The bulk morphologies of blend films were investigated by transmission
electron microscopy (TEM). It is obvious that the PM6:Tz-Clblend possessed a smaller domain size and nano-scale phase separation
(Figure S3), which is well consistent with the results of surface
energy. GIWAXS measurements were further utilized to investigate the
morphological feature of the two blend films. As shown in Figure 4b,
face-on and edge-on crystallites coexisted in the PM6:Tz-Hblend film, which is similar to the neat Tz-H film. Compared
with the bimodal texture of the PM6:Tz-H blend film, the
PM6:Tz-Cl blend film exhibited predominant face-on orientation,
which is beneficial to the charge transport in vertical direction
(Figure 4c). As discussed above, these morphological features indicated
that the Tz-Cl -based blend film exhibited a more favorable
morphology, which might be a crucial reason for achieving better
photovoltaic performance.
In conclusion, the electron-deficient units,
thiazole and 4-chlorothiazole,
were employed to construct two
NFREAs, Tz-H and Tz-Cl , respectively. Compared withTz-H , Tz-Cl possessed a highly-planar backbone,
ascribed to the simultaneous incorporation of S···N and S···Cl NoCLs.
The Tz-Cl -based device delivered a PCE of 11.10%, much higher
than the Tz-H -based control device (6.41%), mainly due to more
efficient exciton dissociation, better and more balanced carrier
mobility, less charge recombination, and more favorable morphology.
Thus, this work provides an effective strategy for designing
high-planarity and low-cost NFREAs via the incorporation of multiple
NoCLs.
The supporting information for this article is available on the WWW
under https://doi.org/10.1002/cjoc.2021xxxxx.
Z. Han and C. Li contributed equally to this work. The authors
acknowledge the financial support from the National Natural Science
Foundation of China (51925306, 52103352, and 52120105006), National Key
R&D Program of China (2018FYA 0305800), Key Research Program of Chinese
Academy of Sciences (XDPB08-2), the Strategic Priority Research Program
of Chinese Academy of Sciences (XDB28000000), the Youth Innovation
Promotion Association of Chinese Academy of Sciences (2022165), and the
Fundamental Research Funds for the Central Universities. DFT results
described in this report were obtained from the National Supercomputing
Center in Shenzhen (Shenzhen Cloud Computing Center).
[1] Wang, J., Zhan, X. From Perylene Diimide Polymers to Fused-Ring
Electron Acceptors: A 15-Year Exploration Journey of Nonfullerene
Acceptors. Chin. J. Chem. 2022, 40, 1592-1607.
[2] Zhang, G.; Zhao, J.; Chow, P. C. Y.; Jiang, K.; Zhang, J.; Zhu,
Z.; Zhang, J.; Huang, F., Yan, H. Nonfullerene Acceptor Molecules for
Bulk Heterojunction Organic Solar Cells. Chem. Rev.2018, 118, 3447-3507.
[3] Lin, Y.; Wang, J.; Zhang, Z.-G.; Bai, H.; Li, Y.; Zhu, D., Zhan,
X. An Electron Acceptor Challenging Fullerenes for Efficient Polymer
Solar Cells. Adv. Mater. 2015, 27, 1170-1174.
[4] Wei, Q.; Liu, W.; Leclerc, M.; Yuan, J.; Chen, H., Zou, Y.
A-DA′D-A non-fullerene acceptors for high-performance organic solar
cells. Sci. China Chem. 2020, 63, 1352-1366.
[5] Yuan, J.; Zhang, Y.; Zhou, L.; Zhang, G.; Yip, H.-L.; Lau,
T.-K.; Lu, X.; Zhu, C.; Peng, H.; Johnson, P. A.; Leclerc, M.; Cao, Y.;
Ulanski, J.; Li, Y., Zou, Y. Single-Junction Organic Solar Cell with
over 15% Efficiency Using Fused-Ring Acceptor with Electron-Deficient
Core. Joule 2019, 3, 1140–1151.
[6] Hou, J.; Inganäs, O.; Friend, R. H., Gao, F. Organic solar cells
based on non-fullerene acceptors. Nat. Mater. 2018,17, 119-128.
[7] Zhu, L.; Zhang, M.; Xu, J.; Li, C.; Yan, J.; Zhou, G.; Zhong,
W.; Hao, T.; Song, J.; Xue, X.; Zhou, Z.; Zeng, R.; Zhu, H.; Chen,
C.-C.; MacKenzie, R. C. I.; Zou, Y.; Nelson, J.; Zhang, Y.; Sun, Y.,
Liu, F. Single-junction organic solar cells with over 19% efficiency
enabled by a refined double-fibril network morphology. Nat.
