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.

Fundamental Limits on Wavelength, Efficiency and Yield of the Charge Separation Triad

In an attempt to optimize a high yield, high efficiency artificial photosynthetic protein we have discovered unique energy and spatial architecture limits which apply to all light-activated photosynthetic systems. We have generated an analytical solution for the time behavior of the core three cofactor charge separation element in photosynthesis, the photosynthetic cofactor triad, and explored the functional consequences of its makeup including its architecture, the reduction potentials of its components, and the absorption energy of the light absorbing primary-donor cofactor. Our primary findings are two: First, that a high efficiency, high yield triad will have an absorption frequency more than twice the reorganization energy of the first electron transfer, and second, that the relative distance of the acceptor and the donor from the primary-donor plays an important role in determining the yields, with the highest efficiency, highest yield architecture having the light absorbing cofactor closest to the acceptor. Surprisingly, despite the increased complexity found in natural solar energy conversion proteins, we find that the construction of this central triad in natural systems matches these predictions. Our analysis thus not only suggests explanations for some aspects of the makeup of natural photosynthetic systems, it also provides specific design criteria necessary to create high efficiency, high yield artificial protein-based triads.

Electrode poling of cellular polypropylene films with short high-voltage pulses

Recently, piezoelectric cellular polypropylene (PP) was proposed as a new type of quasi-ferroelectric. The observed hysteresis of the charge density as a function of the electric field could be explained as field-dependent charging inside the gas-filled voids. Interestingly enough, the measurable poling behavior of the macroscopic dipoles formed by charges that are trapped at the internal void surfaces is phenomenologically completely identical to the cooperative poling behavior of microscopic molecular dipoles in ferroelectric polymers. Therefore, it can be assumed that charge separation (or charge redistribution) and subsequent trapping in cellular PP is a rather fast switching process. In order to examine the poling dynamics, we developed an experimental setup for pulsed poling. High-voltage pulses with a duration of 45 μs (FWHM) were applied in direct contact to two-side metallized cellular PP films. The pulsed poling yields piezoelectricity in the cellular PP. We study and discuss the dependence of the resulting piezoelectricity on the poling field. We also characterize the charge separation during application of higher electric poling fields of up to -10 kV in direct contact to the two-side metallized films for longer times.

Impedance spectroscopy study of solid-state dye-sensitized solar cells with varying Spiro-OMeTAD concentration

This work reports on the changes of performance of solid-state cells dye-sensitized solar cells with the variation of concentration of spiro-OMeTAD between 5% and 25% in the fabrication of the cell. Variations of charge recombination and capacitance correlate with the improvement of current-potential characteristics at increasing spiro-OMeTAD content, which is explained by reduction of transport resistance for hole transport, the increase of charge separation in the dye molecules, and importantly, with the increase of the β-factor in the recombination resistance, that causes a reduction of the diode ideality factor. © 2010 Materials Research Society.

Estudo dos processos de geração e transferência de cargas em corantes cianinas

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Materiais derivados de hidróxidos duplos lamelares: síntese, caracterização e aplicação em adsorção e processos avançados de oxidação

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Charge-orbital ordering and phase separation in the two-orbital model for manganites: Roles of Jahn-Teller phononic and Coulombic interactions

The main properties of realistic models for manganites are studied using analytic mean-field approximations and computational numerical methods, focusing on the two-orbital model with electrons interacting through Jahn-Teller (JT) phonons and/or Coulombic repulsions. Analyzing the model including both interactions by the combination of the mean-field approximation and the exact diagonalization method, it is argued that the spin-charge-orbital structure in the insulating phase of the purely JT-phononic model with a large Hund couphng J(H) is not qualitatively changed by the inclusion of the Coulomb interactions. As an important application of the present mean-held approximation, the CE-type antiferromagnetic state, the charge-stacked structure along the z axis, and (3x(2) - r(2))/(3y(2) - r(2))-type orbital ordering are successfully reproduced based on the JT-phononic model with large JH for the half-doped manganite, in agreement with recent Monte Carlo simulation results. Topological arguments and the relevance of the Heisenberg exchange among localized t(2g) spins explains why the inclusion of the nearest-neighbor Coulomb interaction does not destroy the charge stacking structure. It is also verified that the phase-separation tendency is observed both in purely JT-phononic (large JH) and purely Coulombic models in the vicinity of the hole undoped region, as long as realistic hopping matrices are used. This highlights the qualitative similarities of both approaches and the relevance of mixed-phase tendencies in the context of manganites. In addition, the rich and complex phase diagram of the two-orbital Coulombic model in one dimension is presented. Our results provide robust evidence that Coulombic and JT-phononic approaches to manganites are not qualitatively different ways to carry out theoretical calculations, but they share a variety of common features.

Separation of dielectric and space charge polarizations in CaCu3Ti4O12/CaTiO3 composite polycrystalline systems

The complex analysis of dielectric/capacitance is a very useful approach to separate different polarization contributions existing in polycrystalline ceramics. In this letter, the authors use this type of spectroscopic analysis to separate the bulk's dielectric dipolar relaxation contributions from the polarization contribution due to space charge in the grain boundaries of a CaCu3Ti4O12/CaTiO3 polycrystalline composite system. The bulk dielectric dipolar relaxation was attributed to the self-intertwined domain structures from the CaCu3Ti4O12 phase coupled to the dipole relaxation from the CaTiO3 phase, while the space charge relaxation was attributed to the Schottky-type potential barrier responsible for the highly non-Ohmic properties observed in this composite polycrystalline system.

Two-phase separation observed in thermally treated pellets of ClO4- doped poly(3-methylthiophene) from electron spin resonance measurements

A pressed pellet of CIO (-)(4) poly (3-methylthiophene) (P3MT) was heated for two hours at 85 degrees C and suddenly dropped in liquid nitrogen. A change was observed around 220 K in the Electron Spin Resonance (ESR) spectra when the sample was slowly cooled from room temperature. ESR line asymmetry parameter (A/B) showed two spatially separated phases. One was identified as a small metallic-like phase. The other phase, the larger one, makes a transition to a semiconducting Charge-Density Wave (CDW) state.