Band-edge ultrafast pump-probe spectroscopy of core/shell CdSe/CdS rods: assessing electron delocalization by effective mass calculations.

CdSe/CdS dot/rods nanocrystals show interesting physical properties related to the band-alignment at the hetero-interface, which controls the band-edge electron delocalization over the rods. Here the differential transmission spectra of CdSe/CdS nanorod samples with different core sizes have been measured using excitation resonant to the core transition. The photo bleaching ratio between dot and rod transitions increases with the dot size, indicating a trend towards electron localization. This trend has been further quantified by performing effective mass calculations in which the conduction band misalignment was varied in order to reproduce the observed bleaching feature ratio. The best agreement was found for negligible conduction band misalignment for small dots of around 2.3 nm in diameter, and about -0.1 eV misalignment was estimated for the larger dots, above 3.5 nm in diameter. This shows that the band misalignment might be dependent on the geometry of the system, and we argue that this might be related to different strain developed at the hetero-interface.

Suppression of biexciton auger recombination in CdSe/CdS dot/rods: role of the electronic structure in the carrier dynamics.

We studied carrier dynamics in semiconductor nanocrystals consisting of a small CdSe dot embedded in an elongated, rod-shaped CdS shell, using the ultrafast pump-probe technique. We found clear evidence of a substantial suppression of the Auger nonradiative recombination in the biexciton regime. Moreover, a simple model of the dynamics in which biexcitons show no Auger recombination, and only holes are localized in the dot, fits well the differential transmission observed at all pump densities. The long biexciton lifetime results into an observed long-living gain having a peak that is red shifted with respect to the lowest energy absorption peak. We argue that the origin of the large relative gain observed at large fillings is related to the peculiar structure of the electronic levels, and in particular, to delocalization of electrons in the rod.

Lasing in self-assembled microcavities of CdSe/CdS core/shell colloidal quantum rods.

Colloidal semiconductor quantum rods have demonstrated many advantageous properties as light emitters such as high quantum yield, tunable emission wavelength, and polarized emission. This makes them an interesting optical gain material for laser applications. We report room-temperature gain lifetimes in core/shell CdSe/CdS quantum rods exceeding 300 ps, and show that the long gain lifetimes result from the significant reduction of Auger recombination in our quantum rods, even though the electrons are delocalized over the rod volume. We also fabricate devices by deposition of small droplets of quantum rod solution onto flat substrates. The evaporation dynamics of the droplets are governed by the coffee stain effect which leads to the formation of well defined micron-size stripes. These stripes consist of densely packed, laterally aligned quantum rods and provide optical feedback originating from the abrupt changes of refractive index at the stripe borders. We exploit the optical gain and the coffee stain mediated self-assembly and show that we can fabricate novel microlasers solely by deposition of droplets of quantum rod solutions on flat substrates.

CdSe/CdS/ZnS double shell nanorods with high photoluminescence efficiency and their exploitation as biolabeling probes.

We report the synthesis, the structural and optical characterization of CdSe/CdS/ZnS "double shell" nanorods and their exploitation in cell labeling experiments. To synthesize such nanorods, first "dot-in-a-rod" CdSe(dot)/CdS(rod) core/shell nanocrystals were prepared. Then a ZnS shell was grown epitaxially over these CdSe/CdS nanorods, which led to a fluorescence quantum yield of the final core-shell-shell nanorods that could be as high as 75%. The quantum efficiency was correlated with the aspect ratio of the nanorods and with the thickness of the ZnS shell around the starting CdSe/CdS rods, which varied from 1 to 4 monolayers (as supported by a combination of X-ray diffraction, elemental analysis with inductively coupled plasma atomic emission spectroscopy and high resolution transmission electron microscopy analysis). Pump-probe and time-resolved photoluminescence measurements confirmed the reduction of trapping at CdS surface due to the presence of the ZnS shell, which resulted in more efficient photoluminescence. These double shell nanorods have potential applications as fluorescent biological labels, as we found that they are brighter in cell imaging as compared to the starting CdSe/CdS nanorods and to the CdSe/ZnS quantum dots, therefore a lower amount of material is required to label the cells. Concerning their cytotoxicity, according to the MTT assay, the double shell nanorods were less toxic than the starting core/shell nanorods and than the CdSe/ZnS quantum dots, although the latter still exhibited a lower intracellular toxicity than both nanorod samples.

Tetrapod-shaped colloidal nanocrystals of II-VI semiconductors prepared by seeded growth.

We report a general synthetic approach to tetrapod-shaped colloidal nanocrystals made of various combinations of II-VI semiconductors. Uniform tetrapods were prepared using preformed seeds in the sphalerite structure, onto which arms were grown by coinjection of the seeds and chemical precursors into a hot mixture of surfactants. By this approach, a wide variety of core materials could be chosen (in practice, most of the II-VI semiconductors that could be prepared in the sphalerite phase, namely, CdSe, ZnTe, CdTe); in contrast, the best materials for arm growth were CdS and CdTe. The samples were extensively characterized with the aid of several techniques.

Ultrafast electron-hole dynamics in core/shell CdSe/CdS dot/rod nanocrystals.

We investigated the transient bleaching and absorption of the asymmetric core/shell CdSe/CdS nanorods using the pump-probe technique. We observed ultrafast carrier relaxation and identified hole localization dynamics with 650 +/- 80 fs time constant. Upon pumping the CdSe core, we found an intense bleaching signal in the CdS spectral region, which we assigned to the delocalization of the electronic wave function on the basis of envelope-function theoretical calculations.