Mater. 2022, 21, 656-663.
[8] Sun, R.; Wu, Y.; Yang, X.; Gao, Y.; Chen, Z.; Li, K.; Qiao, J.;
Wang, T.; Guo, J.; Liu, C.; Hao, X.; Zhu, H., Min, J. Single-Junction
Organic Solar Cells with 19.17% Efficiency Enabled by Introducing One
Asymmetric Guest Acceptor. Adv. Mater. 2022, 34,
2110147.
[9] Cui, Y.; Xu, Y.; Yao, H.; Bi, P.; Hong, L.; Zhang, J.; Zu, Y.;
Zhang, T.; Qin, J.; Ren, J.; Chen, Z.; He, C.; Hao, X.; Wei, Z., Hou, J.
Single-Junction Organic Photovoltaic Cell with 19% Efficiency.Adv. Mater. 2021, 33, 2102420.
[10] Wei, Y.; Chen, Z.; Lu, G.; Yu, N.; Li, C.; Gao, J.; Gu, X.;
Hao, X.; Lu, G.; Tang, Z.; Zhang, J.; Wei, Z.; Zhang, X., Huang, H.
Binary Organic Solar Cells Breaking 19% via Manipulating the Vertical
Component Distribution. Adv. Mater. 2022, 34,
2204718.
[11] Gao, J.; Yu, N.; Chen, Z.; Wei, Y.; Li, C.; Liu, T.; Gu, X.;
Zhang, J.; Wei, Z.; Tang, Z.; Hao, X.; Zhang, F.; Zhang, X., Huang, H.
Over 19.2% Efficiency of Organic Solar Cells Enabled by Precisely
Tuning the Charge Transfer State Via Donor Alloy Strategy. Adv.
Sci. 2022, 9, 2203606.
[12] Chen, H.; Zou, Y.; Liang, H.; He, T.; Xu, X.; Zhang, Y.; Ma,
Z.; Wang, J.; Zhang, M.; Li, Q.; Li, C.; Long, G.; Wan, X.; Yao, Z.,
Chen, Y. Lowing the energy loss of organic solar cells by molecular
packing engineering via multiple molecular conjugation extension.Sci. China Chem. 2022, 65, 1362-1373.
[13] Zhang, Z.; Li, Y.; Cai, G.; Zhang, Y.; Lu, X., Lin, Y. Selenium
Heterocyclic Electron Acceptor with Small Urbach Energy for As-Cast
High-Performance Organic Solar Cells. J. Am. Chem. Soc.2020, 142, 18741-18745.
[14] Zhang, X.; Qin, L.; Liu, X.; Zhang, C.; Yu, J.; Xiao, Z.;
Zheng, N.; Wang, B.; Wei, Y.; Xie, Z.; Wu, Y.; Wei, Z.; Wang, K.; Gao,
F.; Ding, L., Huang, H. Enhancing the Photovoltaic Performance of
Triplet Acceptors Enabled by Side-Chain Engineering. Sol. RRL2021, 5, 2100522.
[15] Li, S.; Zhan, L.; Liu, F.; Ren, J.; Shi, M.; Li, C.-Z.;
Russell, T. P., Chen, H. An Unfused-Core-Based Nonfullerene Acceptor
Enables High-Efficiency Organic Solar Cells with Excellent Morphological
Stability at High Temperatures. Adv. Mater. 2018,30, 1705208.
[16] Huang, H.; Guo, Q.; Feng, S.; Zhang, C.; Bi, Z.; Xue, W.; Yang,
J.; Song, J.; Li, C.; Xu, X.; Tang, Z.; Ma, W., Bo, Z. Noncovalently
fused-ring electron acceptors with near-infrared absorption for
high-performance organic solar cells. Nat. Commun. 2019,10, 3038.
[17] Yu, Z.-P.; Liu, Z.-X.; Chen, F.-X.; Qin, R.; Lau, T.-K.; Yin,
J.-L.; Kong, X.; Lu, X.; Shi, M.; Li, C.-Z., Chen, H. Simple non-fused
electron acceptors for efficient and stable organic solar cells.Nat. Commun. 2019, 10, 2152.
[18] Gu, X.-B.; Gao, J.-H.; Han, Z.-Y.; Shi, Y.-H.; Wei, Y.-N.;
Zhang, Y.-C.; Peng, Q.; Wei, Z.-X.; Zhang, X., Huang, H. A Simple
Building Block with Noncovalently Conformational Locks towards
Constructing Low-Cost and High-Performance Nonfused Ring Electron
Acceptors. Chin. J. Polym. Sci., DOI:
10.1007/s10118-10022-12888-10119.
