Enabling Kinetics and Structural Control of Polymer-Grafted Nanoparticle Superstructures via Solvent Vapor Annealing

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NON-TECHNICAL SUMMARY Hybrid materials are enabling new applications and technologies in nanophotonics, nanofabrication, fuel cells, photovoltaics, nanomembranes, batteries, and more. Rationally designed polymer-nanoparticle composites can synergize the attributes of polymeric and inorganic materials, generating new synthesis and processing possibilities and physical properties that are unattainable with a single homogeneous material. With this project, supported by the Solid State and Materials Chemistry program in the Division of Materials Research, Professor Xingchen Ye and his research group at Indiana University are developing multifunctional nanocomposite materials through self-assembly. This research is expanding the synthetic and processing toolbox in order to achieve nanocomposites by design. This project provides training in nanomaterial synthesis and characterization to both graduate and undergraduate students. In addition, summer research opportunities are provided to members of underrepresented groups through partnerships with North Carolina A&T State University and the Groups Scholars Program at Indiana University.TECHNICAL SUMMARY The development of next-generation polymer nanocomposites requires simultaneous advances in the synthesis of nanoparticles and polymer matrices, precise engineering of the organic-inorganic interface, and three-dimensional structural control. Self-assembly promises scalability, provides molecular-level design of building blocks and produces three-dimensional materials. The key challenge in achieving sophisticated control over the spatial distribution of individual nanoparticles through self-assembly lies in the lack of ability to probe and manipulate the pathways of nanocomposite formation. This project, supported by the Solid State and Materials Chemistry program in the Division of Materials Research, is addressing this challenge by using polymer-grafted nanoparticle (PGNP) building blocks to understand and control the kinetic pathways and phase behaviors of PGNP superstructures using solvent vapor annealing. Specifically, this project will (i) establish the versatility of solvent annealing for the synthesis of multicomponent PGNP superstructures, (ii) demonstrate pathway control and polymorph selection by changing solvent annealing parameters, and (iii) assemble shape-anisotropic PGNP into close-packed and low-density superstructures and elucidate assembly pathways. This research will provide fundamental and quantitative insight into the interplay between thermodynamic and kinetic factors that dictate PGNP assembly outcome, and will lay the groundwork for predictive synthesis of ordered PGNP superstructures with kinetic pathway control, unprecedented compositional and structural diversity as well as reconfigurability.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.