© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Design rules are presented for significantly expanding sequential processing (SqP) into previously inaccessible polymer:fullerene systems by tailoring binary solvent blends for fullerene deposition. Starting with a base solvent that has high fullerene solubility, 2-chlorophenol (2-CP), ellipsometry-based swelling experiments are used to investigate different co-solvents for the fullerene-casting solution. By tuning the Flory-Huggins χ parameter of the 2-CP/co-solvent blend, it is possible to optimally swell the polymer of interest for fullerene interdiffusion without dissolution of the polymer underlayer. In this way solar cell power conversion efficiencies are obtained for the PTB7 (poly[(4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)(3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl)]) and PC61BM (phenyl-C61-butyric acid methyl ester) materials combination that match those of blend-cast films. Both semicrystalline (e.g., P3HT (poly(3-hexylthiophene-2,5-diyl)) and entirely amorphous (e.g., PSDTTT (poly[(4,8-di(2-butyloxy)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)-alt-(2,5-bis(4,4'-bis(2-octyl)dithieno[3,2-b:2'3'-d]silole-2,6-diyl)thiazolo[5,4-d]thiazole)]) conjugated polymers can be processed into highly efficient photovoltaic devices using the solvent-blend SqP design rules. Grazing-incidence wide-angle x-ray diffraction experiments confirm that proper choice of the fullerene casting co-solvent yields well-ordered interdispersed bulk heterojunction (BHJ) morphologies without the need for subsequent thermal annealing or the use of trace solvent additives (e.g., diiodooctane). The results open SqP to polymer/fullerene systems that are currently incompatible with traditional methods of device fabrication, and make BHJ morphology control a more tractable problem.

Our program on capacitive energy storage is a comprehensive one that combines experimental and computational components to achieve a fundamental understanding of charge storage processes in redox-based materials, specifically transition metal oxides. Some of the highlights of this program are the identification of intercalation pseudocapacitance in Nb2O 5, which enables high energy density to be achieved at high rates, and the development of a new route for synthesizing mesoporous films in which preformed nanocrystal building blocks are used in combination with polymer templating. The resulting material architectures have large surface areas and enable electrolyte access to the redox active pore walls, while the interconnected mesoporous film provides good electronic conductivity. Select first-principles density-functional theory studies of prototypical pseudocapacitor materials are reviewed, providing insight into the key physical and chemical features involved in charge transfer and ion diffusion. Rigorous multiscale physical models and numerical tools have been developed and used to reproduce electrochemical properties of carbon-based electrochemical capacitors with the ultimate objective of facilitating the optimization of electrode design. For the organic photovoltaic (OPV) program, our focus has been ongoing beyond the trial-and-error Edisonian approaches that have been responsible for the increase in power conversion efficiency of blend-cast (BC) bulk heterojunction blends of polymers and fullerenes. Our first approach has been to use molecular self-assembly to create the ideal nanometer-scale architecture using thermodynamics rather than relying on the kinetics of spontaneous phase segregation. We have created fullerenes that self-assemble into one-dimensional stacks and have shown that use of these self-assembled fullerenes lead to dramatically enhanced OPV performance relative to fullerenes that do not assemble. We also have created self-assembling conjugated polymers that form gels based on electrically continuous cross-linked micelles in solution, opening the possibility for water-processable "green" production of OPVs based on these materials. Our second approach has been to avoid kinetic control over phase separation by using a sequential processing (SqP) technique to deposit the polymer and fullerene materials in separate deposition steps. The polymer layer is deposited first, using solvents and deposition conditions that optimize the polymer crystallinity for swelling and hole mobility. The fullerene layer is then deposited in a second step from a solvent that swells the polymer but does not dissolve it, allowing the fullerene to penetrate into the polymer underlayer to the desired degree. Careful comparison of composition- and thickness-matched BC and SqP devices shows that SqP not only produces more efficient devices but also leads to devices that behave more consistently. © 2014 American Chemical Society.