[19] Li, C.; Zhang, X.; Yu, N.; Gu, X.; Qin, L.; Wei, Y.; Liu, X.;
Zhang, J.; Wei, Z.; Tang, Z.; Shi, Q., Huang, H. Simple Nonfused-Ring
Electron Acceptors with Noncovalently Conformational Locks for Low-Cost
and High-Performance Organic Solar Cells Enabled by End-Group
Engineering. Adv. Funct. Mater. 2022, 32,
2108861.
[20] Zhang, X.; Qin, L.; Yu, J.; Li, Y.; Wei, Y.; Liu, X.; Lu, X.;
Gao, F., Huang, H. High-Performance Noncovalently Fused-Ring Electron
Acceptors for Organic Solar Cells Enabled by Noncovalent Intramolecular
Interactions and End-Group Engineering. Angew. Chem. Int. Ed.2021, 60, 12475-12481.
[21] Zhang, X.; Li, C.; Qin, L.; Chen, H.; Yu, J.; Wei, Y.; Liu, X.;
Zhang, J.; Wei, Z.; Gao, F.; Peng, Q., Huang, H. Side-Chain Engineering
for Enhancing the Molecular Rigidity and Photovoltaic Performance of
Noncovalently Fused-Ring Electron Acceptors. Angew. Chem. Int.
Ed. 2021, 60, 17720-17725.
[22] Huang, H.; Chen, Z.; Ortiz, R. P.; Newman, C.; Usta, H.; Lou,
S.; Youn, J.; Noh, Y.-Y.; Baeg, K.-J.; Chen, L. X.; Facchetti, A.,
Marks, T. Combining Electron-Neutral Building Blocks with Intramolecular
“Conformational Locks” Affords Stable, High-Mobility P- and N-Channel
Polymer Semiconductors. J. Am. Chem. Soc. 2012,134, 10966-10973.
[23] Huang, H.; Yang, L.; Facchetti, A., Marks, T. J. Organic and
Polymeric Semiconductors Enhanced by Noncovalent Conformational Locks.Chem. Rev. 2017, 117, 10291-10318.
[24] Yu, S.; Peng, A.; Zhang, S., Huang, H. Noncovalent
conformational locks in organic semiconductors. Sci. China Chem.2018, 61, 1359-1367.
[25] Zhang, X.; Wei, Y.; Liu, X.; Qin, L.; Yu, N.; Tang, Z.; Wei,
Z.; Shi, Q.; Peng, A., Huang, H. Enhancing Photovoltaic Performances of
Naphthalene-Based Unfused-Ring Electron Acceptors upon
Regioisomerization. Sol. RRL 2021, 5, 2100094.
[26] Zhang, X.; Qin, L.; Li, L.; Liu, X.; Wei, Y., Huang, H. A New
Noncovalently Fused-Ring Electron Acceptor Based on
3,7-Dialkyloxybenzo[1,2-b:4,5-b’]dithiophene for Low-Cost and
High-Performance Organic Solar Cells. Macromol. Rapid Commun.2022, 43, 2200085.
[27] Liu, Y.; Song, J., Bo, Z. Designing high performance conjugated
materials for photovoltaic cells with the aid of intramolecular
noncovalent interactions. Chem. Commun. 2021, 57,
302-314.
[28] Yang, M.; Wei, W.; Zhou, X.; Wang, Z., Duan, C. Non-fused ring
acceptors for organic solar cells. Energy Mater. 2021,1, 100008.
[29] Li, Y.; Yu, J.; Zhou, Y., Li, Z. a. Molecular Insights of
Non-fused Ring Acceptors for High-Performance Non-fullerene Organic
Solar Cells. Chem. - Eur. J. 2022, 28,
e202201675.
[30] Wang, Y.; Liu, Z.; Cui, X.; Wang, C.; Lu, H.; Liu, Y.; Fei, Z.;
Ma, Z., Bo, Z. Small molecule acceptors with a ladder-like core for
high-performance organic solar cells with low non-radiative energy
losses. J. Mater. Chem. A 2020, 8, 12495-12501.
[31] Yoon, N.; Jeong, J.-Y.; Oh, S.; Song, C. E.; Lee, H. K.; Shin,
W. S.; Lee, J.-C.; Moon, S.-J., Lee, S. K. Effects of Electron-Donating
and Electron-Accepting Substitution on Photovoltaic Performance in
Benzothiadiazole-Based A–D–A′–D–A-Type Small-Molecule Acceptor Solar
Cells. ACS Appl. Energy Mater. 2020, 3,
12327-12337.
