Structure and Conductivity of Semiconducting Polymer Hydrogels.

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 (∼10 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.

Extensive Penetration of Evaporated Electrode Metals into Fullerene Films: Intercalated Metal Nanostructures and Influence on Device Architecture.

Although it is known that evaporated metals can penetrate into films of various organic molecules that are a few nanometers thick, there has been little work aimed at exploring the interaction of the common electrode metals used in devices with fullerene derivatives, such as organic photovoltaics (OPVs) or perovskite solar cells that use fullerenes as electron transport layers. In this paper, we show that when commonly used electrode metals (e.g., Au, Ag, Al, Ca, etc.) are evaporated onto films of fullerene derivatives (such as [6,6]-phenyl-C61-butyric acid methyl ester (PCBM)), the metal penetrates many tens of nanometers into the fullerene layer. This penetration decreases the effective electrical thickness of fullerene-based sandwich structure devices, as measured by the device's geometric capacitance, and thus significantly alters the device physics. For the case of Au/PCBM, the metal penetrates a remarkable 70 nm into the fullerene, and we see penetration of similar magnitude in a wide variety of fullerene derivative/evaporated metal combinations. Moreover, using transmission electron microscopy to observed cross-sections of the films, we show that when gold is evaporated onto poly(3-hexylthiophene) (P3HT)/PCBM sequentially processed OPV quasi-bilayers, Au nanoparticles with diameters of ∼3-20 nm are formed and are dispersed entirely throughout the fullerene-rich overlayer. The plasmonic absorption and scattering from these nanoparticles are readily evident in the optical transmission spectrum, demonstrating that the interpenetrated metal significantly alters the optical properties of fullerene-rich active layers. This opens a number of possibilities in terms of contact engineering and light management so that metal penetration in devices that use fullerene derivatives could be used to advantage, making it critical that researchers are aware of the electronic and optical consequences of exposing fullerene-derivative films to evaporated electrode metals.