Comparison of the Mechanical Properties of a Conjugated Polymer Deposited Using Spin Coating, Interfacial Spreading, Solution Shearing, and Spray Coating
Abstract
The mechanical properties of π-conjugated (semiconducting) polymers are a key determinant of the stability and manufacturability of devices envisioned for applications in energy and healthcare. These properties—including modulus, extensibility, toughness, and strength—are influenced by the morphology of the solid film, which depends on the method of processing. To date, the majority of work done on the mechanical properties of semiconducting polymers has been performed on films deposited by spin coating, a process not amenable to the manufacturing of large-area films. Here, we compare the mechanical properties of thin films of regioregular poly(3-heptylthiophene) (P3HpT) produced by three scalable deposition processes—interfacial spreading, solution shearing, and spray coating—and spin coating (as a reference). Our results lead to four principal conclusions. (1) Spray-coated films have poor mechanical robustness due to defects and inhomogeneous thickness. (2) Sheared films show the highest modulus, strength, and toughness, likely resulting from a decrease in free volume. (3) Interfacially spread films show a lower modulus but greater fracture strain than spin-coated films. (4) The trends observed in the tensile behavior of films cast using different deposition processes held true for both P3HpT and poly(3-butylthiophene) (P3BT), an analogue with a higher glass transition temperature. Grazing incidence X-ray diffraction and ultraviolet–visiblemore »
- Authors:
-
- Univ. of California, San Diego, CA (United States)
- Univ. of California, Santa Cruz, CA (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); US Air Force Office of Scientific Research (AFOSR); National Science Foundation (NSF)
- OSTI Identifier:
- 1878574
- Grant/Contract Number:
- AC02-76SF00515; FA9550-19-1-0278; DGE-1144086; 1848069; ECCS-1542148
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Applied Materials and Interfaces
- Additional Journal Information:
- Journal Volume: 13; Journal Issue: 43; Journal ID: ISSN 1944-8244
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; mechanical properties; semiconducting polymers; roll-to-roll deposition; morphology; polymers
Citation Formats
Choudhary, Kartik, Chen, Alexander X., Pitch, Gregory M., Runser, Rory, Urbina, Armando, Dunn, Tim J., Kodur, Moses, Kleinschmidt, Andrew T., Wang, Benjamin G., Bunch, Jordan A., Fenning, David P., Ayzner, Alexander L., and Lipomi, Darren J. Comparison of the Mechanical Properties of a Conjugated Polymer Deposited Using Spin Coating, Interfacial Spreading, Solution Shearing, and Spray Coating. United States: N. p., 2021.
Web. doi:10.1021/acsami.1c13043.
Choudhary, Kartik, Chen, Alexander X., Pitch, Gregory M., Runser, Rory, Urbina, Armando, Dunn, Tim J., Kodur, Moses, Kleinschmidt, Andrew T., Wang, Benjamin G., Bunch, Jordan A., Fenning, David P., Ayzner, Alexander L., & Lipomi, Darren J. Comparison of the Mechanical Properties of a Conjugated Polymer Deposited Using Spin Coating, Interfacial Spreading, Solution Shearing, and Spray Coating. United States. https://doi.org/10.1021/acsami.1c13043
Choudhary, Kartik, Chen, Alexander X., Pitch, Gregory M., Runser, Rory, Urbina, Armando, Dunn, Tim J., Kodur, Moses, Kleinschmidt, Andrew T., Wang, Benjamin G., Bunch, Jordan A., Fenning, David P., Ayzner, Alexander L., and Lipomi, Darren J. Fri .
"Comparison of the Mechanical Properties of a Conjugated Polymer Deposited Using Spin Coating, Interfacial Spreading, Solution Shearing, and Spray Coating". United States. https://doi.org/10.1021/acsami.1c13043. https://www.osti.gov/servlets/purl/1878574.
