CAREER: Advanced Molecular Architectures for Electronically-Active Radical Polymers

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NON-TECHNICAL SUMMARYThe development of new electronic materials is critical to a number of technological fields that range from defense applications to personal electronic devices to biomedical monitoring and drug delivery. This project will develop new kinds of plastic electronic materials that are lightweight, flexible, and stretchable in nature. In particular, it will establish how such polymers can be used in next-generation flexible electronic devices. In addition to having robust mechanical properties these plastics also can be deposited in a manner that is consistent with low-cost production techniques like inkjet printing. Furthermore, these efforts will correlate the mechanical properties of the newly-synthesized materials with electronic properties of plastic materials. In achieving this goal, the project will be able to establish the fundamental design principles that will allow for a new class of plastic conductors to be implemented in a number of energy conversion, energy storage, and biomedical devices, which will aid the nation and individual consumers. Additionally, this effort will support the training of graduate, undergraduate, and high school students in the realm of fundamental and applied polymer science. In particular, a high school research program will be implemented in order to attract a larger number of students from economically-disadvantaged families to the polymer science field so as to increase the diversity of the upcoming population of scientists and engineers. Also, the general public will have access to these same types of polymer science lessons due to the development of a massive open online course (MOOC) that will be focused on polymer synthesis and application. In this way, the effort presented here will offer significant fundamental polymer science, polymer engineering, and educational impacts that will allow for the advancement of new plastic electronic materials in both the near and long terms.TECHNICAL SUMMARYElectronically-active macromolecules have been of intense investigation for their application in a number of advanced energy conversion and energy storage modules. To date, the majority of the effort regarding these polymeric materials and polymer-based devices has focused on closed-shell polymers containing a rather high degree of conjugation along their macromolecular backbones. Recently, however, a new class of oxidation-reduction-active (redox-active), non-conjugated organic entities known as radical polymers (i.e., macromolecules comprised of non-conjugated backbones and with pendant groups bearing stable radical sites) have attracted a great deal of attention for their relatively high performance in electrolyte-supported and solid-state organic electronic device applications. However, it is becoming apparent that, without fundamental advances regarding the polymer chemistry and polymer physics of open-shell macromolecules, the true potential of radical polymer systems will not be established despite the potential advantages that radical polymers could have relative to conjugated polymer systems. This effort will address these issues through the coupling of polymer synthesis with fundamental polymer physics measurements and the electrical characterization of these designer macromolecules. In particular, the PI and his group will: (1) synthesize a suite of targeted macromolecules containing select backbones, stereoregularities, and open-shell architectures; (2) evaluate the structural, thermal, and flow properties of these newly-synthesized materials; (3) correlate the electronic properties of the novel radical polymers to their chemical, thermal, and structural properties; and (4) refine the design of the macromolecules in order to elucidate their fundamental structure-property-performance relationships. In this way, this effort will provide the design principles that should allow for the radical polymers to be translated into commercially-relevant, commodity materials. This, in turn, also will allow open-shell macromolecules to play a larger part in the growing organic electronics industry.