The coupling and competition of crystallization and phase separation, correlating thermodynamics and kinetics in OPV morphology and performances
Abstract
The active layer morphology transition of organic photovoltaics under non-equilibrium conditions are of vital importance in determining the device power conversion efficiency and stability; however, a general and unified picture on this issue has not been well addressed. Using combined in situ and ex situ morphology characterizations, morphological parameters relating to kinetics and thermodynamics of morphology evolution are extracted and studied in model systems under thermal annealing. The coupling and competition of crystallization and demixing are found to be critical in morphology evolution, phase purification and interfacial orientation. A unified model summarizing different phase diagrams and all possible kinetic routes is proposed. The current observations address the fundamental issues underlying the formation of the complex multi-length scale morphology in bulk heterojunction blends and provide useful morphology optimization guidelines for processing devices with higher efficiency and stability.
- Authors:
-
[1];
[2];
[3];
[6];
[6];
[7];
[8];
[3]
- Shanghai Jiao Tong Univ. (China). School of Chemistry and Chemical Engineering. Center of Hydrogen Science. In-situ Center for Physical Science. Frontiers Science Center for Transformative Molecules; Hong Kong Univ. of Science and Technology (Hong Kong). Dept. of Chemistry
- Univ. of Washington, Seattle, WA (United States). Dept. of Materials Science and Engineering
- Shanghai Jiao Tong Univ. (China). School of Chemistry and Chemical Engineering. Center of Hydrogen Science. In-situ Center for Physical Science. Frontiers Science Center for Transformative Molecules
- South China Univ. of Technology (SCUT), Guangzhou (China). State Key Lab. of Luminescent Materials and Devices
- Dongyue Future Hydrogen Energy Materials Company, Shandong (China). State Key Lab. of Fluorinated Functional Membrane Materials
- Univ. of Southern Mississippi, Hattiesburg, MS (United States). Center for Optoelectronic Materials and Devices. School of Polymer Science and Engineering
- Univ. of Washington, Seattle, WA (United States). Dept. of Materials Science and Engineering; City Univ. of Hong Kong (Hong Kong). Dept. of Chemistry
- Hong Kong Univ. of Science and Technology (Hong Kong). Dept. of Chemistry
- Publication Date:
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Natural Science Foundation of China (NSFC); Beijing National Laboratory for Molecular Sciences; US Department of the Navy, Office of Naval Research (ONR); US Air Force Office of Scientific Research (AFOSR); Guangdong Major Project of Basic and Applied Basic Research
- OSTI Identifier:
- 1816568
- Grant/Contract Number:
- AC02-05CH1123; 51973110; 21734009; 21905102; 61805138; BNLMS201902; N00014-17-1-2201; N0001-20-1-2191; FA9550-18-121205002; 2019B030302007
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 12; Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; organic molecules in materials science; solar cells; surfaces, interfaces and thin films
Citation Formats
Wang, Zaiyu, Gao, Ke, Kan, Yuanyuan, Zhang, Ming, Qiu, Chaoqun, Zhu, Lei, Zhao, Zhe, Peng, Xiaobin, Feng, Wei, Qian, Zhiyuan, Gu, Xiaodan, Jen, Alex K. -Y., Tang, Ben Zhong, Cao, Yong, Zhang, Yongming, and Liu, Feng. The coupling and competition of crystallization and phase separation, correlating thermodynamics and kinetics in OPV morphology and performances. United States: N. p., 2021.
Web. doi:10.1038/s41467-020-20515-3.
