Solvent additives have been explored as a reliable way to control the morphology in bulkheterojunction (BHJ) layers for improved device performance. We show that the choice of solvent additives has direct implications on morphological evolution, i.e. poly(3-hexylthiophene) (P3HT): [6,6]-phenyl C61-butyric acid methyl ester (PCBM) BHJ films processed with a small amount of 1,8-diiodooctane or 1-chloronaphthalene have more crystalline PCBM domains compared to crystalline P3HT domains, while the opposite is true for films cast with nitrobenzene additive and films cast purely from chlorobenzene. The BHJ film cross-links when annealed at 300 °C in the presence of 1,8-diiodooctane. Cross-linking is found to occur even in pristine P3HT and PCBM films annealed under similar conditions. NMR spectroscopy is presented as a viable technique for quantitative analysis of the amount of solvents left in the BHJ films before and after heat treatment. Despite differences in the ways the additives affect the morphology of the BHJ layer, device performance remained stable over 300 h for all additives tested. © 2013 Elsevier B.V.

Surface photovoltage spectroscopy (SPS) was used to probe photon induced charge separation in thin films of regioregular and regiorandom poly(3-hexylthiophene) (P3HT) as a function of excitation energy. Both positive and negative photovoltage signals were observed under sub-band-gap (<2.0 eV) and super-band-gap (>2.0 eV) excitation of the polymer. The dependence of the spectra on substrate work function, thermal annealing, film thickness, and illumination intensity was investigated, allowing the identification of interface, charge transfer (CT), and band-gap states in the amorphous and crystalline regions of the polymer films. The ability to probe these states in polymer films will aid the development and optimization of organic electronic devices such as photovoltaics (OPVs), light-emitting diodes (OLEDs), and field effect transistors (OFETs). The direction and size of the observed photovoltage features can be explained using the depleted semiconductor model. © 2013 American Chemical Society.

Surface photovoltage (SPV) spectra are reported for separate films of (6,6)-phenyl-C61-butyric acid methyl ester (PCBM) and for regioregular and regiorandom poly(3-hexylthiophene) (P3HT):PCBM bulk heterojunctions, as a function of wavelength, film thickness, thermal annealing, and substrate. In PCBM films, two photovoltage features are observed at 1.1-1.4 eV (F1) and 1.4-2.3 eV (F2), which are assigned to excitation of charge transfer states at the interface (F1) and in the bulk (F2) of the film. In BHJ films, five different photovoltage features are observed at 0.75-0.9 eV (F1), 0.9-1.3 eV (F2), 1.3-1.8 eV (F3), 1.8-2.0 eV (F4), and 2.0-2.4 eV (F5). This data can be analyzed on the basis of optical absorbance and fluorescence spectra of the films, and using SPV spectra for PCBM and P3HT only films, and for a BHJ film containing P3HT nanofibers for comparison. SPV features are assigned to states at the polymer-substrate interface (F1 and F2), the P3HT:PCBM charge transfer state (F3), the self-ionized (CT) state of P3HT (F4), and the band gap transition of P3HT (F5). This interpretation is also consistent with molecular orbital energy diagrams and electron microscopy-derived topological maps of the films. Photovoltage sign and substrate dependence can be understood with the depleted semiconductor model. Features F1-4 are caused by polarization of electrostatically bound charge pairs by the built-in electric field at the substrate-BHJ interface, whereas F5 is due to transport of free charge carriers through the film and through the substrate film interface. This work will promote the understanding of photochemical charge generation and transport in organic photovoltaic films. © 2014 American Chemical Society.

Living organisms use fractal structures to optimize material and energy transport across regions of differing size scales. Here we test the effect of fractal silver electrodes on light distribution and charge collection in organic semiconducting polymer films made of P3HT and PCBM. The semiconducting polymers were deposited onto electrochemically grown fractal silver structures (5000 nm × 500 nm; fractal dimension of 1.71) with PEDOT:PSS as hole-selective interlayer. The fractal silver electrodes appear black due to increased horizontal light scattering, which is shown to improve light absorption in the polymer. According to surface photovoltage spectroscopy, fractal silver electrodes outperform the flat electrodes when the BHJ film thickness is large (>400 nm, 0.4 V photovoltage). Photocurrents of up to 200 microamperes cm-2 are generated from the bulk heterojunction (BHJ) photoelectrodes under 435 nm LED (10-20 mW cm-2) illumination in acetonitrile solution containing 0.005 M ferrocenium hexafluorophosphate as the electron acceptor. The low IPCE values (0.3-0.7%) are due to slow electron transfer to ferrocenium ion and due to shunting along the large metal-polymer interface. Overall, this work provides an initial assessment of the potential of fractal electrodes for organic photovoltaic cells. This journal is