Nondestructive Encapsulation of CdSe/CdS Quantum Dots in an Inorganic Matrix by Pulsed Laser Deposition.

We report the successful encapsulation of colloidal quantum dots in an inorganic matrix by pulsed laser deposition. Our technique is nondestructive and thus permits the incorporation of CdSe/CdS core/shell colloidal quantum dots in an amorphous yttrium oxide matrix (Y2O3) under full preservation of the advantageous optical properties of the nanocrystals. We find that controlling the kinetic energy of the matrix precursors by means of the oxygen pressure in the deposition chamber facilitates the survival of the encapsulated species, whose well-conserved optical properties such as emission intensity, luminescence spectrum, fluorescence lifetime, and efficiency as single-photon emitters we document in detail. Our method can be extended to different types of nanoemitters (e.g., nanorods, dots-in-rods, nanoplatelets) as well as to other matrices (oxides, semiconductors, metals), opening up new vistas for the realization of fully inorganic multilayered active devices based on colloidal nano-objects.

CdSe/ZnS quantum dots as sensors for the local refractive index.

We explore the potential of CdSe/ZnS colloidal quantum dots (QDs) as probes for their immediate dielectric environment, based on the influence of the local refractive index on the fluorescence dynamics of these nanoemitters. We first compare ensembles of quantum dots in homogeneous solutions with single quantum dots dispersed on various dielectric substrates, which allows us to test the viability of a conceptual framework based on a hard-sphere region-of-influence and the Bruggeman effective-medium approach. We find that all our measurements can be integrated into a coherent description, provided that the conceptualized point-dipole emitter is positioned at a distance from the substrate that corresponds to the geometry of the QD. Three theoretical models for the evolution of the fluorescence decay rate as a function of the local refractive index are compared, showing that the classical Lorentz approach (virtual cavity) is the most appropriate for describing the data. Finally, we use the observed sensitivity of the QDs to their environment to estimate the detection limit, expressed as the minimum number of traceable streptavidin molecules, of a potential QD-nanosensor based on fluorescence lifetime.

Local refractive index probed via the fluorescence decay of semiconductor quantum dots.

We present a novel approach for convenient tuning of the local refractive index around nanostructures. We apply this technique to study the influence of the local refractive index on the radiative decay time of CdSe/ZnS quantum dots with three distinct emission wavelengths. The dependence of the luminescence decay time on the environment is well described by an effective medium approach. A critical distance of about 80 nm is found for the determination of the effective local index of refraction. An estimation for the emitting-state quantum efficiency can be extracted.

Tetranuclear manganese(II) complexes of sulfonylcalix[4]arene macrocycles: synthesis, structure, spectroscopic and magnetic properties.

Two tetranuclear manganese(II) complexes {K(+)[Mn(4)(ThiaSO(2))(2)(OH)](-)} (1) and {K(+)[Mn(4)(ThiaSO(2))(2)(F)](-)} (2) have been synthesized under solvothermal conditions in methanol with p-tert-butylsulfonylcalix[4]arene (ThiaSO(2)). For both complexes, the structure has been established from single-crystal X-ray diffraction. The two complexes are best described as manganese squares sandwiched between two thiacalixarene macrocycles. In both complexes, in the center of the square formed by the four manganese(II) atoms, the unexpected presence of µ(4)-OH(-) or µ(4)-F(-) gives a negative charge to the cluster. The two tetranuclear complexes exhibit strong orange luminescence behavior resulting from the symbiosis between the ThiaSO(2) and the Mn(2+). Despite similar chemical formulation, (1) and (2) present difference in emission intensity and lifetime τ.