Impact of Backbone Rigidity on the Thermomechanical Properties of Semiconducting Polymers with Conjugation Break Spacers

Galuska, Luke A.; McNutt, William W.; Qian, Zhiyuan; Zhang, Song; Weller, Daniel W.; Dhakal, Sujata; King, Eric R.; Morgan, Sarah E.; Azoulay, Jason D.; Mei, Jianguo; Gu, Xiaodan

doi:10.1021/acs.macromol.0c00889

Impact of Backbone Rigidity on the Thermomechanical Properties of Semiconducting Polymers with Conjugation Break Spacers

Journal Article · Fri Jul 17 00:00:00 EDT 2020 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.0c00889· OSTI ID:1659419

Galuska, Luke A. ^[1]; McNutt, William W. ^[2]; Qian, Zhiyuan ^[3]; Zhang, Song ^[3]; Weller, Daniel W. ^[3]; Dhakal, Sujata ^[3]; King, Eric R. ^[3]; ^[3]; ^[3]; ^[2]; ^[3]

Univ. of Southern Mississippi, Hattiesburg, MI (United States); University of Southern Mississippi
Purdue Univ., West Lafayette, IN (United States)
Univ. of Southern Mississippi, Hattiesburg, MI (United States)

There remains a lack of fundamental understanding in theroleofbackbonerigidityonthe thermomechanical properties of conjugated polymers. Here, we provide the first holistic approach to understand the fundamental influence of backbone rigidity on an n-type naphthalene diimide-based conjugated polymer, denoted by PNDI-Cx, through insertion of a flexible conjugation break spacer (CBS). CBS lengths are varied from fully conjugated with zero alkyl spacer (PNDI-C0) to a seven- carbon alkyl spacer (PNDI-C₇), with the CBS engineered into each repeat unit for systematic evaluation. Solution small-angle neutron scattering and oscillatory shear rheometry were employed to provide the first quantitative evidence of CBS influence over conjugated polymer chain rigidity and entanglement molecular weight (M_e), demonstrating a reduction in the Kuhn length from 521 to 36 Å for fully conjugated PNDI-C0 and PNDI-C6, respectively, as well as a nearly consistent Me of ~15 kDa upon the addition of CBS. Thermomechanical properties, such as elastic modulus and glass-transition temperature, were shown to decrease with an increasing length of CBS. An extraordinary ductility, upwards of 400% tensile strain before fracture, was observed for high-molecular-weight PNDI-C4, which we attribute to a high number of entanglements and disruption of crystallization. Furthermore, the deformation mechanism for PNDI-Cx was studied under strain through X-ray diffraction, polarized UV-vis spectroscopy, and atomic force microscopy. Overall, this work sheds light on the important role of backbone rigidity in designing flexible and stretchable conjugated polymers.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Southern Mississippi, Hattiesburg, MI (United States); Univ. of Southern Mississippi, Hattiesburg, MS (United States); University of Southern Mississippi, Hattiesburg, MS (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019361

OSTI ID:: 1659419

Alternate ID(s):: OSTI ID: 1774736
OSTI ID: 1985341

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 14 Vol. 53; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (55)