Wang, Zaiyu, Gao, Ke, Kan, Yuanyuan, Zhang, Ming, Qiu, Chaoqun, Zhu, Lei, Zhao, Zhe, Peng, Xiaobin, Feng, Wei, Qian, Zhiyuan, Gu, Xiaodan, Jen, Alex K. -Y., Tang, Ben Zhong, Cao, Yong, Zhang, Yongming, & Liu, Feng. The coupling and competition of crystallization and phase separation, correlating thermodynamics and kinetics in OPV morphology and performances. United States. https://doi.org/10.1038/s41467-020-20515-3
Wang, Zaiyu, Gao, Ke, Kan, Yuanyuan, Zhang, Ming, Qiu, Chaoqun, Zhu, Lei, Zhao, Zhe, Peng, Xiaobin, Feng, Wei, Qian, Zhiyuan, Gu, Xiaodan, Jen, Alex K. -Y., Tang, Ben Zhong, Cao, Yong, Zhang, Yongming, and Liu, Feng. Tue .
"The coupling and competition of crystallization and phase separation, correlating thermodynamics and kinetics in OPV morphology and performances". United States. https://doi.org/10.1038/s41467-020-20515-3. https://www.osti.gov/servlets/purl/1816568.
@article{osti_1816568,
title = {The coupling and competition of crystallization and phase separation, correlating thermodynamics and kinetics in OPV morphology and performances},
author = {Wang, Zaiyu and Gao, Ke and Kan, Yuanyuan and Zhang, Ming and Qiu, Chaoqun and Zhu, Lei and Zhao, Zhe and Peng, Xiaobin and Feng, Wei and Qian, Zhiyuan and Gu, Xiaodan and Jen, Alex K. -Y. and Tang, Ben Zhong and Cao, Yong and Zhang, Yongming and Liu, Feng},
abstractNote = {The active layer morphology transition of organic photovoltaics under non-equilibrium conditions are of vital importance in determining the device power conversion efficiency and stability; however, a general and unified picture on this issue has not been well addressed. Using combined in situ and ex situ morphology characterizations, morphological parameters relating to kinetics and thermodynamics of morphology evolution are extracted and studied in model systems under thermal annealing. The coupling and competition of crystallization and demixing are found to be critical in morphology evolution, phase purification and interfacial orientation. A unified model summarizing different phase diagrams and all possible kinetic routes is proposed. The current observations address the fundamental issues underlying the formation of the complex multi-length scale morphology in bulk heterojunction blends and provide useful morphology optimization guidelines for processing devices with higher efficiency and stability.},
doi = {10.1038/s41467-020-20515-3},
journal = {Nature Communications},
number = 1,
volume = 12,
place = {United States},
year = {Tue Jan 12 00:00:00 EST 2021},
month = {Tue Jan 12 00:00:00 EST 2021}
}
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:
Bulk Heterojunction Photovoltaic Active Layers via Bilayer Interdiffusion
journal, May 2011
- Chen, Dian; Liu, Feng; Wang, Cheng
- Nano Letters, Vol. 11, Issue 5
Crystallization kinetics of polymer–diluent mixtures. Influence of benzophenone on the spherulitic growth rate of isotactic polystyrene
journal, May 1968
- Boon, J.; Azcue, J. M.
- Journal of Polymer Science Part A-2: Polymer Physics, Vol. 6, Issue 5
Fast Printing and In Situ Morphology Observation of Organic Photovoltaics Using Slot-Die Coating
journal, December 2014
- Liu, Feng; Ferdous, Sunzida; Schaible, Eric
- Advanced Materials, Vol. 27, Issue 5
Morphology Development in Solution-Processed Functional Organic Blend Films: An In Situ Viewpoint
journal, April 2017
- Richter, Lee J.; DeLongchamp, Dean M.; Amassian, Aram
- Chemical Reviews, Vol. 117, Issue 9
Efficient Organic Solar Cell with 16.88% Efficiency Enabled by Refined Acceptor Crystallization and Morphology with Improved Charge Transfer and Transport Properties
journal, March 2020
- Zhu, Lei; Zhang, Ming; Zhou, Guanqing
- Advanced Energy Materials, Vol. 10, Issue 18
In Situ GIWAXS Analysis of Solvent and Additive Effects on PTB7 Thin Film Microstructure Evolution during Spin Coating
journal, October 2017
- Manley, Eric F.; Strzalka, Joseph; Fauvell, Thomas J.