@article{osti_1878574,
title = {Comparison of the Mechanical Properties of a Conjugated Polymer Deposited Using Spin Coating, Interfacial Spreading, Solution Shearing, and Spray Coating},
author = {Choudhary, Kartik and Chen, Alexander X. and Pitch, Gregory M. and Runser, Rory and Urbina, Armando and Dunn, Tim J. and Kodur, Moses and Kleinschmidt, Andrew T. and Wang, Benjamin G. and Bunch, Jordan A. and Fenning, David P. and Ayzner, Alexander L. and Lipomi, Darren J.},
abstractNote = {The mechanical properties of π-conjugated (semiconducting) polymers are a key determinant of the stability and manufacturability of devices envisioned for applications in energy and healthcare. These properties—including modulus, extensibility, toughness, and strength—are influenced by the morphology of the solid film, which depends on the method of processing. To date, the majority of work done on the mechanical properties of semiconducting polymers has been performed on films deposited by spin coating, a process not amenable to the manufacturing of large-area films. Here, we compare the mechanical properties of thin films of regioregular poly(3-heptylthiophene) (P3HpT) produced by three scalable deposition processes—interfacial spreading, solution shearing, and spray coating—and spin coating (as a reference). Our results lead to four principal conclusions. (1) Spray-coated films have poor mechanical robustness due to defects and inhomogeneous thickness. (2) Sheared films show the highest modulus, strength, and toughness, likely resulting from a decrease in free volume. (3) Interfacially spread films show a lower modulus but greater fracture strain than spin-coated films. (4) The trends observed in the tensile behavior of films cast using different deposition processes held true for both P3HpT and poly(3-butylthiophene) (P3BT), an analogue with a higher glass transition temperature. Grazing incidence X-ray diffraction and ultraviolet–visible spectroscopy reveal many notable differences in the solid structures of P3HpT films generated by all four processes. Herein, while these morphological differences provide possible explanations for differences in the electronic properties (hole mobility), we find that the mechanical properties of the film are dominated by the free volume and surface topography. In field-effect transistors, spread films had mobilities more than 1 magnitude greater than any other films, likely due to a relatively high proportion of edge-on texturing and long coherence length in the crystalline domains. Overall, spread films offer the best combination of deformability and charge-transport properties.},
doi = {10.1021/acsami.1c13043},
journal = {ACS Applied Materials and Interfaces},
number = 43,
volume = 13,
place = {United States},
year = {Fri Oct 22 00:00:00 EDT 2021},
month = {Fri Oct 22 00:00:00 EDT 2021}
}
Works referenced in this record:
Comparative study of the nanomorphology of spray and spin coated PTB7 polymer: Fullerene films
journal, April 2016
- Al-Hussein, Mahmoud; Herzig, Eva M.; Schindler, Markus
- Polymer Engineering & Science, Vol. 56, Issue 8
Optimizing Morphology to Trade Off Charge Transport and Mechanical Properties of Stretchable Conjugated Polymer Films
journal, April 2021
- Ding, Zicheng; Liu, Dongle; Zhao, Kui
- Macromolecules, Vol. 54, Issue 9
Electrical and mechanical properties of oriented poly(3-alkylthiophenes): 2. Effect of side-chain length
journal, January 1992
- Moulton, Jeff; Smith, Paul
- Polymer, Vol. 33, Issue 11
Control of the Interchain π−π Interaction and Electron Density Distribution at the Surface of Conjugated Poly(3-hexylthiophene) Thin Films
journal, August 2007
- Hao, X. T.; Hosokai, T.; Mitsuo, N.
- The Journal of Physical Chemistry B, Vol. 111, Issue 35
Glass Transition Phenomenon for Conjugated Polymers
journal, April 2019
- Qian, Zhiyuan; Cao, Zhiqiang; Galuska, Luke
- Macromolecular Chemistry and Physics, Vol. 220, Issue 11
Viability of stretchable poly(3-heptylthiophene) (P3HpT) for organic solar cells and field-effect transistors
journal, May 2015
- Savagatrup, Suchol; Printz, Adam D.; Wu, Haosheng
- Synthetic Metals, Vol. 203
Molecular Origin of Strain‐Induced Chain Alignment in PDPP‐Based Semiconducting Polymeric Thin Films
journal, March 2021
- Zhang, Song; Alesadi, Amirhadi; Mason, Gage T.
