The Curious Case of Fluorination of Conjugated Polymers for Solar Cells
Open accessAbstract
Organic solar cells (OSCs) have been a rising star in the field of renewable energy since the introduction of the bulk heterojunction (BHJ) in 1992. Recent advances have pushed the efficiencies of OSCs to over 13%, an impressive accomplishment via collaborative efforts in rational materials design and synthesis, careful device engineering, and fundamental understanding of device physics. Throughout these endeavors, several design principles for the conjugated donor polymers used in such solar cells have emerged, including optimizing the conjugated backbone with judicious selection of building blocks, side-chain engineering, and substituents. Among all of the substituents, fluorine is probably the most popular one; improved device characteristics with fluorination have frequently been reported for a wide range of conjugated polymers, in particular, donor-acceptor (D-A)-type polymers. Herein we examine the effect of fluorination on the device performance of solar cells as a function of the position of fluorination (on the acceptor unit or on the donor unit), aiming to outline a clear understanding of the benefits of this curious substituent. As fluorination of the acceptor unit is the most adopted strategy for D-A polymers, we first discuss the effect of fluorination of the acceptor units, highlighting the five most widely utilized acceptor units. While improved device efficiency has been widely observed with fluorinated acceptor units, the underlying reasons vary from case to case and highly depend on the chemical structure of the polymer. Second, the effect of fluorination of the donor unit is addressed. Here we focus on four donor units that have been most studied with fluorination. While device-performance-enhancing effects by fluorination of the donor units have also been observed, it is less clear that fluorine will always benefit the efficiency of the OSC, as there are several cases where the efficiency drops, in particular with "over-fluorination", i.e., when too many fluorine substituents are incorporated. Finally, while this Account focuses on studies in which the polymer is paired with fullerene derivatives as the electron accepting materials, non-fullerene acceptors (NFAs) are quickly becoming key players in the field of OSCs. The effect of fluorination of the polymers on the device performance may be different when NFAs are used as the electron-accepting materials, which remains to be investigated. However, the design of fluorinated polymers may provide guidelines for the design of more efficient NFAs. Indeed, the current highest-performing OSC (∼13%) features fluorination on both the donor polymer and the non-fullerene acceptor.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
The conformation and morphology of a conjugated polymer backbone can be modified by fluorination.
“A conformation and morphology of CP backbone can be modified by fluorination.174”
From The Pursuit of Shortwave Infrared-Emitting Nanoparticles with Bright Fluorescence through Molecular Design and Excited-State Engineering of Molecular Aggregates (2022) · cites this paper as [174]
Cites
Liang, Y., Xu, Z., Xia, J., Tsai, S.-T., Wu, Y., Li, G., Ray, C., & Yu, L. (2010) · Advanced Materials · doi:10.1002/adma.200903528 · Cited by 3,651 · see citing works
Aggregation and morphology control enables multiple cases of high-efficiency polymer solar cells