- Advanced Materials, Vol. 29, Issue 43
On the mechanism of pinning in phase‐separating polymer blends
journal, December 1995
- Castellano, Claudio; Glotzer, Sharon C.
- The Journal of Chemical Physics, Vol. 103, Issue 21
Self-decelerated crystallization in blends of polyhydroxyether of bisphenol A and poly(ethylene oxide) upon isothermal crystallization
journal, May 2000
- Zheng, S.; Jungnickel, B. -J.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 38, Issue 9
Extension of theory of growth of chain‐folded polymer crystals to large undercoolings
journal, October 1973
- Lauritzen, John I.; Hoffman, John D.
- Journal of Applied Physics, Vol. 44, Issue 10
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
Understanding the Morphology of PTB7:PCBM Blends in Organic Photovoltaics
journal, October 2013
- Liu, Feng; Zhao, Wei; Tumbleston, John R.
- Advanced Energy Materials, Vol. 4, Issue 5
Real-time X-ray scattering studies of film evolution in high performing small-molecule–fullerene organic solar cells
journal, January 2015
- Engmann, Sebastian; Bokel, Felicia A.; Herzing, Andrew A.
- Journal of Materials Chemistry A, Vol. 3, Issue 16
Rational Design of High Performance Conjugated Polymers for Organic Solar Cells
journal, January 2012
- Zhou, Huaxing; Yang, Liqiang; You, Wei
- Macromolecules, Vol. 45, Issue 2
The influence of molecular orientation on organic bulk heterojunction solar cells
journal, April 2014
- Tumbleston, John R.; Collins, Brian A.; Yang, Liqiang
- Nature Photonics, Vol. 8, Issue 5
Bulk-Heterojunction Organic Solar Cells: Five Core Technologies for Their Commercialization
journal, June 2016
- Kang, Hongkyu; Kim, Geunjin; Kim, Junghwan
- Advanced Materials, Vol. 28, Issue 36
P3HT/PCBM Bulk Heterojunction Organic Photovoltaics: Correlating Efficiency and Morphology
journal, February 2011
- Chen, Dian; Nakahara, Atsuhiro; Wei, Dongguang
- Nano Letters, Vol. 11, Issue 2, p. 561-567
Quantitative relations between interaction parameter, miscibility and function in organic solar cells
journal, February 2018
- Ye, Long; Hu, Huawei; Ghasemi, Masoud
- Nature Materials, Vol. 17, Issue 3
The Temperature Dependence of Relaxation Mechanisms in Amorphous Polymers and Other Glass-forming Liquids
journal, July 1955
- Williams, Malcolm L.; Landel, Robert F.; Ferry, John D.
- Journal of the American Chemical Society, Vol. 77, Issue 14
High-efficiency small-molecule ternary solar cells with a hierarchical morphology enabled by synergizing fullerene and non-fullerene acceptors
journal, September 2018
- Zhou, Zichun; Xu, Shengjie; Song, Jingnan
- Nature Energy, Vol. 3, Issue 11
Green-solvent-processable organic solar cells
journal, November 2016
- Zhang, Shaoqing; Ye, Long; Zhang, Hao
- Materials Today, Vol. 19, Issue 9
Phase Separation in Bulk Heterojunctions of Semiconducting Polymers and Fullerenes for Photovoltaics
journal, April 2014
- Treat, Neil D.; Chabinyc, Michael L.
- Annual Review of Physical Chemistry, Vol. 65, Issue 1
Solvent Additives: Key Morphology-Directing Agents for Solution-Processed Organic Solar Cells
journal, June 2018
- McDowell, Caitlin; Abdelsamie, Maged; Toney, Michael F.
- Advanced Materials, Vol. 30, Issue 33
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
Quantitative analysis of lattice disorder and crystallite size in organic semiconductor thin films
journal, July 2011
- Rivnay, Jonathan; Noriega, Rodrigo; Kline, R. Joseph
- Physical Review B, Vol. 84, Issue 4
Rationalizing Phase Transitions with Thermal Annealing Temperatures for P3HT:PCBM Organic Photovoltaic Devices
journal, January 2012
- Pearson, Andrew J.; Wang, Tao; Jones, Richard A. L.
