We explore two routes to wave function engineering in elongated colloidal CdSe/CdS quantum dots, providing deep insight into the intrinsic physics of these low-dimensional heterostructures. Varying the aspect ratio of the nanoparticle allows control over the electron-hole overlap (radiative rate), and external electric fields manipulate the interaction between the delocalized electron and the localized hole. In agreement with theory, this leads to an exceptional size dependent quantum confined Stark effect with field induced intensity modulations, opening applications as electrically switchable single photon sources.
We investigate the nature of ultrafast exciton dissociation and carrier generation in acceptor-doped conjugated polymers. Using a combination of two-pulse femtosecond spectroscopy with photocurrent detection, we compare the exciton dissociation and geminate charge recombination dynamics in blends of two conjugated polymers, MeLPPP ͓methyl-substituted ladder-type poly͑p-phenylene͔͒ and MDMO-PPV ͓poly͑2-methoxy,5-͑3,7-dimethyloctyloxy͒-1,4-phenylenevinylene͔, with the electron accepting fullerene derivative PCBM ͓1-͑3-methoxycarbonyl͒-propyl-1-phenyl-͑6,6͒C 61 ͔. This technique allows us to distinguish between free charge carriers and Coulombically bound polaron pairs. Our results highlight the importance of geminate pair recombination in photovoltaic devices, which limits the device performance. The comparison of different materials allows us to address the dependence of geminate recombination on the film morphology directly at the polymer:fullerene interface. We find that in the MeLPPP:PCBM blend exciton dissociation generates Coulombically bound geminate polaron pairs with a high probability for recombination, which explains the low photocurrent yield found in these samples. In contrast, in the highly efficient MDMO-PPV:PCBM blend the electron transfer leads to the formation of free carriers. The anisotropy dynamics of electronic transitions from neutral and charged states indicate that polarons in MDMO-PPV relax to delocalized states in ordered domains within 500 fs. The results suggest that this relaxation enlarges the distance of carrier separation within the geminate pair, lowering its binding energy and favoring full dissociation. The difference in geminate pair recombination concurs with distinct dissociation dynamics. The electron transfer is preceded by exciton migration towards the PCBM sites. In MeLPPP:PCBM the exciton migration time decays smoothly with increasing PCBM concentration, indicating a trap-free exciton hopping. In MDMO-PPV:PCBM, however, the exciton migration time is found to show a threshold-like dependence on the PCBM concentration. This observation is explained by efficient interchain energy transfer in ordered MDMO-PPV domains in conjunction with exciton trapping.
Bringing together compounds of intrinsically different functionality, such as inorganic nanostructures and organic molecules, constitutes a particularly powerful route to creating novel functional devices with synergetic properties found in neither of the constituents. We introduce nanophotonic functional elements combining two classes of materials, semiconductor nanocrystals and dyes, whose physical nature arises as a superposition of the properties of the individual components. The strongly absorbing rod-like nanocrystals focus the incident radiation by photopumping the weakly absorbing dye via energy transfer. The CdSe/CdS nanorods exhibit a large quantum-confined Stark effect on the single-particle level, which enables direct control of the spectral resonance between donor and acceptor required for nanoscopic Förster-type energy transfer in single nanorod-dye couples. With this far-field manipulation of a near-field phenomenon, the emission from single dye molecules can be controlled electrically. We propose that this effect could lead to the design of single-molecule optoelectronic switches providing building blocks for more complex nanophotonic circuitry.
One fundamental problem of intelligent organisms pursuing goal-directed behavior is how to dynamically regulate the balance between maintenance and flexibility. The authors show that central dopaminergic activity, as indicated by spontaneous eyeblink rate and dopamine gene polymorphisms, plays an important role in the modulation of this balance. Seventy-two young adults were examined. Participants with high blink rates showed increased cognitive flexibility but decreased cognitive stability compared with participants with low blink rates. This pattern of results was even more pronounced for carriers of the DRD4 exon III 4/7 genotype, even though no main effects were found for DRD4 and COMT polymorphisms. Results converge with neuropsychological models that suggest a modulatory role of prefrontal dopaminergic activity for processes of cognitive control.
A concept to electrically control the scattering of light is introduced. The idea is to embed noble metal nanoparticles in an electro-optical material such as a liquid crystal in order to induce a spectral shift of the particle plasmon resonance by applying an electric field. Light scattering experiments on single gold nanoparticles show that spherically shaped nanoparticles become optically spheroidal when covered by an anisotropic liquid crystal. The two particle plasmon resonances of the optically spheroidal gold nanoparticles can be spectrally shifted by up to 50 meV when electric fields of more than 10 kV/cm are applied.
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