Synergistic In Situ Hybrid Synthesis of Highly Crystalline P3HT/ZnO Nanowires at Elevated Pressures

Abstract

Organic/inorganic hybrid structures are promising systems for a variety of functional devices because of their low cost, light weight, and ease of large-scale production. However, the ability to control the morphology to obtain a large interfacial area for hybrid interactions and continuous transportation pathway for enhanced optoelectronic properties is still a critical issue for advanced applications. Here, we report on a facile development of a hydrothermal method at elevated pressure to manufacture P3HT/ZnO nanohybrid thin films comprising in situ synthesized ZnO nanocrystals embossed on structure-directing long-range order P3HT nanofibrils. The in situ hybrid fabrication method first involves chelating zinc acetate on the sulfur atoms in P3HT as the anchoring sites, followed by utilizing the high pressure (∼9 bar) hydrothermal process to synthesize ZnO nanoparticles on P3HT nanofibrils, synergistically resulting in high crystallinity for both materials in nanoscale. This process demonstrated the ability to synthesize highly crystalline monophasic wurtzite-type ZnO nanoparticles in situ on organic polymers at temperatures (≤150 °C) typically below the melting temperature of the organic polymers to preserve their superior crystalline property, compared with an ambient pressure fabrication process in which in situ grown ZnO nanoparticles in the hybrids remained mostly amorphous at 150 °C. In particular, photophysical property analyses showed that the highly crystalline P3HT/ZnO hybrid films exhibited enhanced UV absorption, photoluminescence quenching, and shorter exciton lifetime. This enhancement in the optoelectronic properties indicated that the hybrid possessed intimate contact at D/A interfaces for photogenerated excitons dissociation and provided continuous nanochannels for efficient charge transfer, thus leading to superior performance of optoelectronic properties. We believe that this study paves the way for fabricating highly functional hybrid materials for future optoelectronic applications.

Crystallization-Driven Solution-State Assembly of Conjugated Block Copolymers in Materials Science

“…Subsequently, Dai and co-workers employed a one-pot synthetic strategy to fabricate self-assembled P3HT/ZnO hybrid nanowires (Figure 6f). 153 The nanowires were prepared as a template for hybrids in the crystallization of P3HT. The sulfur atoms in the P3HT nanowires served as anchoring sites for the coordination of the zinc acetate.…”

“…(f) P3HT/ZnO hybrid nanowires by coordination of Zn ions on the surface of P3HT nanowires. Reproduced with permission from ref .…”

“…Subsequently, Dai and co-workers employed a one-pot synthetic strategy to fabricate self-assembled P3HT/ZnO hybrid nanowires (Figure f) . The nanowires were prepared as a template for hybrids in the crystallization of P3HT.…”

Embossed Hybrid Synthesis of ZnO Nanocrystals on Self‐Organized One‐Dimensional Poly(3‐butylthiophene) Nanowires

“…These disadvantages can be overcome by adopting in situ fabrication of inorganic semiconductor within organic polymer material . In this methodology, π‐conjugated polymer such as P3HT offers a combining response since it encompasses an electron giving sulfur at its monomer unit, a potential harbor site for chelating metal ions . The planar conformation of P3HT can further offer a flat molecular architecture to efficiently induce the growth of inorganic nanocrystals within the polymer matrix.…”