The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. First-principles quantum mechanical calculations show that the exponential-decay law for any metastable state is only an approximation and predict an asymptotically algebraic contribution to the decay for sufficiently long times. In this Letter, we measure the luminescence decays of many dissolved organic materials after pulsed laser excitation over more than 20 lifetimes and obtain the first experimental proof of the turnover into the nonexponential decay regime. As theoretically expected, the strength of the nonexponential contributions scales with the energetic width of the excited state density distribution whereas the slope indicates the broadening mechanism.

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Organic light-emitting diodes (OLEDs) using the red phosphorescent emitter iridium(III)bis(2methyldibenzo[f,h]quinoxaline) (acetylacetonate) [Ir(MDQ) 2 (acac)] are studied by time-resolved electroluminescence measurements. A transient overshoot after voltage turn-off is found, which is attributed to electron accumulation on Ir(MDQ) 2 (acac) molecules. The mechanism is verified via impedance spectroscopy and by application of positive and negative off-voltages. We calculate the density of accumulated electrons and find that it scales linearly with the doping concentration of the emitter. Using thin quenching layers, we locate the position of the emission zone during normal OLED operation and after voltage turn-off. In addition, the transient overshoot is also observed in three-color white-emitting OLEDs. By time-and spectrally resolved measurements using a streak camera, we directly attribute the overshoot to electron accumulation on Ir(MDQ) 2 (acac). We propose that similar processes are present in many state-of-the-art OLEDs and believe that the quantification of charge carrier storage will help to improve the efficiency of OLEDs.

The interaction between the water-soluble anionic conjugated copolymer poly{1,4-phenylene-[9,9-bis(4-phenoxy-butylsulfonate)]fluorene-2,7-diyl} (PBS-PFP) and various surfactants has been studied in aqueous solution by UV-vis absorption spectra, fluorescence and electrical conductivity. It is suggested from the linear dependence of absorbance, fluorescence and electrical conductivity on concentration that in the absence of surfactant, moderately stable dispersions are formed. These are affected in different ways on adding cationic, anionic or neutral surfactants. With the cationic cetyltrimethylammonium bromide, quenching of fluorescence intensity and lifetime, and formation of a new emission occurs at concentrations well below the critical micelle concentration (cmc). Electrical conductivity measurements indicate a discontinuity at surfactant/polymer ratio corresponding to electroneutrality, due to complexation. With the anionic sodium dodecyl sulfate, fluorescence quenching is also observed, but is attributed to formation of some mixed polymer/surfactant aggregate. The most striking changes are observed with the non-ionic pentaethyleneglycol monododecyl ether (C 12 E 5 ), where a blue shift in fluorescence emission, dramatic increases in lifetime and quantum yield, and changes in electrical around the cmc are interpreted in terms of incorporation of single polymer chains in elongated cylindrical micelles. This is supported by 1 H NMR spectroscopic measurements.

In this work we demonstrate the complex excited-state behavior of polyspirobifluorene in the solid state, which, due to the interaction of the spiroconjugated side group, readily forms a charge-transfer (CT) excited state of lower energy than the singlet exciton. The polymer is compared to standard polyfluorene materials using pump-probe and field-assisted pump-probe spectroscopy. It has been found that the small energy barrier between the singlet exciton and the CT state allows for population of the emissive singlet state at room temperature giving rise to a long tail in the singlet lifetime compared to an apparent single-exponential lifetime at low temperature. It is proposed that in devices the CT state is populated on charge recombination before the singlet states are excited by electron transfer from the CT state.

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Using time-resolved and steady-state photoluminescence techniques, fluorene/fluorenone copolymers have been studied to investigate the role of keto defects in degraded polyfluorene. Keto sites can be populated via migration from polyfluorene singlets, thereby quenching the polyfluorene fluorescence, and via direct photon absorption. In the former case, the migration process dominates all thermal and interchain variability in the efficiency of quenching. No annihilation process of fluorenone triplets and no interchain processes such as excimer formation participate in the defect emission itself.