Liu, Y., Zhao, J., Li, Z., Mu, C., Ma, W., Hu, H., Jiang, K., Lin, H., Ade, H. W., & Yan, H. (2014) · Nature Communications · doi:10.1038/ncomms6293 · Cited by 3,105 · see citing works
Molecular Optimization Enables over 13% Efficiency in Organic Solar Cells
Zhao, W., Li, S., Yao, H., Zhang, S., Zhang, Y., Yang, B., & Hou, J. (2017) · Journal of the American Chemical Society · doi:10.1021/jacs.7b02677 · Cited by 2,790 · see citing works
Efficient organic solar cells processed from hydrocarbon solvents
Zhao, J., Li, Y., Yang, G., Jiang, K., Lin, H., Ade, H. W., Ma, W., & Yan, H. (2016) · Nature Energy · doi:10.1038/nenergy.2015.27 · Cited by 2,367 · see citing works
Price, S. C., Stuart, A. C., Yang, L., Zhou, H., & You, W. (2011) · Journal of the American Chemical Society · doi:10.1021/ja1112595 · Cited by 1,505 · see citing works
Self-citationRational Design of High Performance Conjugated Polymers for Organic Solar Cells
Zhou, H., Yang, L., & You, W. (2012) · Macromolecules · doi:10.1021/ma201648t · Cited by 1,502 · see citing works
Self-citationLiang, Y., Feng, D., Wu, Y., Tsai, S.-T., Li, G., Ray, C., & Yu, L. (2009) · Journal of the American Chemical Society · doi:10.1021/ja901545q · Cited by 1,385 · see citing works
A Large‐Bandgap Conjugated Polymer for Versatile Photovoltaic Applications with High Performance
Zhang, M., Guo, X., Ma, W., et al. (2015) · Advanced Materials · doi:10.1002/adma.201502110 · Cited by 1,253 · see citing works
Zhou, H., Yang, L., Stuart, A. C., Price, S. C., Liu, S., & You, W. (2011) · Angewandte Chemie International Edition · doi:10.1002/anie.201005451 · Cited by 1,211 · see citing works
Self-citationFused Nonacyclic Electron Acceptors for Efficient Polymer Solar Cells
Dai, S., Zhao, F., Zhang, Q., Lau, T.-K., Li, T., Liu, K., Ling, Q., Wang, C., Lu, X., You, W., et al. (2017) · Journal of the American Chemical Society · doi:10.1021/jacs.6b12755 · Cited by 864 · see citing works
Self-citationSingle‐Junction Binary‐Blend Nonfullerene Polymer Solar Cells with 12.1% Efficiency
Zhao, F., Dai, S., Wu, Y., Zhang, Q., Wang, J., Jiang, L., Ling, Q., Wei, Z., Ma, W., You, W., et al. (2017) · Advanced Materials · doi:10.1002/adma.201700144 · Cited by 699 · see citing works
Self-citationSon, H. J., Wang, W., Xu, T., Liang, Y., Wu, Y., Li, G., & Yu, L. (2011) · Journal of the American Chemical Society · doi:10.1021/ja108601g · Cited by 576 · see citing works
Stuart, A. C., Tumbleston, J. R., Zhou, H., Li, W., Liu, S., Ade, H. W., & You, W. (2013) · Journal of the American Chemical Society · doi:10.1021/ja309289u · Cited by 561 · see citing works
Self-citationZhang, M., Guo, X., Zhang, S., & Hou, J. (2013) · Advanced Materials · doi:10.1002/adma.201304427 · Cited by 425 · see citing works
Donor polymer design enables efficient non-fullerene organic solar cells
Li, Z., Jiang, K., Yang, G., et al. (2016) · Nature Communications · doi:10.1038/ncomms13094 · Cited by 368 · see citing works
Kawashima, K., Fukuhara, T., Suda, Y., et al. (2016) · Journal of the American Chemical Society · doi:10.1021/jacs.6b05418 · Cited by 342 · see citing works
Mobility-Controlled Performance of Thick Solar Cells Based on Fluorinated Copolymers
Li, W., Albrecht, S., Yang, L., et al. (2014) · Journal of the American Chemical Society · doi:10.1021/ja5067724 · Cited by 267 · see citing works
Increased open circuit voltage in fluorinated benzothiadiazole-based alternating conjugated polymers
Zhang, Y. A., Chien, S.-C., Chen, K., et al. (2011) · Chemical Communications · doi:10.1039/c1cc14586j · Cited by 252 · see citing works