- Advanced Functional Materials, Vol. 31, Issue 21
Branched Polyethylene as a Plasticizing Additive to Modulate the Mechanical Properties of π-Conjugated Polymers
journal, October 2019
- Selivanova, Mariia; Zhang, Song; Billet, Blandine
- Macromolecules, Vol. 52, Issue 20
Probing the Viscoelastic Property of Pseudo Free-Standing Conjugated Polymeric Thin Films
journal, May 2018
- Zhang, Song; Ocheje, Michael U.; Luo, Shaochuan
- Macromolecular Rapid Communications, Vol. 39, Issue 14
Advanced materials and processes for polymer solar cell devices
journal, January 2010
- Helgesen, Martin; Søndergaard, Roar; Krebs, Frederik C.
- J. Mater. Chem., Vol. 20, Issue 1
Low Elastic Modulus and High Charge Mobility of Low-Crystallinity Indacenodithiophene-Based Semiconducting Polymers for Potential Applications in Stretchable Electronics
journal, August 2018
- Li, Yilin; Tatum, Wesley K.; Onorato, Jonathan W.
- Macromolecules, Vol. 51, Issue 16
Molecular packing control enables excellent performance and mechanical property of blade-cast all-polymer solar cells
journal, May 2019
- Lin, Baojun; Zhang, Lin; Zhao, Heng
- Nano Energy, Vol. 59
Role of Polymer Segregation on the Mechanical Behavior of All-Polymer Solar Cell Active Layers
journal, December 2017
- Balar, Nrup; Xiong, Yuan; Ye, Long
- ACS Applied Materials & Interfaces, Vol. 9, Issue 50
Interfacial Drawing: Roll-to-Roll Coating of Semiconducting Polymer and Barrier Films onto Plastic Foils and Textiles
journal, October 2019
- Runser, Rory; Root, Samuel E.; Ober, Derick E.
- Chemistry of Materials, Vol. 31, Issue 21
Effect of solution aging on morphology and electrical characteristics of regioregular P3HT FETs fabricated by spin coating and spray coating
journal, November 2011
- Bielecka, U.; Lutsyk, P.; Janus, K.
- Organic Electronics, Vol. 12, Issue 11
Enhancement of Transport Characteristics in Poly(3-hexylthiophene) Films Deposited with Floating Film Transfer Method
journal, November 2009
- Morita, Takeomi; Singh, Vipul; Nagamatsu, Shuichi
- Applied Physics Express, Vol. 2, Issue 11
Backbone orientation in semiconducting polymers
journal, February 2015
- Osaka, Itaru; Takimiya, Kazuo
- Polymer, Vol. 59
Spray-printed organic field-effect transistors and complementary inverters
journal, January 2013
- Khim, Dongyoon; Baeg, Kang-Jun; Yu, Byung-Kwan
- Journal of Materials Chemistry C, Vol. 1, Issue 7
Highly oriented low-modulus materials from liquid-crystalline polymers: the ultimate penalty for solubilizing alkyl side chains
journal, March 1990
- Postema, Aaldrik R.; Liou, K.; Wudl, Fred
- Macromolecules, Vol. 23, Issue 6
Mechanical Properties of Organic Semiconductors for Stretchable, Highly Flexible, and Mechanically Robust Electronics
journal, March 2017
- Root, Samuel E.; Savagatrup, Suchol; Printz, Adam D.
