Considerable academic and industrial efforts have been dedicated to resolving scientific and technological issues associated with the fabrication of efficient plastic solar cells via solution deposition techniques. The most successful strategy used to generate solution processable devices implements a two component donor-acceptor type system composed of a (p-type) narrow bandgap conjugated polymer donor blended with a (n-type) fullerene acceptor. Due to the limited exciton diffusion lengths (~10 nm) inherent to these materials, efficient photoinduced charge generation requires heterojunction formation (i.e. donor/acceptor interfaces) in close proximity to the region of exciton generation. Maximal charge extraction therefore requires that donor and acceptor components form nanoscale phase separated percolating pathways to their respective electrodes. Devices exhibiting these structural characteristics are termed bulk heterojunction devices (BHJ). Although the BHJ architecture highlights the basic characteristics of functional donor-acceptor type organic solar cells, device optimization requires internal order within each phase and proper organization relative to the substrate in order to maximize charge transport efficiencies and minimize charge carrier recombination losses. The economic viability of BHJ solar cells hinges upon the minimization of processing costs; thus, commercially relevant processing techniques should generate optimal structural characteristics during film formation, eliminating the need for additional post deposition processing steps.

Empirical optimization has shown that solution deposition using high boiling point additives (e.g. octanedithiol (ODT)) provides a simple and widely used fabrication method for maximizing the power conversion efficiencies of BHJ solar cells. This work will show using x-ray scattering that a small percentage of ODT (~2%) in chlorobenzene induces the nucleation of polymeric crystallites within 2 min of deposition, increases the orientational order of specific polymorphs, and promotes further crystallite nucleation over a period longer than 40 min after casting. In addition, three dimensional chemical maps derived from energy filtered transmission electron microtomography (EF-TEMT) are used to demonstrate that subtle changes in the chemistry of the polymer backbone, as well as the use of solvent additives, have dramatic effects on the types of phase separated structures that develop in two different high efficiency solar cell blends. Solvent additives are demonstrated to have the ability both to refine coarser than optimal microstructures and to coarsen finer than optimal microstructures.