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3.
J Phys Chem B ; 113(52): 16513-7, 2009 Dec 31.
Article in English | MEDLINE | ID: mdl-19994835

ABSTRACT

Blends of poly(3-hexylthiophene) (P3HT) and the bis-adduct of [6,6]-phenyl-C(61)-butyric acid methyl ester (bisPCBM) show enhanced performances in bulk-heterojunction solar cells compared to P3HT:PCBM thin films due to their higher open-circuit voltage. However, it is not clear whether the decrease of the short-circuit current observed in P3HT-bisPCBM blends originates from the 100 mV reduction of the offset between the lowest unoccupied molecular orbitals of the donor and the acceptor or from a change in the morphology. The analysis of the photoluminescence dynamics of the various bulk heterojunctions provides information on the dependence of the electron transfer process on their microstructure. We find that in solution, where the donor-acceptor distribution is homogeneous, the photoluminescence dynamics is the same for the bis- and PCBM-based blends, while in thin films the first shows a slower dynamics than the second. This result indicates that the reduction of the LUMO offset of approximately 100 meV does not influence the electron transfer efficiency but that the diversity between the photoluminescence dynamics in thin films should be ascribed to the different microstructure of the bulk heterojunctions fabricated with the two acceptors.

4.
J Phys Chem B ; 113(31): 10566-70, 2009 Aug 06.
Article in English | MEDLINE | ID: mdl-19591508

ABSTRACT

Systematic control of 3D energy transfer (ET) dynamics is achieved in supramolecular nanostructured host-guest systems using spacer-functionalized guest chromophores. Quantum chemistry-based Monte Carlo simulations reveal the strong impact of the spacer length on the ET dynamics, efficiency, and dimensionality. Remarkably high exciton diffusion lengths demonstrate that there is ample scope for optimizing oligomeric or polymeric optoelectronic devices.


Subject(s)
Energy Transfer , Nanostructures/chemistry , Models, Molecular , Molecular Structure , Quantum Theory , Styrenes/chemistry
5.
J Phys Chem B ; 113(27): 9104-9, 2009 Jul 09.
Article in English | MEDLINE | ID: mdl-19526996

ABSTRACT

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.

7.
Inorg Chem ; 44(4): 840-2, 2005 Feb 21.
Article in English | MEDLINE | ID: mdl-15859258

ABSTRACT

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-microm telecom applications. Structural data demonstrate that the complex has a trinuclear structure (Er3Q9) 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 Er3Q9 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.

8.
J Phys Chem B ; 109(46): 21690-3, 2005 Nov 24.
Article in English | MEDLINE | ID: mdl-16853817

ABSTRACT

One-dimensional light amplification in individual p-sexiphenyl nanofibers is investigated. The influence of fiber morphology on light propagation properties is studied via optical and atomic force microscopy. Isolated nanofibers are shown to yield low-threshold random laser emission in the deep blue. Model calculations of coherent light propagation in one-dimensional random media qualitatively reproduce the experimental results. Implications for photonic nanosensors are briefly discussed.

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