- Chemical Reviews, Vol. 117, Issue 9
Strategic design and synthesis of π-conjugated polymers suitable as intrinsically stretchable semiconducting materials
journal, June 2021
- Higashihara, Tomoya
- Polymer Journal, Vol. 53, Issue 10
Enhanced Charge Transport in Polymer Thin-Film Transistors Prepared by Contact Film Transfer Method
journal, October 2009
- Wei, Qingshuo; Miyanishi, Shoji; Tajima, Keisuke
- ACS Applied Materials & Interfaces, Vol. 1, Issue 11
Experimental and modeling study of low-voltage field-effect transistors fabricated with molecularly aligned copolymer floating films
journal, January 2018
- Nawaz, Ali; Tavares, Ana C. B.; Trang Do, Thu
- Flexible and Printed Electronics, Vol. 3, Issue 1
Morphology control strategies for solution-processed organic semiconductor thin films
journal, January 2014
- Diao, Ying; Shaw, Leo; Bao, Zhenan
- Energy Environ. Sci., Vol. 7, Issue 7
Ultrafast formation of air-processable and high-quality polymer films on an aqueous substrate
journal, August 2016
- Noh, Jonghyeon; Jeong, Seonju; Lee, Jung-Yong
- Nature Communications, Vol. 7, Issue 1
Elucidating the Influence of Side-Chain Circular Distribution on the Crack Onset Strain and Hole Mobility of Near-Amorphous Indacenodithiophene Copolymers
journal, August 2020
- Sommerville, Parker J. W.; Li, Yilin; Dong, Ban Xuan
- Macromolecules, Vol. 53, Issue 17
Direct Uniaxial Alignment of a Donor–Acceptor Semiconducting Polymer Using Single-Step Solution Shearing
journal, March 2016
- Shaw, Leo; Hayoz, Pascal; Diao, Ying
- ACS Applied Materials & Interfaces, Vol. 8, Issue 14
Simultaneously Induced Self-Assembly of Poly(3-hexylthiophene) (P3HT) Nanowires and Thin-Film Fabrication via Solution-Floating Method on a Water Substrate
journal, July 2017
- Kim, Yong-Jae; Jung, Hee-Tae; Ahn, Chi Won
- Advanced Materials Interfaces, Vol. 4, Issue 19
Modelling the morphology and thermomechanical behaviour of low-bandgap conjugated polymers and bulk heterojunction films
journal, January 2017
- Root, Samuel E.; Jackson, Nicholas E.; Savagatrup, Suchol
- Energy & Environmental Science, Vol. 10, Issue 2
Solid-Phase Deposition: Conformal Coverage of Micron-Scale Relief Structures with Stretchable Semiconducting Polymers
journal, June 2021
- Esparza, Guillermo L.; Lipomi, Darren J.
- ACS Materials Letters, Vol. 3, Issue 7
Roll-to-roll fabrication of polymer solar cells
journal, January 2012
- Søndergaard, Roar; Hösel, Markus; Angmo, Dechan
- Materials Today, Vol. 15, Issue 1-2
Layer-by-layer coating of oriented conjugated polymer films towards anisotropic electronics
journal, May 2017
- Pandey, Manish; Sadakata, Shifumi; Nagamatsu, Shuichi
- Synthetic Metals, Vol. 227
Physical-Organic Chemistry: A Swiss Army Knife
journal, November 2015
- Whitesides, George M.
- Israel Journal of Chemistry, Vol. 56, Issue 1
Flexible Bottom-Gated Organic Field-Effect Transistors Utilizing Stamped Polymer Layers from the Surface of Water
journal, May 2020
- Sung, Yoori; Shin, Eul-Yong; Noh, Yong-Young
- ACS Applied Materials & Interfaces, Vol. 12, Issue 22
Tuning Mechanical and Optoelectrical Properties of Poly(3-hexylthiophene) through Systematic Regioregularity Control
journal, June 2015
- Kim, Jin-Seong; Kim, Jae-Han; Lee, Wonho
- Macromolecules, Vol. 48, Issue 13
Effect of Solution Shearing Method on Packing and Disorder of Organic Semiconductor Polymers
journal, March 2015
- Giri, Gaurav; DeLongchamp, Dean M.; Reinspach, Julia
- Chemistry of Materials, Vol. 27, Issue 7
Characterization of spray-coating methods for conjugated polymer blend thin films
journal, March 2014
- Noebels, Matthias; Cross, Rachel E.; Evans, D. A.
- Journal of Materials Science, Vol. 49, Issue 12
Recent advances in the orientation of conjugated polymers for organic field-effect transistors
journal, January 2019
- Pandey, Manish; Kumari, Nikita; Nagamatsu, Shuichi
- Journal of Materials Chemistry C, Vol. 7, Issue 43
Sequential Blade‐Coated Acceptor and Donor Enables Simultaneous Enhancement of Efficiency, Stability, and Mechanical Properties for Organic Solar Cells
journal, January 2020
- Wang, Yilin; Zhu, Qinglian; Naveed, Hafiz Bilal
- Advanced Energy Materials, Vol. 10, Issue 7
Navigating the Color Palette of Solution-Processable Electrochromic Polymers
journal, November 2010
- Amb, Chad M.; Dyer, Aubrey L.; Reynolds, John R.
