RESUMEN
Poly(fluorene-alt-thiophene) (PFT) is a conjugated polyelectrolyte that self-assembles into rod-like micelles in water, with the conjugated polymer backbone running along the length of the micelle. At modest concentrations (â¼10 mg/mL in aqueous solutions), PFT forms hydrogels, and this work focuses on understanding the structure and intermolecular interactions in those gel networks. The network structure can be directly visualized using cryo electron microscopy. Oscillatory rheology studies further tell us about connectivity within the gel network, and the data are consistent with a picture where polymer chains bridge between micelles to hold the network together. Addition of tetrahydrofuran (THF) to the gels breaks those connections, but once the THF is removed, the gel becomes stronger than it was before, presumably due to the creation of a more interconnected nanoscale architecture. Small polymer oligomers can also passivate the bridging polymer chains, breaking connections between micelles and dramatically weakening the hydrogel network. Fits to solution-phase small-angle X-ray scattering data using a Dammin bead model support the hypothesis of a bridging connection between PFT micelles, even in dilute aqueous solutions. Finally, time-resolved microwave conductivity measurements on dried samples show an increase in carrier mobility after THF annealing of the PFT gel, likely due to increased connectivity within the polymer network.
Asunto(s)
Hidrogeles/química , Polielectrolitos/química , Microscopía por Crioelectrón , Electricidad , Furanos/química , Cinética , Micelas , Microondas , Modelos Químicos , Reología , Dispersión del Ángulo Pequeño , Soluciones/química , Sustancias Viscoelásticas/química , Agua/química , Difracción de Rayos XRESUMEN
By controlling the polymer/polymer blend self-organization rate, all-polymer solar cells composed of a high-mobility, crystalline, naphthalene diimide-selenophene copolymer acceptor and a benzodithiophene-thieno[3,4-b]thiophene copolymer donor are achieved with a record 7.7% power conversion efficiency and a record short-circuit current density (18.8 mA cm(-2)).
RESUMEN
The efficiency of biological photosynthesis results from the exquisite organization of photoactive elements that promote rapid movement of charge carriers out of a critical recombination range. If synthetic organic photovoltaic materials could mimic this assembly, charge separation and collection could be markedly enhanced. We show that micelle-forming cationic semiconducting polymers can coassemble in water with cationic fullerene derivatives to create photoinduced electron-transfer cascades that lead to exceptionally long-lived polarons. The stability of the polarons depends on the organization of the polymer-fullerene assembly. Properly designed assemblies can produce separated polaronic charges that are stable for days or weeks in aqueous solution.