- Macromolecules, Vol. 45, Issue 3
Phase Diagram of P3HT/PCBM Blends and Its Implication for the Stability of Morphology
journal, February 2009
- Zhao, Jun; Swinnen, Ann; Van Assche, Guy
- The Journal of Physical Chemistry B, Vol. 113, Issue 6, p. 1587-1591
The Scherrer equation versus the 'Debye-Scherrer equation'
journal, August 2011
- Holzwarth, Uwe; Gibson, Neil
- Nature Nanotechnology, Vol. 6, Issue 9
Non-fullerene acceptors for organic solar cells
journal, February 2018
- Yan, Cenqi; Barlow, Stephen; Wang, Zhaohui
- Nature Reviews Materials, Vol. 3, Issue 3
Theory of Cold Crystallization of High Polymers
journal, December 1958
- Wunderlich, B.
- The Journal of Chemical Physics, Vol. 29, Issue 6
New Types of Phase Separation Behavior during the Crystallization Process in Polymer Blends with Phase Diagram
journal, September 1985
- Tanaka, Hajime; Nishi, Toshio
- Physical Review Letters, Vol. 55, Issue 10
Characterization of the morphology of solution-processed bulk heterojunction organic photovoltaics
journal, December 2013
- Liu, Feng; Gu, Yu; Shen, Xiaobo
- Progress in Polymer Science, Vol. 38, Issue 12
Relating Chemical Structure to Device Performance via Morphology Control in Diketopyrrolopyrrole-Based Low Band Gap Polymers
journal, December 2013
- Liu, Feng; Wang, Cheng; Baral, Jayanta K.
- Journal of the American Chemical Society, Vol. 135, Issue 51
Entropy-induced frozen morphology in unstable polymer blends
journal, March 1992
- Kotnis, Mahesh A.; Muthukumar, M.
- Macromolecules, Vol. 25, Issue 6
Melting Point Depression and Kinetic Effects of Cooling on Crystallization in Poly(vinylidene fluoride)-Poly(methyl methacrylate) Mixtures
journal, November 1975
- Nishi, T.; Wang, T. T.
- Macromolecules, Vol. 8, Issue 6
The Impact of Molecular Orientation on the Photovoltaic Properties of a Phthalocyanine/Fullerene Heterojunction
journal, April 2012
- Rand, Barry P.; Cheyns, David; Vasseur, Karolien
- Advanced Functional Materials, Vol. 22, Issue 14
Efficient photodiodes from interpenetrating polymer networks
journal, August 1995
- Halls, J. J. M.; Walsh, C. A.; Greenham, N. C.
- Nature, Vol. 376, Issue 6540, p. 498-500
25th Anniversary Article: Bulk Heterojunction Solar Cells: Understanding the Mechanism of Operation
journal, December 2013
- Heeger, Alan J.
- Advanced Materials, Vol. 26, Issue 1
Single-Junction Organic Solar Cell with over 15% Efficiency Using Fused-Ring Acceptor with Electron-Deficient Core
journal, April 2019
- Yuan, Jun; Zhang, Yunqiang; Zhou, Liuyang
- Joule, Vol. 3, Issue 4
Critical review of the molecular design progress in non-fullerene electron acceptors towards commercially viable organic solar cells
journal, January 2019
- Wadsworth, Andrew; Moser, Maximilian; Marks, Adam
- Chemical Society Reviews, Vol. 48, Issue 6
Glass Forming Acceptor Alloys for Highly Efficient and Thermally Stable Ternary Organic Solar Cells
journal, January 2018
- de Zerio, Amaia Diaz; Müller, Christian
- Advanced Energy Materials, Vol. 8, Issue 28
In Situ Characterization of Polymer–Fullerene Bilayer Stability
journal, January 2015
- Leman, Deborah; Kelly, Mary Allison; Ness, Stuart
- Macromolecules, Vol. 48, Issue 2
In Situ Analysis of Solvent and Additive Effects on Film Morphology Evolution in Spin-Cast Small-Molecule and Polymer Photovoltaic Materials
journal, May 2018
- Manley, Eric F.; Strzalka, Joseph; Fauvell, Thomas J.
