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Stable Postfullerene Solar Cells via Direct C-H Arylation Polymerization. Morphology-Performance Relationships



Subhrangsu Mukherjee, Thomas Aldrich, Weigang Zhu, Lee J. Richter, Eliot Gann, Dean DeLongchamp, Antonio Facchetti, Ferdinand Melkonyan, Tobin Marks


The scope of the environmentally benign direct C-H arylation polymerization (DARP) process is validated and significantly extended in the synthesis of a high-performance benzodithiophene- based copolymer series, PBDT(Ar)-FTTE, with previously untested and systematically varied heteroaryl (Ar) substituents. Bulk-heterojunction (BHJ) polymer solar cells (PSCs) containing the high-performance nonfullerene acceptor (NFA) ITIC-Th and DARP-derived donors are fabricated and evaluated, yielding PCEs as high as 8%. The relationships between Ar-sensitive copolymer structure, BHJ morphology, and PSC performance are elucidated through in-depth characterization of structural order, phase separation, and charge transport using SCLC, AFM, GIWAXS, R-SoXS, and NEXAFS measurements, which conclusively demonstrate the important effects of Ar-tunable, dimensionally smaller, and well-blended copolymer domains for maximum PSC performance. Smaller BHJ copolymer domains having greater ITIC-Th miscibility definitively correlate with enhanced JSC, FF, and PCE metrics. Surprisingly regarding cell performance durability, while unencapsulated PBDTT-FTTE:ITIC-Th PSCs deliver the highest initial PCE, the unencapsulated PBDTTF-FTTE:ITIC-Th devices exhibit the optimum combination of high initial photovoltaic metrics and stability, retaining nearly 90% of the initial PCE after 51 days in ambient conditions and 83% of initial PCE after 180 min under simulated solar illumination. Importantly, for this PBDT(Ar)-FTTE:ITIC-Th series, PSC photovoltaic stability correlates with the presence of large pure BHJ domains, and moreover rivals or exceeds the stability of the analogous fullerene-based PSCs. Together, these results argue that solar cells prepared with the environmentally benign DARP process and NFAs are promising for both greener and more stable solar energy generation.
Chemistry of Materials


organic photovoltaics, scattering, organic electronics


Mukherjee, S. , Aldrich, T. , Zhu, W. , Richter, L. , Gann, E. , DeLongchamp, D. , Facchetti, A. , Melkonyan, F. and Marks, T. (2019), Stable Postfullerene Solar Cells via Direct C-H Arylation Polymerization. Morphology–Performance Relationships, Chemistry of Materials, [online],, (Accessed June 19, 2024)


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Created May 15, 2019, Updated October 12, 2021