Among the parameters that characterize a solar cell and define its power-conversion efficiency, the fill factor is the least well understood, making targeted improvements difficult. Here we quantify the competition between charge extraction and recombination by using a single parameter θ, and we demonstrate that this parameter is directly related to the fill factor of many different bulk-heterojunction solar cells. Our finding is supported by experimental measurements on 15 different donor:acceptor combinations, as well as by drift-diffusion simulations of organic solar cells in which charge-carrier mobilities, recombination rate, light intensity, energy levels and active-layer thickness are all varied over wide ranges to reproduce typical experimental conditions. The results unify the fill factors of several very different donor:acceptor combinations and give insight into why fill factors change so much with thickness, light intensity and materials properties. To achieve fill factors larger than 0.8 requires further improvements in charge transport while reducing recombination.

The authors present efficient all‐polymer solar cells comprising two different low‐bandgap naphthalenediimide (NDI)‐based copolymers as acceptors and regioregular P3HT as the donor. It is shown that these naphthalene copolymers have a strong tendency to preaggregate in specific organic solvents, and that preaggregation can be completely suppressed when using suitable solvents with large and highly polarizable aromatic cores. Organic solar cells prepared from such nonaggregated polymer solutions show dramatically increased power conversion efficiencies of up to 1.4%, which is mainly due to a large increase of the short circuit current. In addition, optimized solar cells show remarkable high fill factors of up to 70%. The analysis of the blend absorbance spectra reveals a surprising anticorrelation between the degree of polymer aggregation in the solid P3HT:NDI copolymer blends and their photovoltaic performance. Scanning near‐field optical microscopy (SNOM) and atomic force microscopy (AFM) measurements reveal important information on the blend morphology. It is shown that films with high degree of aggregation and low photocurrents exhibit large‐scale phase‐separation into rather pure donor and acceptor domains. It is proposed that, by suppressing the aggregation of NDI copolymers at the early stage of film formation, the intermixing of the donor and acceptor component is improved, thereby allowing efficient harvesting of photogenerated excitons at the donor–acceptor heterojunction.

Developing novel materials and device architectures to further enhance the efficiency of polymer solar cells requires a fundamental understanding of the impact of chemical structures on photovoltaic properties. Given that device characteristics depend on many parameters, deriving structure-property relationships has been very challenging. Here we report that a single parameter, hole mobility, determines the fill factor of several hundred nanometer thick bulk heterojunction photovoltaic devices based on a series of copolymers with varying amount of fluorine substitution. We attribute the steady increase of hole mobility with fluorine content to changes in polymer molecular ordering. Importantly, all other parameters, including the efficiency of free charge generation and the coefficient of nongeminate recombination, are nearly identical. Our work emphasizes the need to achieve high mobility in combination with strongly suppressed charge recombination for the thick devices required by mass production technologies.

A long standing question in organic electronics concerns the effects of molecular orientation at donor/acceptor heterojunctions. Given a well-controlled donor/acceptor bilayer system, we uncover the genuine effects of molecular orientation on charge generation and recombination. These effects are studied through the point of view of photovoltaics—however, the results have important implications on the operation of all optoelectronic devices with donor/acceptor interfaces, such as light emitting diodes and photodetectors. Our findings can be summarized by two points. First, devices with donor molecules face-on to the acceptor interface have a higher charge transfer state energy and less non-radiative recombination, resulting in larger open-circuit voltages and higher radiative efficiencies. Second, devices with donor molecules edge-on to the acceptor interface are more efficient at charge generation, attributed to smaller electronic coupling between the charge transfer states and the ground state, and lower activation energy for charge generation.

New polymers with high electron mobilities have spurred research in organic solar cells using polymeric rather than fullerene acceptors due to their potential of increased diversity, stability, and scalability. However, all‐polymer solar cells have struggled to keep up with the steadily increasing power conversion efficiency of polymer:fullerene cells. The lack of knowledge about the dominant recombination process as well as the missing concluding picture on the role of the semi‐crystalline microstructure of conjugated polymers in the free charge carrier generation process impede a systematic optimization of all‐polymer solar cells. These issues are examined by combining structural and photo‐physical characterization on a series of poly(3‐hexylthiophene) (donor) and P(NDI2OD‐T2) (acceptor) blend devices. These experiments reveal that geminate recombination is the major loss channel for photo‐excited charge carriers. Advanced X‐ray and electron‐based studies reveal the effect of chloronaphthalene co‐solvent in reducing domain size, altering domain purity, and reorienting the acceptor polymer crystals to be coincident with those of the donor. This reorientation correlates well with the increased photocurrent from these devices. Thus, efficient split‐up of geminate pairs at polymer/polymer interfaces may necessitate correlated donor/acceptor crystal orientation, which represents an additional requirement compared to the isotropic fullerene acceptors.