Anisotropic Structure and Charge Transport in Highly Strain-Aligned Regioregular Poly(3-hexylthiophene) O'Connor, Brendan; Kline, R. Joseph; Conrad, Brad R. Advanced Functional Materials, Vol. 21, Issue 19 https://doi.org/10.1002/adfm.201100904	journal	August 2011
Mechanical Properties of Conjugated Polymers and Polymer-Fullerene Composites as a Function of Molecular Structure Savagatrup, Suchol; Makaram, Aditya S.; Burke, Daniel J. Advanced Functional Materials, Vol. 24, Issue 8 https://doi.org/10.1002/adfm.201302646	journal	October 2013
Melt-Processing of Complementary Semiconducting Polymer Blends for High Performance Organic Transistors Zhao, Yan; Zhao, Xikang; Roders, Michael Advanced Materials, Vol. 29, Issue 6 https://doi.org/10.1002/adma.201605056	journal	December 2016
Non-Conjugated Flexible Linkers in Semiconducting Polymers: A Pathway to Improved Processability without Compromising Device Performance Schroeder, Bob C.; Chiu, Yu-Cheng; Gu, Xiaodan Advanced Electronic Materials, Vol. 2, Issue 7 https://doi.org/10.1002/aelm.201600104	journal	May 2016
Connecting the Mechanical and Conductive Properties of Conjugated Polymers Xie, Renxuan; Colby, Ralph H.; Gomez, Enrique D. Advanced Electronic Materials, Vol. 4, Issue 10 https://doi.org/10.1002/aelm.201700356	journal	December 2017
The Critical Role of Electron‐Donating Thiophene Groups on the Mechanical and Thermal Properties of Donor–Acceptor Semiconducting Polymers Zhang, Song; Ocheje, Michael U.; Huang, Lifeng Advanced Electronic Materials, Vol. 5, Issue 5 https://doi.org/10.1002/aelm.201800899	journal	March 2019
Glass Transition Phenomenon for Conjugated Polymers Qian, Zhiyuan; Cao, Zhiqiang; Galuska, Luke Macromolecular Chemistry and Physics, Vol. 220, Issue 11 https://doi.org/10.1002/macp.201900062	journal	April 2019
Effect of Broken Conjugation on the Stretchability of Semiconducting Polymers Savagatrup, Suchol; Zhao, Xikang; Chan, Esther Macromolecular Rapid Communications, Vol. 37, Issue 19 https://doi.org/10.1002/marc.201600377	journal	August 2016
Probing the Viscoelastic Property of Pseudo Free-Standing Conjugated Polymeric Thin Films Zhang, Song; Ocheje, Michael U.; Luo, Shaochuan Macromolecular Rapid Communications, Vol. 39, Issue 14 https://doi.org/10.1002/marc.201800092	journal	May 2018
Entanglements in P3HT and their influence on thin-film mechanical properties: Insights from molecular dynamics simulations Tummala, Naga Rajesh; Risko, Chad; Bruner, Christopher Journal of Polymer Science Part B: Polymer Physics, Vol. 53, Issue 13 https://doi.org/10.1002/polb.23722	journal	April 2015
Challenge and Solution of Characterizing Glass Transition Temperature for Conjugated Polymers by Differential Scanning Calorimetry Qian, Zhiyuan; Galuska, Luke; McNutt, William W. Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 23 https://doi.org/10.1002/polb.24889	journal	August 2019
Van Gurp-Palmen-plot: a way to characterize polydispersity of linear polymers Trinkle, Stefan; Friedrich, Christian Rheologica Acta, Vol. 40, Issue 4 https://doi.org/10.1007/s003970000137	journal	July 2001
Structural study of conducting polymers in solution Aimé, J. P.; Bargain, F.; Schott, M. Synthetic Metals, Vol. 28, Issue 1-2 https://doi.org/10.1016/0379-6779(89)90553-5	journal	January 1989
Molecular packing control enables excellent performance and mechanical property of blade-cast all-polymer solar cells Lin, Baojun; Zhang, Lin; Zhao, Heng Nano Energy, Vol. 59 https://doi.org/10.1016/j.nanoen.2019.02.046	journal	May 2019