- Advanced Energy Materials, Vol. 8, Issue 23
Organic solar cells based on non-fullerene acceptors
journal, January 2018
- Hou, Jianhui; Inganäs, Olle; Friend, Richard H.
- Nature Materials, Vol. 17, Issue 2
Deep Absorbing Porphyrin Small Molecule for High-Performance Organic Solar Cells with Very Low Energy Losses
journal, June 2015
- Gao, Ke; Li, Lisheng; Lai, Tianqi
- Journal of the American Chemical Society, Vol. 137, Issue 23
Solution-processed small-molecule solar cells with 6.7% efficiency
journal, November 2011
- Sun, Yanming; Welch, Gregory C.; Leong, Wei Lin
- Nature Materials, Vol. 11, Issue 1, p. 44-48
Donor polymer design enables efficient non-fullerene organic solar cells
journal, October 2016
- Li, Zhengke; Jiang, Kui; Yang, Guofang
- Nature Communications, Vol. 7, Issue 1
Organic and solution-processed tandem solar cells with 17.3% efficiency
journal, August 2018
- Meng, Lingxian; Zhang, Yamin; Wan, Xiangjian
- Science, Vol. 361, Issue 6407
Recent Advances in Bulk Heterojunction Polymer Solar Cells
journal, August 2015
- Lu, Luyao; Zheng, Tianyue; Wu, Qinghe
- Chemical Reviews, Vol. 115, Issue 23
High fabrication yield organic tandem photovoltaics combining vacuum- and solution-processed subcells with 15% efficiency
journal, April 2018
- Che, Xiaozhou; Li, Yongxi; Qu, Yue
- Nature Energy, Vol. 3, Issue 5
Polymer Photovoltaic Cells: Enhanced Efficiencies via a Network of Internal Donor-Acceptor Heterojunctions
journal, December 1995
- Yu, G.; Gao, J.; Hummelen, J. C.
- Science, Vol. 270, Issue 5243, p. 1789-1791
Effects of Thermal Annealing Upon the Morphology of Polymer-Fullerene Blends
journal, August 2010
- Verploegen, Eric; Mondal, Rajib; Bettinger, Christopher J.
- Advanced Functional Materials, Vol. 20, Issue 20
Reducing the efficiency–stability–cost gap of organic photovoltaics with highly efficient and stable small molecule acceptor ternary solar cells
journal, November 2016
- Baran, Derya; Ashraf, Raja Shahid; Hanifi, David A.
- Nature Materials, Vol. 16, Issue 3
The Power of Materials Science Tools for Gaining Insights into Organic Semiconductors
journal, July 2015
- Treat, Neil D.; Westacott, Paul; Stingelin, Natalie
- Annual Review of Materials Research, Vol. 45, Issue 1
New insight of molecular interaction, crystallization and phase separation in higher performance small molecular solar cells via solvent vapor annealing
journal, December 2016
- Gao, Ke; Deng, Wanyuan; Xiao, Liangang
- Nano Energy, Vol. 30
Non-Basic High-Performance Molecules for Solution-Processed Organic Solar Cells
journal, June 2012
- van der Poll, Thomas S.; Love, John A.; Nguyen, Thuc-Quyen
- Advanced Materials, Vol. 24, Issue 27
A Phenomenological Theory of Spherulitic Crystallization
journal, August 1963
- Keith, H. D.; Padden, F. J.
