Citation: Zhi-ming Hu, Hui Chen, Xiao-wei Zhong, Jian-fei Qu, Wei Chen, An-hua Liu, Feng He. Design and Synthesis of Halogen Atom Substituted Benzothiadiazole-based Donor Polymers for Efficient Solar Energy Conversion[J]. Acta Polymerica Sinica, ;2018, (2): 273-283. doi: 10.11777/j.issn1000-3304.2018.17243 shu

Design and Synthesis of Halogen Atom Substituted Benzothiadiazole-based Donor Polymers for Efficient Solar Energy Conversion

Zhi-ming Hu ^1,2 ,
Hui Chen ¹ ,
Xiao-wei Zhong ¹ ,
Jian-fei Qu ¹ ,
Wei Chen ^3,4,, ,
An-hua Liu ^2,, ,
Feng He ^1,,

1.
Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055
2.
College of Materials, Xiamen University, Xiamen 361005
3.
Institute for Molecular Engineering and Materials Science Division, Argonne National Laboratory, Lemont 60439, USA
4.
Institute for Molecular Engineering, The University of Chicago, Chicago 60637, USA

Corresponding author: Wei Chen, wchen@anl.gov An-hua Liu, ahliu@xmu.edu.cn Feng He, hef@sustc.edu.cn
Received Date: 28 August 2017
Revised Date: 25 September 2017

Halogen substituted benzothiadiazole polymers with different length of alkyl side chains were synthesized via Stille coupling and used as donor materials in polymer solar cells (PSC). These polymers exhibited good solubility in common organic solvents, excellent film forming ability, and broad absorption properly towards the sun light. By introducing the halogen atoms to the backbone, in particularly the large chlorine atoms, fullerene-based (PC₇₁BM) bulk heterojunction PSCs of these polymers could achieve enhanced open-circuit voltage and short-circuit current, and eventually the power conversion efficiency could be dramatically improved. It was found that the halogen substitution and various alkyl side chains could highly affect the polymers' band gaps and charge transport properties, through influencing the molecular orientation and crystallinity. With regard to tuning the energy levels, compared with fluorine atom, chlorine atom with a bigger atomic radius could reduce more efficiently the energy levels, thereby further improving the open-circuit voltage of the corresponding PSCs. In this study, the PSCs based on one-chlorine-and-one-fluorine-substituted PCFBT4T-2OD, with PC₇₁BM used as the acceptor, exhibited an open-circuit voltage of 0.72 V, a short-circuit current of 17.61 mA cm^-2, and the highest power conversion efficiency of 8.84%. From the grazing-incidence wide-angle X-ray scattering (GIWAXS) experiments, those polymers with the halogen atoms substitutions showed a mixed "face-on" and "edge-on" conformation in their blended films. The introduction of fluorine atoms in the polymer PCFBT4T-2OD further enhanced the π-π stacking, compared with the one-chlorine substituted PCBT4T-2BO, which was helpful for the charge transport in the active layer and to enhance the device performance in PSCs. Those results demonstrated that the halogen substitution was an effective molecular design strategy to modify the polymer aggregation and morphology for optimized polymer solar cell applications.
- Polymer solar cells,
- Donor materials,
- Halogen atom substitution,
- Open-circuit voltage
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