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 approximately 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 approximately 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.

Red electrophosphorescence from a soluble binaphthol derivative as host and iridium complex as guest.

The investigation of the optical properties, carrier injection, and transport into a soluble small molecule, 6,6'-dicarbazolyl-2,2'-dihexyloxy-1,1'-binaphthol (BA), was reported. The results demonstrated that BA is a blue-emitting molecule, which can be used as a host for the fabrication of electrophosphorescent light-emitting diodes (LEDs). The single-layer electrophosphorescent LEDs fabricated from toluene solution containing BA with tris[2,5-bis-2'-(9',9'-dihexylfluorene)pyridine-kappa(2)NC(3)(')]iridium(III) [Ir(HFP)(3)] emitted red light from Ir(HFP)(3) triplet emission. The results from photoluminescence (PL) and electroluminescence (EL) demonstrated that the dominated operational mechanism in EL was charge trapping rather than Förster transfer, which was the dominated mechanism in PL. The single-layer OLEDs with 1wt % of Ir(HFP)(3) have a luminance (L) of 1000 cd/m(2) at 22 V and a luminous efficiency (LE) of 0.88 cd/A at 11 mA/cm(2). Double-layer electrophosphorescent LEDs fabricated by casting the emitting layer from a solution of BA blended with Ir(HFP)(3) and subsequently thermally depositing tris(8-hydroxyquinoline) aluminum (Alq(3)) film as an electron injection and transport layer yielded L = 1830 cd/m(2) at 30 V and LE = 2.47 cd/A at 18 mA/cm(2). These results demonstrated that electrophosphorescent LEDs can be fabricated from BA via solution processing and that L and LE can be enhanced by changing the device architecture with the goal of better balancing the electron and hole currents.

Solid-state optical properties of linear polyconjugated molecules: pi-stack contra herringbone.

The intermolecular arrangement in the solid state and the consequences on the optical and photophysical properties are studied on different derivatives of oligophenylenevinylenes by UV/VIS absorption and angular-resolved polarized fluorescence spectroscopy. Unsubstituted distyrylbenzene (DSB) organizes in a herringbone manner, with the long axes of the molecules oriented in parallel, but the short axes almost perpendicular to each other. Fluorinated distyrylbenzene (F(12)DSB) as well as the DSB:F(12)DSB cocrystals prefer cofacial pi-stacking in the solid state. For all structures, the consequence of the parallel alignment of the transition moments is a strongly blueshifted H-type absorption spectrum and a low radiative rate constant k(F). Significant differences are observed for the emission spectra: the perpendicular arrangement of the short axes in DSB crystals leads to only very weak intermolecular vibronic coupling. Hence the emission spectrum is well structured, very similar to the one in solution. For F(12)DSB and DSB:F(12)DSB, the cofacial arrangement of the adjacent molecules enables strong intermolecular vibronic coupling of adjacent molecules. Thus, an unstructured and strongly redshifted excimerlike emission spectrum is observed. The differences in the electronic nature of the excited states are highlighted by quantum-chemical calculations, revealing the contribution of interchain excitations to the electronic transitions.

Through-space delocalized water-soluble paracyclophane bichromophores: new fluorescent optical reporters.

Conjugated polymers and oligomers can serve as highly responsive fluorescent reporters for biosensor applications. However, their optical properties in aqueous media are highly dependent upon environmental conditions. The structure of the paracyclophane framework provides a platform for designing optical reporters that show little sensitivity to surfactants, and thus is well-suited for fluorescent assays. The permanent intramolecular delocalization through the paracyclophane core dominates intermolecular perturbations in spontaneously formed aggregates.