Influence of polymer compatibility on the open-circuit voltage in ternary blend bulk heterojunction solar cells

The evolution of the open-circuit voltage (Voc) with composition in ternary blend bulk heterojunction (BHJ) solar cells is correlated with the miscibility of the polymers. Ternary blends based on poly[N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT) and poly(3-hexylthiophene-thiophene-diketopyrrolopyrrole) (P3HTT-DPP-10%) with phenyl-C61-butyric acid methyl ester (PC61BM) acceptor were investigated. The Voc is pinned to the lower value of the P3HTT-DPP-10%:PC61BM binary blend even up to 95% PCDTBT in the polymer fraction. This is in stark contrast to the previously investigated system based on P3HTT-DPP-10%, poly(3-hexylthiophene-co-3-(2-ethylhexyl)thiophene) (P3HT75-co-EHT25), and PC61BM, where the Voc varied regularly across the full composition range, as explained by an organic alloy model, implying strong physical and electronic interaction between the polymers. Photocurrent spectral response (PSR) and external quantum efficiency (EQE) measurements indicate that the present system does not exhibit the hallmarks of alloy formation. Measured values of the surface energies of the polymers support miscibility of P3HTT-DPP-10% with P3HT75-co-EHT25 but not with PCDTBT. Surface energy is proposed as a figure of merit for predicting alloy formation and compositional dependence of the Voc in ternary blend solar cells and miscibility between polymers is proposed as a necessary attribute for polymer pairs that will display alloy behavior.