Expanding the application of the van Gurp-Palmen plot: New insights into polymer melt rheology Qian, Zhiyuan; McKenna, Gregory B. Polymer, Vol. 155 https://doi.org/10.1016/j.polymer.2018.09.036	journal	October 2018
The impact of molecular weight on microstructure and charge transport in semicrystalline polymer semiconductors–poly(3-hexylthiophene), a model study Koch, Felix Peter Vinzenz; Rivnay, Jonathan; Foster, Sam Progress in Polymer Science, Vol. 38, Issue 12 https://doi.org/10.1016/j.progpolymsci.2013.07.009	journal	December 2013
Conjugated Polymers in Bioelectronics Inal, Sahika; Rivnay, Jonathan; Suiu, Andreea-Otilia Accounts of Chemical Research, Vol. 51, Issue 6 https://doi.org/10.1021/acs.accounts.7b00624	journal	May 2018
On the Glass Transition of Polymer Semiconductors and Its Impact on Polymer Solar Cell Stability Müller, Christian Chemistry of Materials, Vol. 27, Issue 8 https://doi.org/10.1021/acs.chemmater.5b00024	journal	March 2015
Mechanical Properties of a Library of Low-Band-Gap Polymers Roth, Bérenger; Savagatrup, Suchol; V. de los Santos, Nathaniel Chemistry of Materials, Vol. 28, Issue 7 https://doi.org/10.1021/acs.chemmater.6b00525	journal	March 2016
Mixing Behavior in Small Molecule:Fullerene Organic Photovoltaics Oosterhout, Stefan D.; Savikhin, Victoria; Zhang, Junxiang Chemistry of Materials, Vol. 29, Issue 7 https://doi.org/10.1021/acs.chemmater.7b00067	journal	March 2017
Tuning the Cross-Linker Crystallinity of a Stretchable Polymer Semiconductor Wang, Ging-Ji Nathan; Zheng, Yu; Zhang, Song Chemistry of Materials, Vol. 31, Issue 17 https://doi.org/10.1021/acs.chemmater.8b04314	journal	November 2018
The Importance of Entanglements in Optimizing the Mechanical and Electrical Performance of All-Polymer Solar Cells Balar, Nrup; Rech, Jeromy James; Henry, Reece Chemistry of Materials, Vol. 31, Issue 14 https://doi.org/10.1021/acs.chemmater.9b01011	journal	June 2019
Aggregation and Solubility of a Model Conjugated Donor–Acceptor Polymer Reid, Daniel R.; Jackson, Nicholas E.; Bourque, Alexander J. The Journal of Physical Chemistry Letters, Vol. 9, Issue 16 https://doi.org/10.1021/acs.jpclett.8b01738	journal	July 2018
Conjugation-Break Spacers in Semiconducting Polymers: Impact on Polymer Processability and Charge Transport Properties Zhao, Yan; Zhao, Xikang; Zang, Yaping Macromolecules, Vol. 48, Issue 7 https://doi.org/10.1021/acs.macromol.5b00194	journal	March 2015
Tuning Mechanical and Optoelectrical Properties of Poly(3-hexylthiophene) through Systematic Regioregularity Control Kim, Jin-Seong; Kim, Jae-Han; Lee, Wonho Macromolecules, Vol. 48, Issue 13 https://doi.org/10.1021/acs.macromol.5b00524	journal	June 2015
Complementary Semiconducting Polymer Blends: The Influence of Conjugation-Break Spacer Length in Matrix Polymers Zhao, Xikang; Zhao, Yan; Ge, Qu Macromolecules, Vol. 49, Issue 7 https://doi.org/10.1021/acs.macromol.6b00050	journal	March 2016
Unravelling the Thermomechanical Properties of Bulk Heterojunction Blends in Polymer Solar Cells Sharma, Anirudh; Pan, Xun; Campbell, Jonathan A. Macromolecules, Vol. 50, Issue 8 https://doi.org/10.1021/acs.macromol.7b00430	journal	April 2017
Glass Transition Temperature of Conjugated Polymers by Oscillatory Shear Rheometry Xie, Renxuan; Lee, Youngmin; Aplan, Melissa P. Macromolecules, Vol. 50, Issue 13 https://doi.org/10.1021/acs.macromol.7b00712	journal	June 2017