- Journal of Applied Physics, Vol. 34, Issue 8
Local phase separation at the growth front of a polymer spherulite during crystallization and nonlinear spherulitic growth in a polymer mixture with a phase diagram
journal, January 1989
- Tanaka, Hajime; Nishi, Toshio
- Physical Review A, Vol. 39, Issue 2
Small-molecule solar cells with efficiency over 9%
journal, November 2014
- Zhang, Qian; Kan, Bin; Liu, Feng
- Nature Photonics, Vol. 9, Issue 1
On the morphology of polymer-based photovoltaics
journal, March 2012
- Liu, Feng; Gu, Yu; Jung, Jae Woong
- Journal of Polymer Science Part B: Polymer Physics, Vol. 50, Issue 15
Next-generation organic photovoltaics based on non-fullerene acceptors
journal, February 2018
- Cheng, Pei; Li, Gang; Zhan, Xiaowei
- Nature Photonics, Vol. 12, Issue 3
Multi-Length-Scale Morphologies Driven by Mixed Additives in Porphyrin-Based Organic Photovoltaics
journal, April 2016
- Gao, Ke; Miao, Jingsheng; Xiao, Liangang
- Advanced Materials, Vol. 28, Issue 23
Solution-Processed Organic Solar Cells Based on Dialkylthiol-Substituted Benzodithiophene Unit with Efficiency near 10%
journal, October 2014
- Kan, Bin; Zhang, Qian; Li, Miaomiao
- Journal of the American Chemical Society, Vol. 136, Issue 44
Scherrer grain-size analysis adapted to grazing-incidence scattering with area detectors
journal, October 2009
- Smilgies, Detlef-M.
- Journal of Applied Crystallography, Vol. 42, Issue 6
Highly Efficient All‐Small‐Molecule Organic Solar Cells with Appropriate Active Layer Morphology by Side Chain Engineering of Donor Molecules and Thermal Annealing
journal, April 2020
- Qiu, Beibei; Chen, Zeng; Qin, Shucheng
- Advanced Materials, Vol. 32, Issue 21
A Quantitative Study of PCBM Diffusion during Annealing of P3HT:PCBM Blend Films
journal, November 2009
- Watts, Benjamin; Belcher, Warwick J.; Thomsen, Lars
- Macromolecules, Vol. 42, Issue 21
Crystallization-Induced Phase Separation in Solution-Processed Small Molecule Bulk Heterojunction Organic Solar Cells
journal, February 2014
- Sharenko, Alexander; Kuik, Martijn; Toney, Michael F.
- Advanced Functional Materials, Vol. 24, Issue 23
Organic photovoltaics
journal, January 2009
- Kippelen, Bernard; Brédas, Jean-Luc
- Energy & Environmental Science, Vol. 2, Issue 3
Molecular Weight Dependence of the Morphology in P3HT:PCBM Solar Cells
journal, October 2014
- Liu, Feng; Chen, Dian; Wang, Cheng
- ACS Applied Materials & Interfaces, Vol. 6, Issue 22
Thermodynamics of Crystallization in High Polymers. IV. A Theory of Crystalline States and Fusion in Polymers, Copolymers, and Their Mixtures with Diluents
journal, March 1949
- Flory, Paul J.
- The Journal of Chemical Physics, Vol. 17, Issue 3
Binary Organic Photovoltaic Blends: A Simple Rationale for Optimum Compositions
journal, August 2008
- Müller, Christian; Ferenczi, Toby A. M.; Campoy-Quiles, Mariano
- Advanced Materials, Vol. 20, Issue 18
Colloidal Jamming at Interfaces: A Route to Fluid-Bicontinuous Gels
journal, September 2005
- Stratford, K.; Adhikari, R.; Pagonabarraga, I.
- Science, Vol. 309, Issue 5744, p. 2198-2201
In Situ X-ray Scattering Studies of the Influence of an Additive on the Formation of a Low-Bandgap Bulk Heterojunction
journal, February 2017
- Bokel, Felicia A.; Engmann, Sebastian; Herzing, Andrew A.
- Chemistry of Materials, Vol. 29, Issue 5