TY - JOUR
T1 - Synthesis of Crown Ether End-Capped PM6 Copolymers with Tunable Molecular Weight for Organic Solar Cells
AU - Li, Yiming
AU - Liu, Jiaqing
AU - Shui, Ke
AU - Xie, Fan
AU - Li, Xuan
AU - Lin, Yi
AU - Zhou, Zehua
AU - Zhang, Qing
AU - Guo, Fengqi
AU - Li, Lijun
AU - Xiao, Jinchong
AU - Wang, Meng
AU - Ma, Chang Qi
N1 - Funding Information:
This study is jointly supported by the NSFC (52203249), the Young Innovation Leading Talents of Suzhou Innovation and Entrepreneurship Leading Talents Program (ZXL2022462), the Young Elite Scientists Sponsorship Program by the Suzhou Association for Science and Technology (E2391303), and the Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences (E1511401). The authors would also like to thank the technical support for Nano-X from the Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Science (No. A2107).
Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023
Y1 - 2023
N2 - Poly-[(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2-b:4,5-b′]dithiophene))-alt-(5,5-(1′,3′-di-2-thienyl-5′,7′-bis(2-ethylhexyl)benzo[1′,2′-c:4′,5′-c′]dithiophene-4,8-dione))] (PM6) is one of the star molecules in organic solar cells (OSCs). However, PM6 has been suffering from molecular weight control and unreacted terminal groups. Thus, synthesizing high-quality polymers without batch-to-batch variations has been challenging for many years. Herein, a one-step protocol of both end-capping and polymerization at the same time was developed to prepare end-capped PM6 with molecular weight controlled by changing the monomer ratio. Specifically, non-end-capped PM67 and a series of PM6En with different molecular weights were synthesized and characterized. Our research findings indicated that (1) these copolymers’ number-average molecular weights (Mns) and weight-average molecular weights (Mws) were measured to be almost linearly increased. Although textbooks have mentioned the nonequivalent ratio monomer strategy to regulate the molecular weight of polymers, the end-capping yield has not been reported in the research of OSCs due to a lack of efficient experiments and instruments to measure the low percentage of end groups in the polymer. (2) Since the selected end-caping reagent 4′-bromobenzo-18-crown-6 (EBr) can be easily distinguished from the PM6 main backbone, we first measured the end-capping yield by both nuclear magnetic resonance (NMR) and matrix-assisted laser desorption/ionization time-of-flight mass spectra (MALDI-TOF-MS). We applied this approach for the first time to synthesize polymers with reasonable end-capping yields (40-97%) for OSCs. (3) Surprisingly, 18-crown-6 can reduce end-group defects, lower the polydispersity index (PDI) of the polymer, and achieve suitable morphology and mobility. As a result, the end-capped PM6E7-based device exhibited the best stability and power conversion efficiency (PCE) compared to those of the other end-capped or non-end-capped polymers. Both the end groups and molecular weight significantly affect the performance of the OSCs. PM6 and other copolymers could be finely tuned by subtly changing the molecular weights or end-cap groups with functional building blocks. Our research will stimulate the development of OSCs and other applications of copolymers.
AB - Poly-[(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2-b:4,5-b′]dithiophene))-alt-(5,5-(1′,3′-di-2-thienyl-5′,7′-bis(2-ethylhexyl)benzo[1′,2′-c:4′,5′-c′]dithiophene-4,8-dione))] (PM6) is one of the star molecules in organic solar cells (OSCs). However, PM6 has been suffering from molecular weight control and unreacted terminal groups. Thus, synthesizing high-quality polymers without batch-to-batch variations has been challenging for many years. Herein, a one-step protocol of both end-capping and polymerization at the same time was developed to prepare end-capped PM6 with molecular weight controlled by changing the monomer ratio. Specifically, non-end-capped PM67 and a series of PM6En with different molecular weights were synthesized and characterized. Our research findings indicated that (1) these copolymers’ number-average molecular weights (Mns) and weight-average molecular weights (Mws) were measured to be almost linearly increased. Although textbooks have mentioned the nonequivalent ratio monomer strategy to regulate the molecular weight of polymers, the end-capping yield has not been reported in the research of OSCs due to a lack of efficient experiments and instruments to measure the low percentage of end groups in the polymer. (2) Since the selected end-caping reagent 4′-bromobenzo-18-crown-6 (EBr) can be easily distinguished from the PM6 main backbone, we first measured the end-capping yield by both nuclear magnetic resonance (NMR) and matrix-assisted laser desorption/ionization time-of-flight mass spectra (MALDI-TOF-MS). We applied this approach for the first time to synthesize polymers with reasonable end-capping yields (40-97%) for OSCs. (3) Surprisingly, 18-crown-6 can reduce end-group defects, lower the polydispersity index (PDI) of the polymer, and achieve suitable morphology and mobility. As a result, the end-capped PM6E7-based device exhibited the best stability and power conversion efficiency (PCE) compared to those of the other end-capped or non-end-capped polymers. Both the end groups and molecular weight significantly affect the performance of the OSCs. PM6 and other copolymers could be finely tuned by subtly changing the molecular weights or end-cap groups with functional building blocks. Our research will stimulate the development of OSCs and other applications of copolymers.
UR - http://www.scopus.com/inward/record.url?scp=85167833001&partnerID=8YFLogxK
U2 - 10.1021/acs.macromol.3c00798
DO - 10.1021/acs.macromol.3c00798
M3 - Article
AN - SCOPUS:85167833001
SN - 0024-9297
VL - 56
SP - 6276
EP - 6289
JO - Macromolecules
JF - Macromolecules
IS - 16
ER -