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Recent experiments have reported intriguing trends for the molecular weight (MW) dependence of the conductivity of block copolymer lamellae that contrast with the behavior of homopolymer matrices. By using coarse-grained simulations of the sorption and transport of penetrant cations, we probe the possible mechanisms underlying such behavior. Our results indicate that the MW dependence of conductivity of homopolymeric and block copolymeric matrices arise from different mechanisms. On the one hand, the solvation energies of cations, and, in turn, the charge carrier concentrations, themselves, exhibit a MW dependence in block copolymer matrices. Such trends are shown to arise from variations in the thickness of the conducting phase relative to that of the interfacial zones. Moreover, distinct mechanisms are shown to be responsible for the diffusivities of ions in homopolymer and block copolymer matrices. In the former, diffusivity effects associated with the free ends of the polymers play an important role. In contrast, in block copolymer lamellae, the interfacial zone between the blocks presents a zone of hindered diffusivity for ions and manifests as a molecular weight dependence of the ionic diffusivity. Together, the preceding mechanisms are shown to provide a plausible explanation for the experimentally observed trends for the conductivity of block copolymer matrices.

We present results obtained using a drift-diffusion model for the structure−property correlations in photovoltaic devices based on self-assembly of rod−coil block copolymers. We use a self-consistent field theory model to generate the self-assembly morphologies of rod−coil block copolymers in confined situations. The density and orientational order parameter profiles so-obtained are then used as input to a recently proposed drift-diffusion model which predicts the photovoltaic device characteristics. The latter model allows for prescription of arbitrary morphologies of donor and acceptor phases while simultaneously incorporating the role of anisotropic charge transport of holes and excitons that arise in the ordered phases of rod−coil block copolymers. We present results elucidating the role of morphology of self-assembly, orientation of lamellar phases, domain widths, and the degree of phase separation and orientational ordering, upon the photovoltaic device characteristics.

The Flory−Huggins interaction is measured for a model rod−coil block copolymer system, poly(alkoxyphenylenevinylene-b-isoprene), by fitting the interfacial segregation of block copolymer to a homopolymer interface and by using the random phase approximation (RPA) for block copolymers. The measured interfacial segregation of a block copolymer to the interface between homopolymers, fit with a self-consistent field theory (SCFT) simulation using χ as a variable parameter, gives a functional form χ = 34.8/T − 0.091. When RPA is applied to neutron scattering curves for the rod−coil system above the order−disorder transition, the theoretical structure factors are inconsistent with observed scattering curves due to complex aggregated structures formed in the nematic and isotropic states. Using the Flory−Huggins parameter and a previously measured value of the Maier−Saupe parameter, the PPV-b-PI phase diagram may be converted from system-specific variables to dimensionless parameters. Under the assumptions that t...

We present a new model based on self-consistent field theory (SCFT) approach and complement it by strong segregation theory (SST) based calculations to characterize the self-assembly behavior in si...