[32] Liu, X.; Wei, Y.; Zhang, X.; Qin, L.; Wei, Z., Huang, H. An
A-D-A’-D-A type unfused nonfullerene acceptor for organic solar cells
with approaching 14% efficiency. Sci. China Chem. 2021,64, 228-231.
[33] Zhou, X.; Pang, S.; Wu, B.; Zhou, J.; Tang, H.; Lin, K.; Xie,
Z.; Duan, C.; Huang, F., Cao, Y. Noncovalent Interactions Induced by
Fluorination of the Central Core Improve the Photovoltaic Performance of
A-D-A′-D-A-Type Nonfused Ring Acceptors. ACS Appl. Energy Mater.2022, 5, 7710-7718.
[34] Luo, D.; Jiang, Z.; Yang, W.; Guo, X.; Li, X.; Zhou, E.; Li,
G.; Li, L.; Duan, C.; Shan, C.; Wang, Z.; Li, Y.; Xu, B., Kyaw, A. K. K.
Dual-functional ambipolar non-fused ring electron acceptor as third
component and designing similar molecular structure between two
acceptors for high-performance ternary organic solar cells. Nano
Energy 2022, 98, 107186.
[35] Geng, S.-Z.; Yang, W.-T.; Gao, J.; Li, S.-X.; Shi, M.-M.; Lau,
T.-K.; Lu, X.-H.; Li, C.-Z., Chen, H.-Z. Non-fullerene Acceptors with a
Thieno[3,4-c]pyrrole-4,6-dione (TPD) Core for Efficient Organic
Solar Cells. Chin. J. Polym. Sci. 2019, 37,
1005-1014.
[36] Li, Y.; Fu, H.; Wu, Z.; Wu, X.; Wang, M.; Qin, H.; Lin, F.;
Woo, H. Y., Jen, A. K. Y. Regulating the Aggregation of Unfused
Non-Fullerene Acceptors via Molecular Engineering towards Efficient
Polymer Solar Cells. ChemSusChem 2021, 14,
3579-3589.
[37] Hu, T.-Y.; Zhang, Y.; Lu, B.-S.; Ma, Y.-F.; Zhu, Y.-N.; Wang,
Y.-T.; Zhang, B.-Y.; Zhang, Z.-Q.; Wang, J.; Yang, Y., Zhang, H.-L.
Unfused-ring small molecule acceptors based on A1-D-A2-D-A1 architecture
with low non-radiative energy loss and excellent air stability.Mater. Today Energy 2021, 21, 100802.
[38] Lin, Y.; Fan, H.; Li, Y., Zhan, X. Thiazole-Based Organic
Semiconductors for Organic Electronics. Adv. Mater.2012, 24, 3087-3106.
[39] Zhang, L.; Deng, W.; Wu, B.; Ye, L.; Sun, X.; Wang, Z.; Gao,
K.; Wu, H.; Duan, C.; Huang, F., Cao, Y. Reduced Energy Loss in
Non-Fullerene Organic Solar Cells with Isomeric Donor Polymers
Containing Thiazole π-Spacers. ACS Appl. Mater. Interfaces2020, 12, 753-762.
[40] Ando, S.; Murakami, R.; Nishida, J.-i.; Tada, H.; Inoue, Y.;
Tokito, S., Yamashita, Y. n-Type Organic Field-Effect Transistors with
Very High Electron Mobility Based on Thiazole Oligomers with
Trifluoromethylphenyl Groups. J. Am. Chem. Soc. 2005,127, 14996-14997.
[41] Jung, I. H.; Jung, Y. K.; Lee, J.; Park, J.-H.; Woo, H. Y.;
Lee, J.-I.; Chu, H. Y., Shim, H.-K. Synthesis and electroluminescent
properties of fluorene-based copolymers containing electron-withdrawing
thiazole derivatives. J. Polym. Sci. A Polym. Chem.2008, 46, 7148-7161.
[42] Spano, F. C. The Spectral Signatures of Frenkel Polarons in H-
and J-Aggregates. Acc. Chem. Res. 2010, 43,
429-439.
[43] Kyaw, A. K. K.; Wang, D. H.; Wynands, D.; Zhang, J.; Nguyen,
T.-Q.; Bazan, G. C., Heeger, A. J. Improved Light Harvesting and
Improved Efficiency by Insertion of an Optical Spacer (ZnO) in
Solution-Processed Small-Molecule Solar Cells. Nano Lett.2013, 13, 3796-3801.