Bronstein, H. A., Frost, J. M., Hadipour, A., et al. (2013) · Chemistry of Materials · doi:10.1021/cm301910t · Cited by 240 · see citing works
Deng, Y., Liu, J., Wang, J., et al. (2013) · Advanced Materials · doi:10.1002/adma.201303586 · Cited by 203 · see citing works
Yum, S., An, T. K., Wang, X., et al. (2014) · Chemistry of Materials · doi:10.1021/cm4042346 · Cited by 190 · see citing works
Schroeder, B. C., Huang, Z., Ashraf, R. S., et al. (2012) · Advanced Functional Materials · doi:10.1002/adfm.201102941 · Cited by 187 · see citing works
Impact of Backbone Fluorination on π-Conjugated Polymers in Organic Photovoltaic Devices: A Review
Leclerc, N., Chávez, P., Ibraikulov, O. A., et al. (2016) · Polymers · doi:10.3390/polym8010011 · Cited by 175 · see citing works
Zhang, S., Qin, Y., Uddin, M. A., et al. (2016) · Macromolecules · doi:10.1021/acs.macromol.6b00248 · Cited by 159 · see citing works
Molecular Engineering of Conjugated Polymers for Solar Cells: An Updated Report
Xiao, S., Zhang, Q., & You, W. (2016) · Advanced Materials · doi:10.1002/adma.201601391 · Cited by 156 · see citing works
Self-citationFluorination of Polythiophene Derivatives for High Performance Organic Photovoltaics
Jo, J. W., Jung, J. W., Wang, H., et al. (2014) · Chemistry of Materials · doi:10.1021/cm502229k · Cited by 147 · see citing works
Liu, P., Zhang, K., Liu, F., et al. (2014) · Chemistry of Materials · doi:10.1021/cm500953e · Cited by 142 · see citing works
Li, Z., Lu, J., Tse, S.-C., Zhou, J., Du, X., Tao, Y., & Ding, J. (2011) · Journal of Materials Chemistry · doi:10.1039/c0jm04166a · Cited by 131 · see citing works
Fluorinated conjugated polymers in organic bulk heterojunction photovoltaic solar cells
Meyer, F. (2015) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2015.04.007 · Cited by 130 · see citing works
Uy, R. L., Price, S. C., & You, W. (2012) · Macromolecular Rapid Communications · doi:10.1002/marc.201200129 · Cited by 119 · see citing works
Self-citationLiu, D., Zhao, W., Zhang, S., et al. (2015) · Macromolecules · doi:10.1021/acs.macromol.5b00829 · Cited by 112 · see citing works
Li, Z., Lin, H., Jiang, K., et al. (2015) · Nano Energy · doi:10.1016/j.nanoen.2015.05.016 · Cited by 101 · see citing works
Wolf, J., Cruciani, F., Labban, A. E., et al. (2015) · Chemistry of Materials · doi:10.1021/acs.chemmater.5b01520 · Cited by 99 · see citing works
Ko, S., Hoang, Q. V., Song, C. E., et al. (2017) · Energy & Environmental Science · doi:10.1039/c6ee03051c · Cited by 96 · see citing works
Kim, J., Song, C. E., Kim, H. U., et al. (2013) · Chemistry of Materials · doi:10.1021/cm401527b · Cited by 83 · see citing works
Isoindigo fluorination to enhance photovoltaic performance of donor–acceptor conjugated copolymers
Yang, Y., Wu, R.-M., Wang, X., et al. (2013) · Chemical Communications · doi:10.1039/c3cc47677d · Cited by 77 · see citing works
Thiophene fluorination to enhance photovoltaic performance in low band gap donor–acceptor polymers
Fei, Z., Shahid, M., Yaacobi‐Gross, N., et al. (2012) · Chemical Communications · doi:10.1039/c2cc35079c · Cited by 70 · see citing works
Iyer, A., Bjorgaard, J. A., Anderson, T. E., et al. (2012) · Macromolecules · doi:10.1021/ma3009788 · Cited by 69 · see citing works
Recent progress towards fluorinated copolymers for efficient photovoltaic applications
Xu, X., Li, Y., Luo, M., et al. (2016) · Chinese Chemical Letters · doi:10.1016/j.cclet.2016.05.006 · Cited by 65 · see citing works
