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Polymer-fullerene bilayer heterostructures are suited to study excitonic processes in conjugated polymers. Excitons are efficiently quenched at the polymer-fullerene interface, whereas the polymer-vacuum interface is often considered as an exciton-reflecting interface. Here, we report about efficient exciton quenching close to the polymer-vacuum interface of spin-coated MDMO-PPV (poly[2-methoxy-5-(2′-ethyl-hexyloxy)-p-phenylenevinylene]) films. The quenching efficiency is estimated to be as high as that of the polymer-fullerene interface. This efficient quenching is consistent with enhanced intermolecular interactions close to the polymer-vacuum interface due to the formation of a "skin layer" during the spin-coating procedure. In the skin layer, the polymer density is higher; that is, the intermolecular distances are shorter than in the rest of the film. The effect of exciton quenching at the polymer-vacuum interface should be taken into account when the thickness of the polymer film is on the order of the exciton diffusion length; in particular, in the determination of the exciton diffusion length. © 2009 American Chemical Society.

The temperature dependence of the exciton dynamics in a conjugated polymer is studied using time-resolved spectroscopy. Photoluminescence decays were measured in heterostructured samples containing a sharp polymer-fullerene interface, which acts as an exciton quenching wall. Using a 1D diffusion model, the exciton diffusion length and diffusion coefficient were extracted in the temperature range of 4-293 K. The exciton dynamics reveal two temperature regimes: in the range of 4-150 K, the exciton diffusion length (coefficient) of approximately 3 nm (approximately 1.5 x 10 (-4) cm2/s) is nearly temperature independent. Increasing the temperature up to 293 K leads to a gradual growth up to 4.5 nm (approximately 3.2 x 10 (-4) cm2/ s). This demonstrates that exciton diffusion in conjugated polymers is governed by two processes: an initial downhill migration toward lower energy states in the inhomogenously broadened density of states, followed by temperature activated hopping. The latter process is switched off below 150 K.

Erbium quinolinolates, commonly assumed to be mononuclear species with octahedral co-ordination geometry, have been proposed as promising materials for photonic devices but difficulties in obtaining well defined products have so far limited their use. We report here the conditions to obtain in high yields three different kinds of pure neutral erbium quinolinolates by mixing an erbium salt with 8-quinolinol (HQ) and 5,7-dihalo-8-quinolinol (H5,7XQ: X=Cl and Br): i) the trinuclear complex Er 3 Q 9 (1) which is obtained with HQ deprotonated by NH 3 in water or ethanol/water mixtures; ii) the already known dimeric complexes based on the unit [Er(5,7XQ) 3 (H 2 O) 2 ] [X=Cl (2) and Br (3)]; iii) the mononuclear [Er(5,7XQ)2(H5,7XQ) 2 Cl] [X= Cl (4) and Br (5)] complexes, obtained in organic solvents without base addition, where the ion results coordinated to four ligands, two deprotonated chelating, and two as zwitterionic monodentate oxygen donors. These results represent a further progress with respect to a recent reinvestigation on this reaction, which has shown that obtaining pure and anhydrous octahedral ErQ 3 , the expected reaction product, is virtually impossible, but failed in the isolation of 1 and of the neutral tetrakis species based on H5,7XQ ligands. Structural data provide a detailed description of the molecules and of their packing which involves short contacts between quinoxaline ligands, due to π-π interactions. Electronic and vibrational studies allow to select the fingerprints to distinguish the different products and to identify the presence of water. The structure/property relationship furnishes a satisfactory interpretation of the photo-physical properties. Experimental evidence confirms that the most important quenchers for the erbium emission are the coordinated water molecules and shows that the ligand emission is significantly affected by the π-π interactions.

We report the first combined optical and structural investigation of the water free Er-quinolinolate complex, an organo-lanthanide system of interest for 1.5-mum telecom applications. Structural data demonstrate that the complex has a trinuclear structure (Er(3)Q(9)) which provides the Er metals with an octa-coordination by the organic ligand and prevents solvent and water molecules from entering the lanthanide coordination sphere. The results of the structural analysis allow us to infer that the strong Er luminescence quenching exhibited by the Er(3)Q(9) complex is due uniquely to resonant energy transfer to the aromatic C-H vibrations of the ligand, providing the correct tools to design more efficient emitters.

We investigate sensitization efficiency of near-infrared emission and population saturation of trivalent erbium in erbium-quinolinolato complexes photoexcited into the absorption band of the organic sensitizer. At low-excitation levels, we find high (∼80%) sensitization efficiencies. We observe excited-state populationsaturationatinversionthresholdundersubnanosecondpumpingatthe level of one injected photoexcitation per complex. SECTION Kinetics, Spectroscopy

The photophysical characterization of three soluble derivatives of single-wall carbon nanotubes (SWCNTs), functionalized with poly(ethylene glycol) (PEG), co-functionalized with PEG and aminofluorene and co-functionalized with PEG and aminoanthracene is reported. The peculiar excellent solubility of these derivatives allows, for the first time in covalently functionalized SWCNTs, the study of their excitation dynamics by monitoring the near-infra-red emission. Moreover, the aminoanthracene derivative shows higher photoluminescence efficiency in the visible range than the aminofluorene derivative, demonstrating the possibility to tune extensively the photophysical properties of these functionalized SWCNTs. (C) 2009 Elsevier Ltd. All rights reserved.

In this letter we compare the transistor performances of two solution-processed perylene derivatives: N,N'-bis (n-octyl)- dicyanoperylene-3,4:9,10-bis(dicarboximide) (PDI8-CN(2)) and N,N'-1H,1H-perfluorobutyl dicyanoperylenediimide (PDIF-CN(2)). Perylenediimide nitrogen functionalization with perfluoroalkyl vs. alkyl chains improves the electron mobility of solution-processed organic field effect transistors (OFETs) by one order of magnitude. Time resolved spectroscopy allows attributing this increment to a higher degree of co-facial arrangement of the fluorinated molecules. This supramolecular arrangement enhances the pi-pi overlap leading to more efficient electron transport.

We investigate the quenching of the near infrared light emission in Er3+ complexes induced by the resonant dipolar interaction between the rare-earth ion and high frequency vibrations of the organic ligand. The nonradiative decay rate of the lanthanide ion is discussed in terms of a continuous medium approximation, which depends only on a few, easily accessible spectroscopic and structural data. The model accounts well for the available experimental results in Er3+ complexes, and predicts an ∼100% light emission quantum yield in fully halogenated systems.