In this study, we developed a novel in situ hydrothermal method to fabricate self-assembled P3HT/TiO2 hybrid nanowires for solar cell applications.

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A series of 3‐substituted polythiophene copolymers having different side chain arrangements of hexyl and hexyloxyl groups has been synthesized via the Grignard metathesis (GRIM) method. Despite differences in monomer reactivity ratios for the nickel‐catalyzed transfer chain polymerization, random sequences of hexyl‐ and hexyloxy‐substituted polythiophenes with different monomer compositions and adjustable band‐gap energies can be synthesized according to their respective comonomer feed ratio. This study shows potential for synthesizing random copolymers with different monomer reactivities via the GRIM method for further optoelectronic application.

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In this study, we demonstrate a facile in situ synthetic strategy to fabricate self-assembled organic/inorganic hybrid nanowires, wherein a “pre-crystallization” approach was first utilized to co-organize P3HT molecules and zinc precursors into highly elongated nanowires, followed by a thermal oxidation treatment to directly grow ZnO nanocrystals on the existing nanofibrillar template. By further thermal annealing the ZnO embossed hybrid nanowires, a unique superhighway-like architecture which composed of alternating parallel channels of P3HT nanofibrils and ZnO nanocrystals could be further obtained. This donor/acceptor (D/A) parallel-channel structure gave access to the improvements in the exciton dissociation and charge transport, thereby enhancing photoluminescence quenching, charge transport, and device performance. The photovoltaic devices with the D/A parallel-lane structure gave a high PCE of 0.61% as compared to only 0.07% from a conventional P3HT/ZnO bulk heterojuction solar cell. Our approach offers a versatile route to coassemble inorganic nanocrystals with π-conjugated polymer hosts, forming uniform one-dimensional hybrid nanochannels potentially useful in optoelectronic applications.