Heterogeneity in Polymer Solar Cells: Local Morphology and Performance in Organic Photovoltaics Studied with Scanning Probe Microscopy

The use of organic photovoltaics (OPVs) could reduce production costs for solar cells because these materials are solution processable and can be manufactured by roll-to-roll printing. The nanoscale texture, or film morphology, of the donor/acceptor blends used in most OPVs is a critical variable that can dominate both the performance of new materials being optimized in the lab and efforts to move from laboratory-scale to factory-scale production. Although efficiencies of organic solar cells have improved significantly in recent years, progress in morphology optimization still occurs largely by trial and error, in part because much of our basic understanding of how nanoscale morphology affects the optoelectronic properties of these heterogeneous organic semiconductor films has to be inferred indirectly from macroscopic measurements. In this Account, we review the importance of nanoscale morphology in organic semiconductors and the use of electrical scanning probe microscopy techniques to directly probe the local optoelectronic properties of OPV devices. We have observed local heterogeneity of electronic properties and performance in a wide range of systems, including model polymer fullerene blends such as poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C-61-butyric acid methyl ester (PCBM), newer polyfluorene copolymer PCBM blends, and even all polymer donor acceptor blends. The observed heterogeneity in local photocurrent poses important questions, chiefly what information is contained and what is lost when using average values obtained from conventional measurements on macroscopic devices and bulk samples? We show that in many cases OPVs are best thought of as a collection of nanoscopic photodiodes connected in parallel, each with their own morphological and therefore electronic and optical properties. This local heterogeneity forces us to carefully consider the adequacy of describing OPVs solely by average properties such as the bulk carrier mobility. Characterizing this local heterogeneity in the morphology of an OPV and the consequent variations in local performance is vital to understanding OPV operation.