Harnessing Compositional Gradients to Elucidate Phase Behaviors toward High Performance Polymer Semiconductor Blends

Polymer semiconductor/insulator blends offer a promising avenue to achieve desired mechanical properties, environmental stability, and high device performance in organic field-effect transistors. A comprehensive understanding of process-structure-property relationships necessitates a thorough exploration of the composition space to identify transitions in performance, morphology, and phase behavior. Hence, this study employs a high-throughput gradient thin film library, enabling rapid and continuous screening of composition-morphology-device performance relationships in conjugated polymer blends. Applied to a donor-acceptor copolymer blend, this technique efficiently surveys a broad composition range, capturing trends in device performance across the gradient. Furthermore, characterizing the gradient library using microscopy and depth profiling techniques pinpointed composition-dependent transitions in morphology. To validate the results and gain deeper insights, uniform-composition experiments were conducted on select compositions within and outside the gradient range. Depth profiling experiments on the constant composition films unveil the presence of the semiconducting polymer at the air interface, with apparent enrichment of the semiconductor at the substrate interface at low ratios of the semiconducting component, transitioning to a more even distribution within the bulk of the film at higher ratios. The generalizability of the gradient approach was further confirmed by its application to a homopolymer under different solution processing conditions.