- Chemistry of Materials, Vol. 23, Issue 3
Crystalline Ultrasmooth Self-Assembled Monolayers of Alkylsilanes for Organic Field-Effect Transistors
journal, July 2009
- Ito, Yutaka; Virkar, Ajay A.; Mannsfeld, Stefan
- Journal of the American Chemical Society, Vol. 131, Issue 26
Effect of Confinement on Stiffness and Fracture of Thin Amorphous Polymer Films
journal, November 2011
- Lee, Jung-Hyun; Chung, Jun Young; Stafford, Christopher M.
- ACS Macro Letters, Vol. 1, Issue 1
Patterning technology for solution-processed organic crystal field-effect transistors
journal, March 2014
- Li, Yun; Sun, Huabin; Shi, Yi
- Science and Technology of Advanced Materials, Vol. 15, Issue 2
Polymer-based solar cells having an active area of 1.6 cm 2 fabricated via spray coating
journal, December 2015
- Scarratt, N. W.; Griffin, J.; Wang, T.
- APL Materials, Vol. 3, Issue 12
Morphological, Chemical, and Electronic Changes of the Conjugated Polymer PTB7 with Thermal Annealing
journal, April 2018
- Savikhin, Victoria; Jagadamma, Lethy K.; Purvis, Lafe J.
- iScience, Vol. 2
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
Tensile testing of ultra-thin films on water surface
journal, October 2013
- Kim, Jae-Han; Nizami, Adeel; Hwangbo, Yun
- Nature Communications, Vol. 4, Issue 1
A Facile Approach to Improve Interchain Packing Order and Charge Mobilities by Self-Assembly of Conjugated Polymers on Water
journal, October 2018
- Yang, Yizhou; Liu, Zitong; Chen, Jianmei
- Advanced Science, Vol. 5, Issue 11
Beyond Stretchability: Strength, Toughness, and Elastic Range in Semiconducting Polymers
journal, August 2020
- Chen, Alexander X.; Kleinschmidt, Andrew T.; Choudhary, Kartik
- Chemistry of Materials, Vol. 32, Issue 18
Understanding Marangoni flow-driven solidification of polymer semiconducting films on an aqueous substrate
journal, January 2020
- Choi, Giheon; Lee, Kanghuck; Oh, Seungtaek
- Journal of Materials Chemistry C, Vol. 8, Issue 29
Rapid Formation and Macroscopic Self-Assembly of Liquid-Crystalline, High-Mobility, Semiconducting Thienothiophene
journal, January 2018
- Pandey, Manish; Gowda, Ashwathanarayana; Nagamatsu, Shuichi
- Advanced Materials Interfaces, Vol. 5, Issue 6
Correlating Stiffness, Ductility, and Morphology of Polymer:Fullerene Films for Solar Cell Applications
journal, November 2012
- Awartani, Omar; Lemanski, Bethany I.; Ro, Hyun Wook
- Advanced Energy Materials, Vol. 3, Issue 3
Measuring the Glass Transition Temperature of Conjugated Polymer Films with Ultraviolet–Visible Spectroscopy
journal, March 2017
- Root, Samuel E.; Alkhadra, Mohammad A.; Rodriquez, Daniel
- Chemistry of Materials, Vol. 29, 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
Competition between deformability and charge transport in semiconducting polymers for flexible and stretchable electronics
journal, June 2016
- Printz, Adam D.; Lipomi, Darren J.
- Applied Physics Reviews, Vol. 3, Issue 2
Glass transition temperature from the chemical structure of conjugated polymers
journal, February 2020
- Xie, Renxuan; Weisen, Albree R.; Lee, Youngmin
- Nature Communications, Vol. 11, Issue 1
Charge Transport in Highly Face-On Poly(3-hexylthiophene) Films
journal, August 2013
- Gargi, Deepak; Kline, R. Joseph; DeLongchamp, Dean M.
- The Journal of Physical Chemistry C, Vol. 117, Issue 34