbone Organization of Polymer Semiconductors through Semifluoroalkyl Side Chains
journal, January 2016
- Kang, Boseok; Kim, Ran; Lee, Seon Baek
- Journal of the American Chemical Society, Vol. 138, Issue 11
Indacenodithiophene Semiconducting Polymers for High-Performance, Air-Stable Transistors
journal, August 2010
- Zhang, Weimin; Smith, Jeremy; Watkins, Scott E.
- Journal of the American Chemical Society, Vol. 132, Issue 33
Fluorinated Thiophene Units Improve Photovoltaic Device Performance of Donor–Acceptor Copolymers
journal, July 2017
- Zhang, Qianqian; Yan, Liang; Jiao, Xuechen
- Chemistry of Materials, Vol. 29, Issue 14
Molecular Basis of Mesophase Ordering in a Thiophene-Based Copolymer
journal, August 2008
- DeLongchamp, Dean M.; Kline, R. Joseph; Jung, Youngsuk
- Macromolecules, Vol. 41, Issue 15
All-Atom Molecular Dynamics Simulation of Temperature Effects on the Structural, Thermodynamic, and Packing Properties of the Pure Amorphous and Pure Crystalline Phases of Regioregular P3HT
journal, March 2013
- Alexiadis, Orestis; Mavrantzas, Vlasis G.
- Macromolecules, Vol. 46, Issue 6
Identification of C—H resonances in the -shell excitation spectra of gas-phase, chemisorbed, and polymeric hydrocarbons
journal, August 1987
- Stöhr, J.; Outka, D. A.; Baberschke, K.
- Physical Review B, Vol. 36, Issue 5
Thermal and Structural Characteristics of Oligo(3-hexylthiophene)s (3HT) n , n = 4–36
journal, September 2013
- Koch, Felix Peter Vinzenz; Heeney, Martin; Smith, Paul
- Journal of the American Chemical Society, Vol. 135, Issue 37
Temperature Induced Order–Disorder Transition in Solutions of Conjugated Polymers Probed by Optical Spectroscopy
journal, December 2016
- Panzer, Fabian; Bässler, Heinz; Köhler, Anna
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 1
Modeling disorder in polymer aggregates: The optical spectroscopy of regioregular poly(3-hexylthiophene) thin films
journal, June 2005
- Spano, Frank C.
- The Journal of Chemical Physics, Vol. 122, Issue 23
Near edge x-ray-absorption fine-structure determination of alkyl-chain orientation: Breakdown of the ‘‘building-block’’ scheme
journal, August 1991
- Hähner, G.; Kinzler, M.; Wöll, Ch.
- Physical Review Letters, Vol. 67, Issue 7
Unconventional Face-On Texture and Exceptional In-Plane Order of a High Mobility n-Type Polymer
journal, July 2010
- Rivnay, Jonathan; Toney, Michael F.; Zheng, Yan
- Advanced Materials, Vol. 22, Issue 39
The Crystal Structure of Lower Paraffins. V. Cell Dimensions of Nonane, Decane, Undecane, Dodecane, Tridecane, Tetradecane, and Hexadecane.
journal, January 1972
- Norman, N.; Mathisen, H.; Andresen, Arne F.
- Acta Chemica Scandinavica, Vol. 26
Aggregation and morphology control enables multiple cases of high-efficiency polymer solar cells
journal, November 2014
- Liu, Yuhang; Zhao, Jingbo; Li, Zhengke
- Nature Communications, Vol. 5, Issue 1
Nika : software for two-dimensional data reduction
journal, March 2012
- Ilavsky, Jan
- Journal of Applied Crystallography, Vol. 45, Issue 2
Near-Edge X-ray Absorption Fine Structure Spectroscopy of MDI and TDI Polyurethane Polymers
journal, June 1999
- Urquhart, Stephen G.; Smith, Archie P.; Ade, Harald W.
- The Journal of Physical Chemistry B, Vol. 103, Issue 22
Liquid-crystalline semiconducting polymers with high charge-carrier mobility
journal, March 2006
- McCulloch, Iain; Heeney, Martin; Bailey, Clare
- Nature Materials, Vol. 5, Issue 4
Connecting Molecular Conformation to Aggregation in P3HT Using Near Edge X-ray Absorption Fine Structure Spectroscopy
journal, September 2017
- Urquhart, Stephen G.; Martinson, Mercedes; Eger, Shaylin
- The Journal of Physical Chemistry C, Vol. 121, Issue 39
Trends in the Carbonyl Core (C 1S, O 1S) → π* C=O Transition in the Near-Edge X-ray Absorption Fine Structure Spectra of Organic Molecules
journal, August 2002
- Urquhart, S. G.; Ade, H.
