Browsing by Author "Sumpter, Bobby G."

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    Amphiphilic Bottlebrush Block Copolymers: Analysis of Aqueous Self-Assembly by Small-Angle Neutron Scattering and Surface Tension Measurements
    (American Chemical Society, 2019) Alaboalirat, Mohammed; Qi, Luqing; Arrington, Kyle J.; Qian, Shuo; Keum, Jong K.; Mei, Hao; Littrell, Kenneth C.; Sumpter, Bobby G.; Carrillo, Jan-Michael Y.; Verduzco, Rafael; Matson, John B.
    A systematic series of 16 amphiphilic bottlebrush block copolymers (BCPs) containing polystyrene and poly(N-acryloylmorpholine) (PACMO) side chains were prepared by a combination of atom-transfer radical polymerization (ATRP), photoiniferter polymerization, and ring-opening metathesis polymerization (ROMP). The grafting-through method used to prepare the polymers enabled a high degree of control over backbone and side-chain molar masses for each block. Surface tension measurements on the self-assembled amphiphilic bottlebrush BCPs in water revealed an ultralow critical micelle concentration (cmc), 1–2 orders of magnitude lower than linear BCP analogues on a molar basis, even for micelles with >90% PACMO content. Combined with coarse-grained molecular dynamics simulations, fitting of small-angle neutron scattering traces (SANS) allowed us to evaluate solution conformations for individual bottlebrush BCPs and micellar nanostructures for self-assembled macromolecules. Bottlebrush BCPs showed an increase in anisotropy with increasing PACMO content in toluene-d8, which is a good solvent for both blocks, reflecting an extended conformation for the PACMO block. SANS traces of bottlebrush BCPs assembled into micelles in D2O, a selective solvent for PACMO, were fitted to a core–shell–shell model, suggesting the presence of a partially hydrated inner shell. Results showed an average micelle diameter of 40 nm with combined shell diameters ranging from 16 to 18 nm. A general trend of increased stability of micelles (i.e., resistance to precipitation) was observed with increases in PACMO content. These results demonstrate the stability of bottlebrush polymer micelles, which self-assemble to form spherical micelles with ultralow (<70 nmol/L) cmc’s across a broad range of compositions.
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    An experimental and computational study of donor–linker–acceptor block copolymers for organic photovoltaics
    (Wiley, 2018) Hu, Zhiqi; Jakowski, Jacek; Zheng, Chenyu; Collison, Christopher J.; Strzalka, Joseph; Sumpter, Bobby G.; Verduzco, Rafael
    Block copolymers with donor and acceptor conjugated polymer blocks provide an approach to dictating the donor–accepter interfacial structure and understanding its relationship to charge separation and photovoltaic performance. We report the preparation of a series of donor‐linker‐acceptor block copolymers with poly(3‐hexylthiophene) (P3HT) donor blocks, poly((9,9‐dioctylfluorene)‐2,7‐diyl‐alt‐[4,7‐bis(thiophen‐5‐yl)‐2,1,3‐benzothiadiazole]‐2′,2″‐diyl) (PFTBT) acceptor blocks, and varying lengths of oligo‐ethylene glycol (OEG) chains as the linkers. Morphological analysis shows that the linkers increase polymer crystallinity while a combination of optical and photovoltaic measurements shows that the insertion of a flexible spacer reduces fluorescence quenching and photovoltaic efficiencies of solution processed photovoltaic devices. Density functional theory (DFT) simulations indicate that the linking groups reduce both charge separation and recombination rates, and block copolymers with flexible linkers will likely rotate to assume a nonplanar orientation, resulting in a significant loss of overlap at the donor–linker–acceptor interface. This work provides a systematic study of the role of linker length on the photovoltaic performance of donor–linker–acceptor block copolymers and indicates that linkers should be designed to control both the electronic properties and relative orientations of conjugated polymers at the interface.