We examine the significance of hot exciton dissociation in two archetypical polymer-fullerene blend solar cells. Rather than evolving through a bound charge transfer state, hot processes are proposed to convert excitons directly into free charges. But we find that the internal quantum yields of carrier photogeneration are similar for both excitons and direct excitation of charge transfer states. The internal quantum yield, together with the temperature dependence of the current-voltage characteristics, is consistent with negligible impact from hot exciton dissociation.

Evidence is presented for the formation of a weak ground‐state charge‐transfer complex in the blend films of poly[9,9‐dioctylfluorene‐co‐N‐(4‐methoxyphenyl)diphenylamine] polymer (TFMO) and [6,6]‐phenyl‐C61 butyric acid methyl ester (PCBM), using photothermal deflection spectroscopy (PDS) and photoluminescence (PL) spectroscopy. Comparison of this polymer blend with other polyfluorene polymer/PCBM blends shows that the appearance of this ground‐state charge‐transfer complex is correlated to the ionization potential of the polymer, but not to the optical gap of the polymer or the surface morphology of the blend film. Moreover, the polymer/PCBM blend films in which this charge‐transfer complex is observed also exhibit efficient photocurrent generation in photovoltaic devices, suggesting that the charge‐transfer complex may be involved in charge separation. Possible mechanisms for this charge‐transfer state formation are discussed as well as the significance of this finding to the understanding and optimization of polymer blend solar cells.

The performance of organic photovoltaic (OPV) devices is currently limited by modest short-circuit current densities. Approaches toward improving this output parameter may provide new avenues to advance OPV technologies and the basic science of charge transfer in organic semiconductors. This work highlights how steric control of the charge separation interface can be effectively tuned in OPV devices. By introducing an octylphenyl substituent onto the investigated polymer backbones, the thermally relaxed charge-transfer state, and potentially excited charge-transfer states, can be raised in energy. This decreases the barrier to charge separation and results in increased photocurrent generation. This finding is of particular significance for nonfullerene OPVs, which have many potential advantages such as tunable energy levels and spectral breadth, but are prone to poor exciton separation efficiencies. Computational, spectroscopic, and synthetic methods were combined to develop a structure-property relationship that correlates polymer substituents with charge-transfer state energies and, ultimately, device efficiencies.

This letter reports on highly sensitive optical absorption measurements on organic donor-acceptor solar cells, using Fourier-transform photocurrent spectroscopy ͑FTPS͒. The spectra cover an unprecedented dynamic range of eight to nine orders of magnitude making it possible to detect defect and disorder related sub-band gap transitions. Direct measurements on fully encapsulated solar cells with an active layer of poly͓2-methoxy-5-͑3Ј ,7Ј -dimethyl-octyloxy͔͒-p-phenylene-vinylene:͑6,6͒-phenyl-C61-butyric-acid ͑1:4 weight ratio͒ enabled a study of the intrinsic defect generation due to UV illumination. Solar cell temperature annealing effects in poly͑3-hexylthiophene͒:PCBM ͑1:2 weight ratio͒ cells and the induced morphological changes are related to the changes in the absorption spectrum, as determined with FTPS.

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A methodology to link an atomistic description of a polymeric semiconductor with the experimental electrical characteristics of real devices is proposed. Microscopic models of poly(3-hexylthiophene) (P3HT) of different regioregularity are generated using molecular dynamics and their electronic structure determined via an approximate quantum chemistry scheme. The resulting density of trap states and distribution of localized and delocalized states is then compared with that obtained from thin film transistor measurements of P3HT at different regioregularities. The two complementary methodologies provide a converging description of the electron transport in semicrystalline P3HT and the role of regioregularity. States at the valence band edge are localized, but delocalized "band-like" states are thermally accessible and quantitatively characterized. Both theory and experiment agree that contrary to a commonly held belief the trap density and the DOS shape are little affected by the presence of regioregularity defects.

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The microstructure of MDMO-PPV:PCBM blends as used in bulk hetero-junction organic solar cells was studied by Atomic Force Microscopy (AFM) and Kelvin Force Microscopy (KFM) to image the surface morphology and by means of Transmission Electron Microscopy (TEM) to reveal images of the film's interior.By introducing KFM, it was possible to demonstrate that phase separated domains have different local electrical properties than the surrounding matrix. Since blend morphology clearly influences global electrical properties and photovoltaic performance, an attempt to control the morphology by means of casting conditions was undertaken. By using AFM, it has been proven that not only the choice of solvent, but also drying conditions dramatically influence the blend structure. Therefore, the possibility of discovering the blend morphology by AFM, KFM and TEM makes them powerful tools for understanding today's organic photovoltaic performances and for screening new sets of materials.