CAREER: Directed Self-Assembly of 2D Plasmonic Nanoparticles in Block Copolymer Nanofibers to Form Hierarchical Nanostructures

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PART 1: NON-TECHNICAL SUMMARYPolymers containing two-dimensional (2D) plasmonic nanoparticles could contribute to transformative technologies such as waveguides, photovoltaics, sensors, actuators, and photo-responsive adhesives. This CAREER project addresses the fundamental issue of designing the interface between polymers and 2D plasmonic nanoparticles. The solutions to this issue will lay the foundation for integrating 2D plasmonic nanoparticles into polymeric materials and creating hybrid functional composites with advanced optical, photo-thermal, and plasmonic properties. In particular, fibers and filaments of polymers with hierarchically stacked 2D plasmonic nanoparticles can be used as inks for additive manufacturing of plasmonic functional constructs. The hybrid material can help design photovoltaics with superior power conversion efficiencies, as well as other functional devices in energy and environmental sciences that are of industrial and societal importance.The educational impacts involve the training of underrepresented and first-generation college students in Appalachia. In particular, a mini summer research camp for underrepresented students from neighboring Historically Black Colleges and Universities (HBCUs)will be developed, and the PI will serve as a senior fellow in the university's Residential College to promote STEM and improve the success rate of underrepresented and first-generation college students. In this way, the effort presented here will train underrepresented local youth, especially first-generation college students in isolated Appalachia, to become future polymer scientists and engineers who will build and reshape the regional polymer industries.PART 2: TECHNICAL SUMMARYFibers possess attractive properties that thin films and bulk samples lack, for instance, large surface area, low density, high strength, and peripherally confined self-assembly. The goal of the proposed project is to exploit electrospinning and block copolymer directed self-assembly to create hierarchical structures of block copolymers and 2D plasmonic nanoparticles in fibers, which have fascinating structural and photo-thermal properties. The main scopes are to understand the mechanism of polymer brush formation on 2D plasmonic nanoparticles and design tailored polymer/nanoparticle interfaces for creating hierarchical nanostructures in fibers. The central hypothesis states that, by exploiting the unique plasmonic properties of 2D plasmonic nanoparticles, the polymer brush formation mechanism will be discovered, block copolymer/2D plasmonic nanoparticle interface for hierarchical directed self-assembly in fibers will be prepared, and structural and photothermal properties that are distinctive features of plasmonic polymers will be understood. The proposed goal will be realized via three main tasks: 1) employ 2D plasmonic nanoparticles to unveil the mechanism of polymer brush formation, 2) utilize block copolymers to direct the self-assembly of 2D plasmonic nanoparticles and form hierarchical structures in fibers, 3) understand the domain spacing and photothermal properties of block copolymers upon mixing with 2D plasmonic nanoparticles. The block copolymers are expected to exhibit preferred domain orientation in the fibers, and the 2D nanoparticles to form stacked layers with monolayers of 2D nanoparticles in each block copolymer domain. The hierarchical nanostructures will bestow on polymers novel plasmonic properties and be active candidates for applications in waveguides, photovoltaics, adhesives, and 3D printing inks.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.