We have studied the influence of three different fullerene derivatives on the charge generation and recombination dynamics of polymer/fullerene bulk heterojunction (BHJ) solar cell blends. Charge generation in APFO3/[70]PCBM and APFO3/[60]PCBM is very similar and somewhat slower than charge generation in APFO3/[70]BTPF. This difference qualitatively matches the trend in free energy change of electron transfer estimated from the LUMO energies of the polymer and fullerene derivatives. The first order (geminate) charge recombination rate is significantly different for the three fullerene derivatives studied and increases in the order APFO3/[70]PCBM < APFO3/[60]PCBM < APFO3/[70]BTPF. The variation in electron transfer rate cannot be explained from the LUMO energies of the fullerene derivatives and single-step electron transfer in the Marcus inverted region and simple considerations of expected trends for the reorganization energy and free energy change. Instead we suggest that geminate charge recombination occurs from a state where electrons and holes have separated to different distances in the various materials because of an initially high charge mobility, different for different materials. In a BHJ thin film this charge separation distance is not sufficient to overcome the electrostatic attraction between electrons and holes and geminate recombination occurs on the nanosecond to hundreds of nanoseconds time scale. In a BHJ solar cell, we suggest that the internal electric field in combination with polarization effects and the dynamic nature of polarons are key features to overcome electron-hole interactions to form free extractable charges.

Plastic solar cells were fabricated using a low-band-gap alternating copolymer of fluorene and a donor–acceptor–donor moiety (APFO-Green1), blended with [6,6]-phenyl-C61-butyric acid methylester or 3′-(3,5-Bis-trifluoromethylphenyl)-1′-(4-nitrophenyl)pyrazolino[60]fullerene as electron acceptors. The polymer shows optical absorption in two wavelength ranges from 300&lt;λ&lt;500nm and 650&lt;λ&lt;1000nm. Devices based on APFO-Green1 blended with the later fullerene exhibit an outstanding photovoltaic behavior at the infrared range, where the external quantum efficiency is as high as 8.4% at 840nm and 7% at 900nm, while the onset of photogeneration is found at 1μm. A photocurrent density of 1.76mA∕cm2, open-circuit voltage of 0.54V, and power conversion efficiency of 0.3% are achieved under the illumination of AM1.5 (1000W∕m2) from a solar simulator.

A soluble, functionalized Py-SWNT has been synthesized and characterized by solution (1)H and (13)C NMR, FT-Raman, and electron microscopy. Experimental data indicate that Py-SWNT has short tubes with pentyl esters at the tips and pyridyl isoxazolino units along the walls. The synthesis of Py-SWNT is based on a 1,3-dipolar cycloaddition of a nitrile oxide on the SWNT walls, similar to 1,3-dipolar cycloadditions that are common for fullerene functionalization. The resulting Py-SWNT forms a complex with a zinc porphyrin (ZnPor) in a way similar to that reported for pyridyl-functionalized [60]-fullerenes. Formation of this metal-ligand complex was firmly established by a detailed electrochemical study. However, in contrast to the behavior observed for the ZnPor/Py-C(60) complex, photochemical excitation of the complex between ZnPor/Py-SWNT does not lead to electron transfer with the generation of charge-separated states. Fluorescence and laser flash studies indicate that the main process is energy transfer from the singlet ZnPor excited state to the Py-SWNT with observation of emission from Py-SWNT. Triplet ZnPor excited-state quenching by Py-SWNT is only observed in polar solvents such as DMF, but not in benzonitrile.

The first Diels-Alder cycloaddition of o-quinodimethane to SWNT has been performed under microwave irradiation.

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Plastic solar cells have been fabricated using a low‐bandgap alternating copolymer of fluorene and a donor–acceptor–donor moiety (APFO‐Green1), blended with 3′‐(3,5‐bis‐trifluoromethylphenyl)‐1′‐(4‐nitrophenyl)pyrazolino[70]fullerene (BTPF70) as electron acceptor. The polymer shows optical absorption in two wavelength ranges, λ < 500 nm and 600 < λ < 1000 nm. The BTPF70 absorbs light at λ < 700 nm. A broad photocurrent spectral response in the wavelength range 300 < λ < 1000 nm is obtained in solar cells. A photocurrent density of 3.4 mA cm–2, open‐circuit voltage of 0.58 V, and power‐conversion efficiency of 0.7 % are achieved under illumination of AM1.5 (1000 W m–2) from a solar simulator. Synthesis of BTPF70 is presented. Photoluminescence quenching and electrochemical studies are used to discuss photoinduced charge transfer.

Photoinduced processes in fullerenopyrrolidine and fullerenopyrazoline derivatives substituted with an oligophenylenevinylene moiety Armaroli, N.; Accorsi, G.; Gisselbrecht, J.P.; Gross, M.; Krasnikov, V.V.; Tsamouras, D.; Hadziioannou, G; Gomez-Escalonilla, M.J.; Langa, F.; Eckert, J.F.

Dye is coabsorbed with CdSe nanocrystals (see image), strongly increasing the amount of charge injected into TiO2 from CdSe nanocrystals and providing an additional degree of control over the electron charge‐transfer process. This could have important implications in the development of supracollectors with enhanced absorption and charge‐separation properties for photovoltaic devices.