Nonhalogenated Solvent Processable and Printable High-Performance Polymer Semiconductor Enabled by Isomeric Nonconjugated Flexible Linkers Wang, Ging-Ji Nathan; Molina-Lopez, Francisco; Zhang, Hongyi Macromolecules, Vol. 51, Issue 13 https://doi.org/10.1021/acs.macromol.8b00971	journal	June 2018
Importance of Nucleation during Morphology Evolution of the Blade-Cast PffBT4T-2OD-Based Organic Solar Cells Bi, Zhaozhao; Naveed, Hafiz Bilal; Mao, Yimin Macromolecules, Vol. 51, Issue 17 https://doi.org/10.1021/acs.macromol.8b01156	journal	August 2018
Local Chain Alignment via Nematic Ordering Reduces Chain Entanglement in Conjugated Polymers Xie, Renxuan; Aplan, Melissa P.; Caggiano, Nicholas J. Macromolecules, Vol. 51, Issue 24 https://doi.org/10.1021/acs.macromol.8b01840	journal	December 2018
Linear Rheology of a Series of Second-Generation Dendronized Wedge Polymers Qian, Zhiyuan; Koh, Yung P.; Pallaka, Madhusudhan R. Macromolecules, Vol. 52, Issue 5 https://doi.org/10.1021/acs.macromol.8b02122	journal	February 2019
Influence of Systematic Incorporation of Conjugation-Break Spacers into Semi-Random Polymers on Mechanical and Electronic Properties Melenbrink, Elizabeth L.; Hilby, Kristan M.; Alkhadra, Mohammad A. ACS Applied Materials & Interfaces, Vol. 10, Issue 38 https://doi.org/10.1021/acsami.8b10608	journal	September 2018
N-Type Complementary Semiconducting Polymer Blends McNutt, William W.; Gumyusenge, Aristide; Galuska, Luke A. ACS Applied Polymer Materials, Vol. 2, Issue 7 https://doi.org/10.1021/acsapm.0c00261	journal	June 2020
Influence of Acceptor Side-Chain Length and Conjugation-Break Spacer Content on the Mechanical and Electronic Properties of Semi-Random Polymers Melenbrink, Elizabeth L.; Hilby, Kristan M.; Choudhary, Kartik ACS Applied Polymer Materials, Vol. 1, Issue 5 https://doi.org/10.1021/acsapm.9b00115	journal	April 2019
Extensive Studies on π-Stacking of Poly(3-alkylthiophene-2,5-diyl)s and Poly(4-alkylthiazole-2,5-diyl)s by Optical Spectroscopy, NMR Analysis, Light Scattering Analysis, and X-ray Crystallography Yamamoto, Takakazu; Komarudin, Dharma; Arai, Minoru Journal of the American Chemical Society, Vol. 120, Issue 9 https://doi.org/10.1021/ja973873a	journal	March 1998
High-Field-Effect Mobility of Low-Crystallinity Conjugated Polymers with Localized Aggregates Son, Sung Y.; Kim, Yebyeol; Lee, Junwoo Journal of the American Chemical Society, Vol. 138, Issue 26 https://doi.org/10.1021/jacs.6b01046	journal	May 2016
Measuring Molecular Order in Poly(3-alkylthiophene) Thin Films with Polarizing Spectroscopies Gurau, Marc C.; Delongchamp, Dean M.; Vogel, Brandon M. Langmuir, Vol. 23, Issue 2 https://doi.org/10.1021/la0618972	journal	January 2007
Structure and Dynamics of Nondilute Polyfluorene Solutions Fytas, G.; Nothofer, H. G.; Scherf, U. Macromolecules, Vol. 35, Issue 2 https://doi.org/10.1021/ma011416f	journal	January 2002
Polymer Chain Shape of Poly(3-alkylthiophenes) in Solution Using Small-Angle Neutron Scattering McCulloch, Bryan; Ho, Victor; Hoarfrost, Megan Macromolecules, Vol. 46, Issue 5 https://doi.org/10.1021/ma302463d	journal	February 2013
Predicting Chain Dimensions of Semiflexible Polymers from Dihedral Potentials Zhang, Wenlin; Gomez, Enrique D.; Milner, Scott T. Macromolecules, Vol. 47, Issue 18 https://doi.org/10.1021/ma500923r	journal	September 2014
Scattering Functions of Semiflexible Polymers with and without Excluded Volume Effects Pedersen, Jan Skov; Schurtenberger, Peter Macromolecules, Vol. 29, Issue 23 https://doi.org/10.1021/ma9607630	journal	January 1996
