Blends of conjugated polymers with fullerenes, polymers, or nanocrystals make promising materials for low-cost photovoltaic applications. Different processing conditions affect the efficiencies of these solar cells by creating a variety of nanostructured morphologies, however, the relationship between film structure and device efficiency is not fully understood. We introduce time-resolved electrostatic force microscopy (EFM) as a means to measure photoexcited charge in polymer films with a resolution of 100 nm and 100 micros. These EFM measurements correlate well with the external quantum efficiencies measured for a series of polymer photodiodes, providing a direct link between local morphology, local optoelectronic properties and device performance. The data show that the domain centres account for the majority of the photoinduced charge collected in polyfluorene blend devices. These results underscore the importance of controlling not only the length scale of phase separation, but also the composition of the domains when optimizing nanostructured solar cells.

The performance of organic solar cells is highly dependent on film morphology. However, directly correlating local film structures with device performance remains challenging. We demonstrate that photoconductive atomic force microscopy (pcAFM) can be used to map local photocurrents with 20 nm resolution in donor/acceptor blend solar cells of the conjugated polymer poly[2-methoxy-5-(3',7'-dimethyloctyl-oxy)-1,4-phenylene vinylene] (MDMO-PPV) with the fullerene (6,6)-phenyl-C61-butyric acid methyl ester (PCBM) spin-coated from various solvents. We present photocurrent maps under short-circuit conditions (zero applied bias) as well as under various applied voltages. We find significant variation in the short-circuit current between regions that appear identical in AFM topography. These variations occur from one domain to another as well as on larger length scales incorporating multiple domains. These results suggest that the performance of polymer-fullerene blends can still be improved through better control of morphology.

A general but limiting characteristic in excitonic photovoltaics is that a portion of the incident photon energy appears necessary for converting excitons into electrical charges, resulting in a loss of efficiency. Currently, the mechanism underlying this process is unclear. Here, we describe the development of an experimental method for measuring charge creation yields in organic solar cell materials. We use this method to examine a series of conjugated polymer:fullerene blend films and observe two unexpected features: the existence of an optimal driving force and a loss in conversion efficiency if this force is exceeded. These observations have implications for the design of excitonic photovoltaic devices and can be explained by a simple Marcus formulation that introduces the importance of reorganization energy.

We report a rapid-prototyping method for controlling nanoscale phase separation and pattern formation in conjugated polymer blend films using Dip-Pen Nanolithography (DPN). We use DPN to generate patterned alkylthiol monolayers with feature sizes down to 50 nm on gold surfaces and show how such patterns can nucleate the formation of lateral domains in blends of poly-3-hexylthiophene (P3HT) and polystyrene (PS) cast from solution. We show that this process can be used to probe phase nucleation at heterogeneous surface sites ranging in size from 50 to 750 nm, and that polymer features smaller than 150 nm in diameter can be achieved. We anticipate this method will be useful for studying polymer film responses to nanoscale surface fluctuations as well as for correlating nanoscale phase separation with optoelectronic processes in organic films used in light-emitting diode and photovoltaic devices.