Collado‐Fregoso, E., Boufflet, P., Fei, Z., et al. (2015) · Chemistry of Materials · doi:10.1021/acs.chemmater.5b02948 · Cited by 56 · see citing works
Wang, M., Ford, M. J., Lill, A. T., et al. (2017) · Advanced Materials · doi:10.1002/adma.201603830 · Cited by 50 · see citing works
Chen, W., Du, Z., Han, L., et al. (2014) · Journal of Materials Chemistry A · doi:10.1039/c4ta06350c · Cited by 44 · see citing works
Kelly, M. A., Roland, S., Zhang, Q., et al. (2017) · The Journal of Physical Chemistry C · doi:10.1021/acs.jpcc.6b10993 · Cited by 27 · see citing works
Self-citationWang, J., Bao, X., Ding, D., Qiu, M., Du, Z., Wang, J., Liu, J., Sun, M., & Yang, R. (2016) · Journal of Materials Chemistry A · doi:10.1039/c6ta04059d · Cited by 24 · see citing works
Wang, Z., Zhao, J., Li, Y., & Peng, Q. (2014) · Polymer Chemistry · doi:10.1039/c4py00273c · Cited by 23 · see citing works
Keshtov, M. L., Khokhlov, A. R., Kuklin, S. A., et al. (2016) · Polymer Chemistry · doi:10.1039/c6py01173j · Cited by 12 · see citing works
Gong, X., Li, G., Chen, J., et al. (2017) · Organic Electronics · doi:10.1016/j.orgel.2017.04.009 · Cited by 3 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
Fluoropolymers in Biomedical Applications: State-of-the-Art and Future Perspectives
Lv, J., & Cheng, Y. (2021) · Chemical Society Reviews · doi:10.1039/d0cs00258e · Cited by 316 · see citing works
Fluorination Enhances NIR‐II Fluorescence of Polymer Dots for Quantitative Brain Tumor Imaging
Liu, Y., Liu, J., Chen, D., Wang, X., Zhang, Z., Yang, Y., Jiang, L., Qi, W., Ye, Z., He, S., et al. (2020) · Angewandte Chemie International Edition · doi:10.1002/anie.202007886 · Cited by 173 · see citing works
Piwoński, H., Nozue, S., & Habuchi, S. (2022) · ACS Nanoscience Au · doi:10.1021/acsnanoscienceau.1c00038 · Cited by 39 · see citing works
“174 In general, fluorination introduces higher degrees of main-chain planarity, rigidity order, and packing tightness.”
- Authors
- Zhang, Q., Kelly, M. A., Bauer, N., & You, W.
- Affiliations
- University of North Carolina at Chapel Hill (US)
- Corresponding author
- You, Wei
- Venue
- Accounts of Chemical Research
- Publisher
- American Chemical Society (ACS)
- Published
- 2017-09-05
- Volume
- 50
- Issue
- 9
- Pages
- 2401-2409
- ISSN
- 0001-4842 (ISSN-L)
- 1520-4898
- OpenAlex
- W2753819773
- Cited by
- 379
- References
- 47
- Citations by year
- 2026: 12 · 2025: 28 · 2024: 38 · 2023: 31 · 2022: 46 · 2021: 49 · 2020: 59 · 2019: 68 · 2018: 42 · 2017: 6
- FWCI
- 19.88
- Type
- journal article
- Language
- en
- Open access
- green
- doi.org
- Locations
- Accounts of Chemical Research (publishedVersion)
- PubMed (publishedVersion)
- Carolina Digital Repository (University of North Carolina at Chapel Hill) (submittedVersion)
- UNC Libraries
- Funders
- Office of Naval Research (N000141410221)
- Division of Chemical, Bioengineering, Environmental, and Transport Systems (1639429)
- Division of Materials Research (1507249)
- Topics
- Physical Sciences › Engineering › Electrical and Electronic Engineering › Organic Electronics and Photovoltaics
- Physical Sciences › Engineering › Electrical and Electronic Engineering › Organic Light-Emitting Diodes Research
- Physical Sciences › Engineering › Electrical and Electronic Engineering › Silicon and Solar Cell Technologies
- Keywords
- organic solar cells, fluorination, conjugated polymers, donor-acceptor polymers, non-fullerene acceptors, fullerene acceptors, bulk heterojunction, device efficiency, side-chain engineering, building blocks
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review
