Ultrafast dynamics of excitons in semiconductor quantum dots on a plasmonically active nano-structured silver film

The excited state dynamics of core-shell type semiconductor quantum dots (QDs) of various sizes in close contact with a plasmonically active silver thin film has been demonstrated by using picosecond resolved fluorescence spectroscopy. The non-radiative energy transfer from the QDs to the metal surface is found to be of Föster resonance energy transfer (FRET) type rather than the widely expected nano-surface energy transfer (NSET) type. The slower rate of energy transfer processes compared to that of the electron transfer from the excited QDs to an organic molecule benzoquinone reveals an insignificant possibility of charge migration from the QDs to the metallic film

Functionalization of manganite nanoparticles and their interaction with biologically relevant small ligands: picosecond time-resolved FRET studies

We report molecular functionalization of the promising manganite nanoparticles La0.67Sr0.33MnO3 (LSMO) for their solubilization in aqueous environments. The functionalization of individual NPs with the biocompatible citrate ligand, as confirmed by Fourier transform infrared (FTIR) spectroscopy, reveals that citrates are covalently attached to the surface of the NPs. UV-VIS spectroscopic studies on the citrate functionalized NPs reveals an optical band in the visible region. Uniform size selectivity (2.6 nm) of the functionalization process is confirmed from high resolution transmission electron microscope (HRTEM). In the present study we have used the optical band of the functionalized NPs to monitor their interaction with other biologically important ligands. Forster resonance energy transfer (FRET) of a covalently attached probe 4-nitrophenylanthranilate (NPA) with the capped NPs confirm the attachment of the NPA ligands to the surface functional group (-OH) of the citrate ligand. The FRET of a DNA base mimic, 2-aminopurine (2AP), with the NPs confirms the surface adsorption of 2AP. Our study may find relevance in the study of the interaction of individual manganite NPs with drug/ligand molecules

Dynamics of light harvesting in ZnO nanoparticles

We have explored light harvesting of the complex of ZnO nanoparticles with the biological probe Oxazine 1 in the near-infrared region using picosecond-time-resolved fluorescence decay studies. We have used ZnO nanoparticles and Oxazine 1 as a model donor and acceptor, respectively, to explore the efficacy of the Förster resonance energy transfer (FRET) in the nanoparticle-dye system. It has been shown that FRET from the states localized near the surface and those in the bulk of the ZnO nanoparticles can be resolved by measuring the resonance efficiency for various wavelengths of the emission spectrum. It has been observed that the states located near the surface for the nanoparticles (contributing to visible emission at λ≈550 nm) can contribute to very high efficiency (>90%) FRET. The efficiency of light harvesting dynamics of the ZnO nanorods has also been explored in this study and they were found to have much less efficiency (∼40%) for energy transfer compared to the nanoparticles. The possibility of an electron transfer reaction has been ruled out from the picosecond-resolved fluorescence decay of the acceptor dye at the ZnO surface

Charge-tunnelling and self-trapping: common origins for blinking, grey-state emission and photoluminescence enhancement in semiconductor quantum dots

Understanding instabilities in the photoluminescence (PL) from light emitting materials is crucial to optimizing their performance for different applications. Semiconductor quantum dots (QDs) offer bright, size tunable emission, properties that are now being exploited in a broad range of developing technologies from displays and solar cells to biomaging and optical storage. However, instabilities such as photoluminescence intermittency, enhancement and bleaching of emission in these materials can be detrimental to their utility. Here, we report dielectric dependent blinking, intensity-“spikes” and low-level, “grey”-state emission, as well as PL enhancement in ZnS capped CdSe QDs; observations that we found consistent with a charge-tunnelling and self-trapping (CTST) description of exciton-dynamics on the QD–host system. In particular, modulation of PL in grey-states and PL enhancement are found to have a common origin in the equilibrium between exciton charge carrier core and surface-states within the CTST framework. Parameterized in terms of size and electrostatic properties of the QD and its nanoenvironment, the CTST offers predictive insight into exciton-dynamics in these nanomaterials

Ultrafast dynamics of excitons in semiconductor quantum dots on a plasmonically active nano-structured silver film

The excited state dynamics of core–shell type semiconductor quantum dots (QDs) of various sizes in close contact with a plasmonically active silver thin film has been demonstrated by using picosecond resolved fluorescence spectroscopy. The non-radiative energy transfer from the QDs to the metal surface is found to be of Förster resonance energy transfer (FRET) type rather than the widely expected nano-surface energy transfer (NSET) type. The slower rate of energy transfer processes compared to that of the electron transfer from the excited QDs to an organic molecule benzoquinone reveals an insignificant possibility of charge migration from the QDs to the metallic film

Role of resonance energy transfer in light harvesting of zinc oxide-based dye-sensitized solar cells

In this contribution we have studied the dynamics of light harvesting of ZnO nanoparticles (NPs) to a surface adsorbed sensitizing dye (SD) N719. By using the picosecond resolved Frster resonance energy transfer (FRET) technique we have explored that the excited ZnO NPs resonantly transfer visible optical radiation to the SD N719. The consequence of the energy transfer on the performance of the overall efficiency of a model ZnO NP-based dye-sensitized solar cell (DSSC) has also been explored. We have demonstrated that the overall efficiency of a ZnO NP-based solar cell significantly depends on the presence of high-energy photons in the solar radiation. In a control experiment on a model TiO2 NP-based solar cell it has been demonstrated that the presence of high-energy photon has a minimal effect on the performance of the cell as the TiO2 NPs are incapable of harvesting high-energy photons from solar radiation. The possibility of the back electron transfer from the excited NPs to the SD has also been investigated by studying the NPs in the presence of an ideal electron accepting organic molecule, benzoquinone (BQ). The time constants and nonradiative rate constant obtained for the ZnO/N719 system are found to be different from those of the ZnO/BQ system, which rules out the possibility of back electron transfer from ZnO NPs to SD N719. Moreover, the observed FRET dynamics in the light harvesting process of the nanocrystalites may be efficient in the further use of the nanoparticles in the development of new photodevices