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Poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole) (PCDTBT) is a copolymer composed of alternating thiophene–benzothiadiazole–thiophene (TBT) and carbazole (Cbz) repeat units widely used for stable organic photovoltaics. However, the solubility of PCDTBT is limited, which decreases polymer yield and makes synthesis and purification tedious. Here, we introduce a strategy to increase both solubility and luminescence by the statistical incorporation of additional hexyl side chains at the TBT unit (hex-TBT). An increasing amount of hex-TBT as comonomer from 0 to 100% enhances solubility, leads to backbone torsion, and causes a blue-shift in the absorption and emission spectra. While photovoltaic performance of both PCDTBT:P3HT blends and PCDTBT:PC71BM blends decreases with increasing content of hex-TBT due to weaker and blue-shifted absorption, the luminescence properties can be systematically improved. Both photo- and electroluminescence (PL and EL) quantum efficienci...

PCDTBT: From Polymer Photovoltaics to Light-Emitting Diodes by Side-Chain-Controlled Luminescence