Tandem solar cells, in which two solar cells with different absorption characteristics are linked to use a wider range of the solar spectrum, were fabricated with each layer processed from solution with the use of bulk heterojunction materials comprising semiconducting polymers and fullerene derivatives. A transparent titanium oxide (TiO(x)) layer separates and connects the front cell and the back cell. The TiO(x) layer serves as an electron transport and collecting layer for the first cell and as a stable foundation that enables the fabrication of the second cell to complete the tandem cell architecture. We use an inverted structure with the low band-gap polymer-fullerene composite as the charge-separating layer in the front cell and the high band-gap polymer composite as that in the back cell. Power-conversion efficiencies of more than 6% were achieved at illuminations of 200 milliwatts per square centimeter.

The presence of interchain species in the photophysics of conjugated polymer films has been the subject of a great deal of controversy. In this paper, we present strong evidence that interchain species do form in conjugated polymer films, and that the degree of interchain interactions can be controlled by varying the solvent and polymer concentration of the solution from which the films are cast. Thus, much of the controversy in the literature can be resolved by noting that the polymer samples in different studies had different side groups or were prepared in different ways and thus have different degrees of interchain interaction. The photoluminescence (PL) of poly(2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylene vinylene), MEH-PPV, changes both its spectral shape and quantum yield when the films are prepared from different solutions or when the morphology is varied by annealing. Increasing the amount of interchain interactions enhances the red portion of the film's PL, a result assigned to a combination of changes in the vibronic structure of the PL of the exciton and increased numbers of weakly emissive interchain species. Photoluminescence excitation spectroscopy shows that excitation to the red edge of the absorption band preferentially enhances the red emission, suggesting that the interchain species are aggregates with a distinct ground state absorption. Scanning force microscopy shows topographic features that correlate with the degree of interchain interactions, verifying that the morphology of conjugated polymer films changes with polymer concentration, choice of solvent, and spin-casting speed. Even at low excitation intensities, photooxidative damage occurs quickly in MEH-PPV films excited in air, and the rate at which damage occurs is sensitive to the packing of the polymer chains. For samples under vacuum at low excitation intensity, a long-lived emissive tail, in combination with excitedstate absorption dynamics that do not match those of the emissive species, provide direct evidence for the production of interchain aggregates. Annealing an MEH-PPV film produces a photophysical signature similar to photooxidation, implying that defects in conjugated polymer films are intrinsic and depend on the details of how the chains are packed. At higher excitation intensities, we find that exciton-exciton annihilation occurs, and that the probability for annihilation can vary by an order of magnitude depending on the degree of interchain contact in the film. Finally, we show that changing the film morphology has a direct effect on the performance of MEH-PPV-based light-emitting diodes. Higher degrees of interchain interaction enhance the mobility of carriers at the expense of lower quantum efficiencies for electroluminescence. Taken together, the results reconcile much of the contradictory literature and provide a prescription for the optimization of conjugated polymer films for particular device applications.

Research relating to organic solar cells based on solution‐processed, bulk heterojunction (BHJ) films has been dominated by polymeric donor materials, as they typically have better film‐forming characteristics and film morphology than their small‐molecule counterparts. Despite these morphological advantages, semiconducting polymers suffer from synthetic reproducibility and difficult purification procedures, which hinder their commercial viability. Here, a non‐polymeric, diketopyrrolopyrrole‐based donor material that can be solution processed with a fullerene acceptor to produce good quality films is reported. Thermal annealing leads to suitable phase separation and material distribution so that highly effective BHJ morphologies are obtained. The frontier orbitals of the material are well aligned with those of the fullerene acceptor, allowing efficient electron transfer and suitable open‐circuit voltages, leading to power conversion efficiencies of 4.4 ± 0.4% under AM1.5G illumination (100 mW cm−2). Small molecules can therefore be solution processed to form high‐quality BHJ films, which may be used for low‐cost, flexible organic solar cells.

We present evidence that the degree of interchain interactions and morphology in conjugated polymer films can be controlled by altering the chain conformation in the solution from which the film is cast. Light scattering experiments show that the physical size of poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) chains can vary by a factor of 2 in different solvents such as chlorobenzene (CB) or tetrahydrofuran (THF). Photoluminescence and wavelength-dependent excitation indicate that MEH-PPV forms aggregate species with an absorption and luminescence spectra that are distinctly red-shifted from the intrachain exciton. The degree of aggregation is both concentration and solvent dependent; for solutions with concentrations typical of those used in spin casting, aggregates comprise a significant fraction of the total number of excited state species. The overall photoluminescence quantum yield is found to depend both on how restricted the polymer conformation is due to the choice of solvent and on aggregation due to polymer concentration. The excited state aggregates have a longer lifetime than their intrachain exciton counterparts, as evidenced by a near-infrared transient absorption in femtosecond pump-probe and anisotropy measurements. Memory of the chain conformation and the extent of aggregation of MEH-PPV in solution is carried into cast films. Thus, many conflicting results presented on the degree of interchain interactions can be explained by noting that the film samples in different studies were cast from precursor solutions with different solvents and concentrations. Overall, a careful choice of the solution (both solvent and concentration) can be used to produce MEH-PPV films with desired interchain interactions for particular device applications.