Remarkable Order of a High-Performance Polymer Takacs, Christopher J.; Treat, Neil D.; Krämer, Stephan Nano Letters, Vol. 13, Issue 6 https://doi.org/10.1021/nl4005805	journal	May 2013
Segregated versus Mixed Interchain Stacking in Highly Oriented Films of Naphthalene Diimide Bithiophene Copolymers Brinkmann, Martin; Gonthier, Eric; Bogen, Stéfan ACS Nano, Vol. 6, Issue 11 https://doi.org/10.1021/nn304213h	journal	October 2012
Intrinsically stretchable and healable semiconducting polymer for organic transistors Oh, Jin Young; Rondeau-Gagné, Simon; Chiu, Yu-Cheng Nature, Vol. 539, Issue 7629 https://doi.org/10.1038/nature20102	journal	November 2016
Skin electronics from scalable fabrication of an intrinsically stretchable transistor array Wang, Sihong; Xu, Jie; Wang, Weichen Nature, Vol. 555, Issue 7694 https://doi.org/10.1038/nature25494	journal	February 2018
Increased elasticity of a low-bandgap conjugated copolymer by random segmentation for mechanically robust solar cells Printz, Adam D.; Savagatrup, Suchol; Burke, Daniel J. RSC Adv., Vol. 4, Issue 26 https://doi.org/10.1039/C4RA00029C	journal	January 2014
Controlling conjugated polymer morphology and charge carrier transport with a flexible-linker approach Gasperini, A.; Bivaud, S.; Sivula, K. Chem. Sci., Vol. 5, Issue 12 https://doi.org/10.1039/C4SC02073A	journal	January 2014
Chain conformations and phase behavior of conjugated polymers Kuei, Brooke; Gomez, Enrique D. Soft Matter, Vol. 13, Issue 1 https://doi.org/10.1039/C6SM00979D	journal	January 2017
Effects of flexibility and branching of side chains on the mechanical properties of low-bandgap conjugated polymers Sugiyama, Fumitaka; Kleinschmidt, Andrew T.; Kayser, Laure V. Polymer Chemistry, Vol. 9, Issue 33 https://doi.org/10.1039/C8PY00820E	journal	January 2018
Influence of amide-containing side chains on the mechanical properties of diketopyrrolopyrrole-based polymers Ocheje, Michael U.; Selivanova, Mariia; Zhang, Song Polymer Chemistry, Vol. 9, Issue 46 https://doi.org/10.1039/C8PY01207E	journal	January 2018
A photoluminescence study of poly(phenylene vinylene) derivatives: The effect of intrinsic persistence length Gettinger, C. L.; Heeger, A. J.; Drake, J. M. The Journal of Chemical Physics, Vol. 101, Issue 2 https://doi.org/10.1063/1.468438	journal	July 1994
Highly stretchable polymer semiconductor films through the nanoconfinement effect Xu, Jie; Wang, Sihong; Wang, Ging-Ji Nathan Science, Vol. 355, Issue 6320 https://doi.org/10.1126/science.aah4496	journal	January 2017
Engineering semiconducting polymers for efficient charge transport Himmelberger, Scott; Salleo, Alberto MRS Communications, Vol. 5, Issue 3 https://doi.org/10.1557/mrc.2015.44	journal	June 2015
Milligram Size Rheology of Molten Polymers Costanzo, Salvatore; Pasquino, Rossana; Läuger, Jörg Fluids, Vol. 4, Issue 1 https://doi.org/10.3390/fluids4010028	journal	February 2019

Similar Records

Mechanical, Morphological, and Charge Transport Properties of NDI Polymers with Variable Built‐in Π‐Conjugation Lengths Probed by Simulation and Experiment

Journal Article · Sat Oct 14 20:00:00 EDT 2023 · Advanced Functional Materials · OSTI ID:2580507

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Conjugated polymers
Flexibility
Polymers
Scattering
Stiffness

Impact of Backbone Rigidity on the Thermomechanical Properties of Semiconducting Polymers with Conjugation Break Spacers

Citation Formats

References (55)

Similar Records

Related Subjects