A new semiconducting polymer based on terthiophene-thienopyrrolodione alternating building blocks with a deep HOMO energy level (5.66 eV) is presented. The polymer is prepared by a direct heteroarylation polycondensation reaction, which is a low-cost and green alternative to the standard Stille coupling reaction and thus avoids any use of toxic stannyl derivatives. Integrating the polymer into bulk heterojunction solar cells with [6,6]-phenyl C71-butyric acid methyl ester (PCBM) leads to a PCE of over 6% and a high open-circuit voltage of up to 0.94 V. To obtain these results a unique processing additive, 1-chloronaphthalene, is used, and a relatively low concentration of PCBM is used in the blend solution.
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