Nanostructured photovoltaic materials using block polymer assemblies

Mastroianni, Sarah Elizabeth
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University of Delaware
Despite its potential as an abundant, sustainable alternative to non-renewable energy sources, solar energy currently is underutilized. Photovoltaics, which convert energy from sunlight into electricity, commonly are made from inorganic semiconductor materials that require expensive manufacturing and processing techniques. Alternatively, organic materials can be used to produce flexible and lightweight organic photovoltaic (OPV) devices, which can be prepared using solution-based processing techniques. However, OPV devices are limited by low efficiencies and short lifetimes compared to their inorganic counterparts. In OPV systems, charge carriers are generated in the active layer via the separation of excitons (electron-hole pairs) at interfaces between donor and acceptor materials. Because excitons have a limited diffusion length (∼10 nm), they may recombine before reaching a donor-acceptor interface if domain sizes are large. This exciton recombination can limit device efficiency; thus, the design parameters for improved active layer morphologies include large interfacial areas, small size scales, and continuous conducting pathways. Currently, most OPV devices are prepared by blending donor and acceptor materials in bulk heterojunction (BHJ) devices, often resulting in non-ideal, process-dependent morphologies. Alternatively, the self-assembly of block polymers (BP)s offers a reproducible means to generate nanostructured active layers. The work presented in this dissertation examines the synthetic approaches to preparing BPs containing different electroactive materials: non-conjugated, amorphous poly(vinyl- m -triphenylamine) [PVm TPA] and conjugated poly(3-alkythiophene) [P3AT] p -type materials as well as fullerene-based n -type materials. The synthesis and self-assembly of a model poly(methyl methacrylate)- b -PVmTPA system is presented. This work was extended to synthesize PVm TPA BPs with complementary poly(methyl methacrylate- co -hydroxyethyl methacrylate) [P(MMA-co -HEMA)] blocks onto which fullerenes were grafted using post-polymerization coupling reactions. P3AT BP synthetic techniques also were explored but largely were limited by P3AT purity and end-functionalization. Nevertheless, reversible addition-fragmentation chain-transfer (RAFT) polymerization offered a viable method to incorporate all three of the examined electroactive materials into BPs. The approaches presented in this dissertation provide the tools to design, synthesize, and characterize new BPs for OPVs that can reproducibly self-assemble into well-defined nanostructures.