- The Journal of Physical Chemistry B, Vol. 106, Issue 34
Calibrated NEXAFS spectra of some common polymers
journal, January 2003
- Dhez, O.; Ade, H.; Urquhart, S. G.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 128, Issue 1
Influence of molecular weight on polymorphs and temperature-induced structure evolution of regioregular poly(3-dodecylthiophene)
journal, January 2014
- Guo, Yan; Wang, Lei; Han, Yuanyuan
- Polym. Chem., Vol. 5, Issue 6
Study on π–π Interaction in H- and J-Aggregates of Poly(3-hexylthiophene) Nanowires by Multiple Techniques
journal, June 2015
- Yuan, Yuan; Shu, Jie; Liu, Ping
- The Journal of Physical Chemistry B, Vol. 119, Issue 26
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
Carbon K-shell excitation spectra of linear and branched alkanes
journal, January 1987
- Hitchcock, A. P.; Ishii, I.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 42, Issue 1
Inner shell excitation of thiophene and thiolane: Gas, solid, and monolayer states
journal, November 1986
- Hitchcock, A. P.; Horsley, J. A.; Stöhr, J.
- The Journal of Chemical Physics, Vol. 85, Issue 9
Fluorinated Polymer Yields High Organic Solar Cell Performance for a Wide Range of Morphologies
journal, February 2013
- Tumbleston, John R.; Stuart, Andrew C.; Gann, Eliot
- Advanced Functional Materials, Vol. 23, Issue 27
Temperature-Dependent Evolution of Poly(3-Hexylthiophene) Type-II Phase in a Blended Thin Film
journal, November 2015
- Lee, Si Woo; Keum, Hee-Sung; Kim, Han Seong
- Macromolecular Rapid Communications, Vol. 37, Issue 3
Three-Phase Morphology of Semicrystalline Polymer Semiconductors: A Quantitative Analysis
journal, September 2015
- Remy, Roddel; Wei, Sujun; Campos, Luis M.
- ACS Macro Letters, Vol. 4, Issue 9
Ordered Stacking of Regioregular Head-to-Tail Polyalkylthiophenes: Insights from the Crystal Structure of Form I′ Poly(3-n-butylthiophene)
journal, January 2009
- Arosio, Paolo; Moreno, Margherita; Famulari, Antonino
- Chemistry of Materials, Vol. 21, Issue 1, p. 78-87
The Current Performance of the Wide Range (90–2500 eV) Soft X-ray Beamline at the Australian Synchrotron
conference, January 2010
- Cowie, B. C. C.; Tadich, A.; Thomsen, L.
- SRI 2009, 10TH INTERNATIONAL CONFERENCE ON RADIATION INSTRUMENTATION, AIP Conference Proceedings
XPS and XAS investigation of condensed and adsorbed n-octane on a Cu(110) surface
journal, February 2003
- Weiss, K.; Öström, H.; Triguero, L.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 128, Issue 2-3
Tuning charge transport in solution-sheared organic semiconductors using lattice strain
journal, December 2011
- Giri, Gaurav; Verploegen, Eric; Mannsfeld, Stefan C. B.
- Nature, Vol. 480, Issue 7378, p. 504-508
Spectroscopic Signature of Two Distinct H-Aggregate Species in Poly(3-hexylthiophene)
journal, February 2015
- Panzer, Fabian; Sommer, Michael; Bässler, Heinz
- Macromolecules, Vol. 48, Issue 5
The Melting Point Alternation in the Short-Chainn-Alkanes: Single-Crystal X-Ray Analyses of Propane at 30 K and ofn-Butane ton-Nonane at 90 K
journal, April 1999
- Boese, Roland; Weiss, Hans-Christoph; Bläser, Dieter
- Angewandte Chemie International Edition, Vol. 38, Issue 7
Determining exciton bandwidth and film microstructure in polythiophene films using linear absorption spectroscopy
journal, April 2009
- Clark, Jenny; Chang, Jui-Fen; Spano, Frank C.
- Applied Physics Letters, Vol. 94, Issue 16, Article No. 163306
About different packing states of alkyl groups in comb-like polymers with rigid backbones
journal, January 2016
- Babur, Tamoor; Gupta, Gaurav; Beiner, Mario
- Soft Matter, Vol. 12, Issue 39
Confined Dynamics and Crystallization in Self-Assembled Alkyl Nanodomains
journal, December 2010
- Pankaj, Shireesh; Beiner, Mario
- The Journal of Physical Chemistry B, Vol. 114, Issue 47
Modulating the Molecular Packing and Nanophase Blending via a Random Terpolymerization Strategy toward 11% Efficiency Nonfullerene Polymer Solar Cells
journal, July 2017
- Chen, Shanshan; Cho, Hye Jin; Lee, Jungho
- Advanced Energy Materials, Vol. 7, Issue 21
Side chain crystallization and non-equilibrium phenomena in nanophase separated poly(3-alkyl thiophenes)
conference, January 2010
- Pankaj, Shireesh; Beiner, Mario; D’Amore, A.
- V INTERNATIONAL CONFERENCE ON TIMES OF POLYMERS (TOP) AND COMPOSITES, AIP Conference Proceedings