Photoinduced hole-transfer in semiconducting polymer/low-bandgap cyanine dye blends: evidence for unit charge separation quantum yield

Power-conversion efficiencies of organic heterojunction solar cells can be increased by using semiconducting donor-acceptor materials with complementary absorption spectra extending to the near-infrared region. Here, we used continuous wave fluorescence and absorption, as well as nanosecond transient absorption spectroscopy to study the initial charge transfer step for blends of a donor poly(p-phenylenevinylene) derivative and low-band gap cyanine dyes serving as electron acceptors. Electron transfer is the dominant relaxation process after photoexcitation of the donor. Hole transfer after cyanine photoexcitation occurs with an efficiency close to unity up to dye concentrations of similar to 30 wt%. Cyanines present an efficient self-quenching mechanism of their fluorescence, and for higher dye loadings in the blend, or pure cyanine films, this process effectively reduces the hole transfer. Comparison between dye emission in an inert polystyrene matrix and the donor matrix allowed us to separate the influence of self-quenching and charge transfer mechanisms. Favorable photovoltaic bilayer performance, including high open-circuit voltages of similar to 1 V confirmed the results from optical experiments. The characteristics of solar cells using different dyes also highlighted the need for balanced adjustment of the energy levels and their offsets at the heterojunction when using low-bandgap materials, and accentuated important effects of interface interactions and solid-state packing on charge generation and transport.

Dielectric behavior of PVDF/POMA blends that have a low doped POMA content

The real (epsilon') and imaginary (epsilon) components of the complex permittivity of blends of PVDF [poly(vinylidene fluoride)] with POMA [poly(o-methoxyaniline)] doped with toluenosulfonic acid (TSA) containing 1, 2.5, and 5 wt % POMA-TSA were determined in the frequency interval between 10(2) and 3 X 10(6) Hz and in the temperature range from -120 up to 120degreesC. It was observed that the values of epsilon' and epsilon had a greater increase with the POMA-TSA content and with a temperature in the region of frequencies below 10 kHz. This effect decreased with frequency and it was attributed to interfacial polarization. This polarization was caused by the blend heterogeneity, formed by conductive POMA-TSA agglomerates dispersed in an insulating matrix of PVDF. The equation of Maxwell-Garnett, modified by Cohen, was used to evaluate the permittivity and conductivity behavior of POMA-TSA in the blends. A strong decrease was observed in POMA-TSA conductivity in the blend, which was bigger the lower the POMA-TSA content in the blend. This decrease could have been caused either by the POMA dedoping during the blend preparation process or by its dispersion into the insulating matrix. (C) 2002 Wiley Periodicals, Inc.

Morphology variation as a function of composition for blends of PVDF and a polyaniline derivative

Blends of poly(vinylidene fluoride), PVDF, and poly(o-methoxyaniline), POMA doped with toluene sulfonic acid, TSA, were prepared by casting at various compositions and studied by scanning electron microscopy, X-ray diffraction and differential scanning calorimetry. The blend composition has a great influence on the morphology obtained. As the concentration of POMA-TSA is increased in the blend an interconnecting fibrillar-like morphology is formed and the spherulites characteristic of pure PVDF are destroyed. The variation of blend morphology is further discussed based on X-ray diffraction and differential scanning calorimetry analysis. (C) 1998 Elsevier B.V. Ltd. All rights reserved.